DE2545163A1 - QUARTERLY CONNECTIONS - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Koenigsberger Dipl.-Phys. R. Holzbauei - Dipi.-Ino. F clinching iron - Dr. F. Zumstein jun.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 22 5341

TELEX 529979 TELEGRAMS: ZUMPAT

CHECK ACCOUNT: MUNICH 91139-809. Bank code 700 100 80 BANK ACCOUNT: BANKHAUS H. AUFHÄUSER

ACCOUNT NO. 397997. BLZ 70030600

8 MUNICH 2,

BRÄUHAUSSTRASSE 4

97 / n
Case 4111

KemaNord, Stockholm / Sweden

Quaternary connections

The invention relates to new quaternary compounds and, more particularly, to those compounds which are both a quaternary Nitrogen atom as well as a functional group that can react with nucleophilic groups.

The compounds of the invention are useful as cationizing agents valuable for paper additives, since the quaternary nitrogen atom imparts cationic properties and the functional group can react with paper chemicals. The new compounds can also be used as plasticizers and antistatic agents can be used for textile and cellulosic materials.

During the manufacture of paper, various additives are added to the pulp in order to improve the properties of the paper, such as dry strength, wet strength, hydrophobicity, etc. to improve. The cellulose fiber itself is slightly negative loaded, and this is often exploited when various additives are used such that these made slightly positive so that better retention on the fibers is obtained. Alternatively, a relative

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highly cationic compounds such as papermaking alum are added to the fibers to recharge them, after which anionic additives can be used.

When cationic (cation-active) additives are used, the cation-active component is often tertiary nitrogen atoms. A disadvantage of many of these is that when the _pH value exceeds 8, the cationic activity generally decreases so that they are less useful in the manufacture of paper in these p "values.

The present invention relates to new compounds containing a quaternary nitrogen atom and a reactive group capable of reacting with the material to be treated. The quaternary nitrogen atom retains its cation-active properties even with a high p _R value, and paper additives which are treated with the compounds according to the invention can thus be used in the production of paper with high p n values.

The new compounds have the following general formula:

ΘΘ

R. and R ₂ each independently represent aliphatic groups with up to 2 2 carbon atoms,

Rg is a benzyl group or a lower alkyl group represents with up to 6 carbon atoms,

R. and Rr independently of one another are hydrogen or a Represent methyl group,

η represents 0 to 6,

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X represents a group reactive with nucleophiles, such as groups of the formula -Cl, -0-CH ₂ -Cl, -0-C (O) -Cl, -0-C (S) -Cl, -0-P (O) -Cl ₂ , -0-S (O) ₂ -Cl or 40-> pP (O) -Cl, the latter combining with two quaternized alkylene oxide adducts, and

Y represents an anion.

X preferably represents the group -Cl or -0-C (O) -Cl. The anions that can be used are the chloride, bromide, hydroxyl, methyl sulfate or sulfate ions. The latter is thus the anion for two quaternary groups.

The groups R ^ and Rp are, independently of one another, straight-chain or branched aliphatic groups of up to 22 carbon atoms. As examples of suitable aliphatic groups alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, 2-ethylhexyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and higher alkyl groups with up to 22 carbon atoms, alkenyl groups, such as decenyl, tridecenyl, heptadecenyl, octadecenyl, eicosenyl. Any of the aliphatic groups can be inert be substituted and can contain an amide, ether or ester group. Preferably the aliphatic groups are R ^ and Rp alkyl groups with up to 6 carbon atoms or Alkyl or alkenyl groups of 12 to 18 carbon atoms.

- page 3a -

6 0 9 8 1 B / 1 Π 7 7

The new compounds are suitably made up of a secondary one Amine produced, which reacted in a first stage with ethylene oxide or propylene oxide or a mixture thereof is, after which the alkylene oxide adduct obtained is quaternized. A suitable quaternizing agent is a benzyl or lower alkyl halide, preferably chloride or bromide, or a di-lower alkyl sulfate, in which the lower alkyl group contains up to 6 carbon atoms, used.

