SUBSTOICHIOMETRIC ALKOXYLATED POLYETHERS

Abstract

Provided herein are polymers obtainable by a process including the steps a) and b) described below. In Step a) at least one component a1) is condensed to obtain a polyether having remaining hydroxyl groups. Component a1) is at least one component selected from N-(hydroxyalkyl) am ins according to formula (Ia) and/or (Ib) as defined below. Besides component a1), further components can be present in the condensation step a). In step b) a part of the remaining hydroxyl groups are reacted with at least one alkylene oxide. The alkoxylation according to step b) is carried out in a substoichiometric way. The ratio of i) the alkylene oxide versus ii) the sum of the amount of the remaining hydroxyl groups is >0:1 to <1:1 [mol/mol]. Further provided herein is a process for preparing such polymers and derivatives of the polymers by quaternization, protonation, sulphation and/or phosphation.

Claims

1. A polymer obtainable by a process comprising steps a) and b): a) condensing at least one component a1), optionally at least one component a2), and/or optionally at least one component a3), which are defined as follows: a1) is at least one compound selected from N-(hydroxyalkyl)amines of formulae (I.a) and/or (I.b), ##STR00006## wherein A is independently selected from C.sub.1-C.sub.6-alkylene, R.sup.1, R.sup.1*, R.sup.2, R.sup.2*, R.sup.3, R.sup.3*, R.sup.4, R.sup.4*, R.sup.5, R.sup.5* and R.sup.6 are independently of one another selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted, and a2) is at least one compound selected from polyols of formula Y(OH).sub.n, wherein n is an integer from 2 to 4, and Y denotes a bivalent, trivalent or tetravalent aliphatic, cycloaliphatic or aromatic radical having 2 to 10 carbon atoms, and a3) is at least one compound selected from polyamines of formula
Y(NHR.sup.y).sub.m, wherein m is an integer from 2 to 4, Y denotes a bivalent, trivalent or tetravalent aliphatic, cycloaliphatic or aromatic radical having 2 to 10 carbon atoms, and R.sup.y has one of the meanings given for R.sup.6 or two radicals R.sup.y together may form a C.sub.1-C.sub.6-alkylene group, wherein the sum of the amount of components a1), a2) and a3) is more than 70 wt.-% in relation to the sum of the amount of all monomers employed in the condensation according to step a) in order to obtain a polyether having remaining hydroxyl groups and optionally remaining secondary amino groups, and b) reacting a part of the remaining hydroxy groups and optionally a part of the remaining secondary amino groups of the polyether obtained in step a) with at least one alkylene oxide, wherein the ratio of i) the alkylene oxide versus ii) the sum of the amount of the remaining hydroxyl groups and optionally the remaining secondary amino groups is >0:1 to <1:1 [mol/mol].

2. The polymer obtainable by the process according to claim 1, wherein in