The quaternized alkylene oxide adduct is then reacted with a compound for introducing the reactive group X. In these cases, compounds in which X is Cl are prepared by reaction with thionyl chloride, phosphorus trichloride or phosphorus pentachloride. Compounds in which X is -O-CHp-Cl are obtained by reacting the alkylene oxide adduct with formaldehyde and hydrochloric acid, and compounds in which X is the group -0-C (O) -Cl are prepared by reacting the alkylene oxide adduct with phosgene. By reacting the adduct with phosphoryl or sulfuryl chloride, compounds are obtained in which the reactive group X 4O4 ₂ P (O) -Cl, -0-P (O) -Cl ₂ or -0-S (O) ₂ Cl is. When compounds in which η = 0 are prepared, dialkylaminoethanol or propanol is quaternized in a first stage, after which the quaternary compound obtained is reacted with any of the compounds mentioned to introduce the reactive group X.

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The paper additives made with the present compounds suitably those which have nucleophilic groups, preferably hydroxyl groups, are primary and contain secondary amino groups. Examples of such paper additives are starch or derivatives thereof, Cellulose or derivatives thereof, such as carboxymethyl cellulose, alkyl cellulose, hydroxyalkyl cellulose, alkyl hydroxyalkyl cellulose, Polyvinyl alcohol, carbide resins, melamine resins, polyamine resins, Polyamine polyamide resins, etc. are called. The compounds are used in amounts of at least 0.01% by weight, based on the paper additive.

When the additives are cationized, an aqueous solution or dispersion of the additives with the compounds according to the invention at room temperature or slightly elevated temperature and preferably at atmospheric pressure treated. The ρ value and the time are known in a known manner, depending on the type of reactive group X and the nucleophilic group of the paper chemical.

The compounds of the invention can also be used to treat textile and cellulosic materials. she reduce the static electricity of the materials and also have a softening effect on them when they are in Quantities of at least 0.01% by weight, based on the material to be treated, can be used. The connections will preferably used in amounts of 0.5 to 2% by weight. The connections are preferably added in the manufacture of textile and cellulosic materials and are used in most Cases covalently bound to this. Materials treated with the compounds of the invention resist thus several washing processes. The compounds according to the invention can of course also be used when rinsing the Materials of the type mentioned above can be used to achieve an antistatic and softening effect. A certain effect is also achieved when they are used in the actual washing process. When the connections are used to treat textile and cellulose materials, at least one of the alkyl

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254b163

groups R ^, and Rp preferably a higher alkyl group, i. an alkyl group having at least 7 carbon atoms.

The following examples illustrate the invention without, however, restricting it. Parts and percentages relate based on weight unless otherwise specified.

example 1

Production of

Et

Bu-N - (CH ₀ CH ₀ O) ₁ , -CH ₀ CH ₀ Cl Bu

Br

a) alkoxylation

129.3 g of dibutylamine were introduced into an autoclave at -5 ° C. with 132 g of ethylene oxide and 10 g of NaOH. The temperature was kept at 100 to 120 ^° C., the pressure being approximately 2.04 kp / cm (200 kPa). The reaction was interrupted after 24 hours and, according to the analysis of the ethoxy group and the neutralization number, based on the total amine content, 2.7 ethoxy groups were added to the amine.

b) Quaternization

12.8 g of the product according to a) were dissolved in 32 ml of acetonitrile and introduced into the reactor at 10 ° C. with 28 g of ethyl bromide. The temperature was held at 100 ° C for 5 hours with stirring, the pressure being 2.55 kp / cm (250 kPa). To cooling was added acetonitrile and excess quaternizing agent stripped. Analysis of the quaternary amine and BrU indicated a conversion of 80%. .

c) introduction of the reactive group

8.8 g of the quaternized ethylene oxide adduct according to b) were dissolved in 20 ml of acetonitrile and with slow stirring for 30 minutes at a temperature of 0 to 10 ° C to 3.0 g Thionyl chloride added. After the addition was complete, the temperature

temperature increased to 80 to 85 C, and the mixture was stirred for 3 hours. The solvent and S0 ~ formed were then stripped off.

The final product obtained was a brownish-red syrup. The analysis of the organically bound chlorine and the analysis of the Hydroxy number corresponded to a conversion of 72%.

Example 2

Production of

^C 18 ^H 37

N - CH ₂ -CH ₂ -0-CH ₂ -CH ₂ Cl

Θ Θ

Cl

Distearylamine was analyzed and the neutralization number (neutralization number, based on the total breath content = n,

dead

based on the primary amine content = N,, based

I *

on the secondary amine content = N., based on the ter-

II

tertiary amine content = N,) became N = 69.7, N, = 3.9,

. = 63.7 and N, II III

= 2.1 determined.

a) alkoxylation

52.3 g (0.1 mol) of distearylamine were placed in a flask which was heated to 230 ° C. without a catalyst. Ethylene oxide at 20 ° C was introduced in an amount of 200 ml / minute with stirring. The gas flow was stopped when 0.8 mol of ethylene oxide had been added. The product was rated in terms of ethoxy groups and neutralization number analyzed, N. = 59.7, N. = 0.6, N. = 2.4 and N.

dead I II III

56.7.

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b) quaternization

10 g of the product according to a) were placed in a flask together with 4 g of isopropyl alcohol. The mixture was on 50 ° C heated. 12 g of methyl chloride were added, the temperature was increased and at 85 ° C. and a pressure of 3.06 kp / cm ' (300 kPa) held. When a test indicated N, = 0.5, the reaction was stopped. Excess methyl chloride and isopropyl alcohol were stripped with nitrogen gas.

^c ) introduction of the reactive group

4.4 g of the product according to b) were dissolved in 7 ml of chloroform, and the solution was added to 0.87 g of thionyl chloride at 0 to 5 ° C. for 30 minutes. The temperature was then increased to 25 ° C. The mixture was stirred for 3 hours and the formed SO ₂ and chloroform were then stripped under vacuum. The product obtained was analyzed with regard to the organically bound chlorine and the hydroxyl number, which resulted in an 83% yield of the end product

-Zr ₇ CH,

37> v j 3 N

- CH ₅ -CH "-0-CH ₀ -CH ₀ Cl

c. d. d. ά

Cl

indicated.

Example 3

a) 10 g of potato starch were added to 170 g of water, p "= 8.1 g of the product from Example 2, finely dispersed in 19 g of water, was then added with vigorous stirring. The temperature was increased to 90 ° C. for 2 hours. The starch solution was cooled and the _pH value was adjusted to 5. The starch was precipitated in ethanol, washed and dried, after which Kjeldahl analysis indicated a nitrogen content of 0.14% corresponding to a conversion of 80%.

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- jf-

b) A 20% starch solution from a) above was added to an unbleached sulfate pulp. The amount of dry starch was 1 % of the dry fiber content. Laboratory sheets were prepared and the dry tensile length thereof was determined. In the same way, laboratory sheets containing the same amount of untreated potato starch and also comparison sheets without starch were prepared. The results are given in the table.

comparison Potato starch Cationic
sxerte
Strength according to
d.Example ■ Dry tear length
(km) 1.10 1.30 5.15

Example 4
Production of

CH ₂ -C ₆ H ₅

N- (CH ₂ -CH ₂ -O) -CH ₂ -CH ₂ -OC-Cl

^C 18 ^H 37

Cl

Distearylamine was used according to Example 2 a).

a) Alkoxylationunq

52.3 g (0.1 mol) of distearylamine were used with 5 g of NaOH as a catalyst placed in a flask. Otherwise, the synthesis was carried out according to Example 2 a). The analysis after Addition of 1.2 moles of ethylene oxide showed that an average of 4 moles of ethylene oxide per mole of amine were added.

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b) Quaternization

7.49 g of the product according to a) were placed in a flask together with 200 ml of ethanol, and the mixture was heated to 45.degree. When all of the benzyl chloride had been charged, the temperature was increased to 75 ° C over 5 hours. The determination of the neutralization number corresponded to a conversion of 91 % to quaternary amine.

c) introduction of the reactive group

6.0 g of the product according to b) were added to a solution of phosgene in toluene at 15 ° C. After 10 hours at 40 ° C Excess phosgene and solvent were stripped off. The IR spectra of the end product showed a clear chloroformate absorption at 1785 cm, and the analysis of the organically bound chlorine and the hydroxyl number corresponded to one Conversion of 89%.

Example 5

The product was reacted a) described with starch in the same manner as in Example 3, except that the _pH value of the aqueous solution was always maintained at the fifth Kjeldahl analysis of nitrogen showed a yield of 73 %.

The starch was added to a fiber pulp in the same manner as described in Example 3 b), and the dry breaking length was decided. The results are given in the table below.

comparison potato
strength Cationis.
Strength according to
the example Dry tear length
(km) 4.10 4.30 5.25

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Example 6

Production of

Et

Et - N - CH ₂ - CH ₂ - 0 - C-

Cl

Et

a) Quaternization

11.7 g of diethylethanolamine were dissolved in 15 ml of acetonitrile and introduced into an autoclave at 10 ° C. together with 21.8 g of ethyl bromide. ^{The temperature was kept at 100 °} C. for 2 hours with stirring, the pressure being 2.55 kp / cm ² (250 kPa). After 2 hours the white crystals were filtered off. Analysis for Br vL / indicated a yield of 99 % .

b) introduction of the reactive group

10 g of the product according to a) were added to a 20% strength solution of phosgene in toluene. The temperature was kept at 20 ° C. during the addition and then increased to 50 ° C. for 2 hours. Excess phosgene and solvent were stripped off. The product had a characteristic IR peak at 1775 cm " ¹ .

The analysis of the organically bound chlorine showed a yield of 52%.

Example 7

a ^s ) 1.0 g of the product prepared according to Example 6 was reacted with starch according to Example 3a). Kjeldahl analysis showed a nitrogen content of 0.18%, which corresponds to a conversion of 82%.

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b) The starch solution according to a) above became one Fiber pulp was added in the same way as described in Example 3 b). The dry tear length was obtained for the Arcs were determined and the results are given in the table below.

Comparison Potato starch Cationizing
te strength
according to example Dry tear length 4.10 4.30 5.20

Example 8

By varying the starting materials with regard to R ^, R- and R ₄ and by using different compounds for introducing Rq or the reactive group X, a large number of compounds were produced which can be used as cationizing agents for paper chemicals or for treating textiles and cellulosic materials contain nucleophilic groups, are suitable.

a) Alkoxylationunq

Amines containing different substituents R ^ and Rp were analyzed by determining the neutralization number and with ethylene or propylene oxide for the preparation of compounds of the general formula

I I

R ₁ -N- (CH ₂ - CH ₂ - 0 -) _n - CH ₂ - CH - OH

implemented

The reaction conditions are given in Table I.

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43

Λ (ΰ E

Ά
U Sl VO r-i ο • CM O ■ «J VO O \ ϋ ϋ ο α O O I. in Il \ A. CM
I.
O E O - = r ιη
££ \ CM ιη ■ ΦΟ \ H IA #1 \ η O I. ΐ-Η O O
CM
CD γΗ O 2. VO VO CM ( ϋ
I. I.
O
ιη ■ = r O ϋ r-i l-t K • a
CM O C.
φ O cn ο ΐ-Η ιη OO
»Rl VO O γ-Ι
I.
O »-L»
O
M.
Ot ϋ O t-i I. H ΐΰ νο σ ΐΰ O O ο O VO f \
«· Il Λ CM Of \ in ιη ο ^ r cc: ιη H ^ J ^ -% ι ο O O A. νο ο ►ο κ \ VO O CM CM CM O I. I. I. O Ό O CM O O CD O
.. f χ ιΗ m O I 1 I. a * C. (0 (0 fH CM Φ CM 4-> ω J-I , _) O (0> ιθ >, tA O υ υ (0 ^; ιπ +> VO ϋ ιΗ I. -P I. ] U (XM - = r O OO I. Ό C Ή > ί · Η Ο XES O <- C.

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The ethylene or propylene adducts obtained were through Ethoxy or propoxy groups and neutralization number identified. The number of alkoxy groups added was calculated as an average.

b) Quaternization

The crude reaction products from a) were then dissolved in a solvent and mixed with various quaternizing agents converted to compounds of the general formula

R ₁ -N- (CH XI

CH ₂ - 0 -) _n - CH ₂

CH

^R 5

- OH

.Y

to manufacture.

The reaction conditions and reactants are listed in Table II.

Table II

Solution
. middle For example: acetonitrile, isopropanol ⁰ Ii " ° 6
3.06-5.1
(300 - 500) CH ₃ - C ₆ H ₅ -CH ₂ - 300 ^R 3 CH - CH ₂ - 240-360 ^so n ² ' Cl " • 70-75 Y Cl ", Br" 100-130 ^C l ~ ^C 22
1.02
(.100) ^C l " ^C 22
1.02
(100) ' R- ^ j R ₂
Pressure ρ
kp / cm
(kPa) C ₁ -C ₃
1.02-3.06
(100 - 300) Time
Minutes 120-240 Temp. ° c

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The quaternization was carried out in all cases up to a yield of > 80 % ,

e) Ginbrinqen der_ Reactive group X.

pie preparation of compounds of the general formula

CH -

such that a reactant containing the group X, dissolved in a solvent, the quaternized Product according to b) was added at temperatures below room temperature. The reaction was then at Derpelben Temperature or at an elevated temperature for a few hours. After the reaction was complete stripped off excess reactants and solvents, pie reaction conditions and the various reaction ε participants are listed in Table III.

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Table III

X -Cl -OCH ₂ Cl 0
-OC-Cl Cl
I.
-OP-Cl
l!
0 V ¹ Ϊ
-OC-Cl U
(I.
-Of-Cl
0 Reacti
ons-
part -
take it SOCl ₂
PCl ₃
PC1 _C ClL, 0. HCl COCl ₂ POCl ₃ POCl ₃ CSCl ₂ So ₂ Ci ₂ Encore
temp. ° c ro 5 nj 5 PJ 20 A / 20 10 rJ 20 Reactive
ons-
temp? C 80 5 30th 40 40 30th 20th Total-
reactive
on time
Minutes 180 180 180 600 .600 300 600

The final products were identified in appropriate cases by IR analysis identified, and the yield was determined by analyzing the organically bound chlorine, which was determined with the aid of the determination the hydroxyl number was supplemented, determined.

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Claims (4)

Claims R ^ and Rp, independently of one another, are each aliphatic groups represent with up to 22 carbon atoms, Ro is a benzy group or a lower alkyl group represents with up to 6 carbon atoms, R- and Rt- independently of one another are hydrogen or one Represent methyl group, η is 0 to 6, X represents a group reactive with nucleophiles and Y is an anion. 2. Compounds according to claim 1, characterized in that X represents the group -Cl, -0-CH ₂ -Cl, -0-C (O) -Cl, -0-C (S) -Cl, 404 ₂ P (O ) -Cl, -0-P (O) -Cl ₂ or -0-S (O) ₂ -Cl. 2. Compounds according to claim 1 or 2, characterized in that X is the group -Cl or -0-C (O) -Cl. 4. Compounds according to one of the preceding claims, characterized in that Y is a chloride, bromide or Sulfate ion is. 609816/1077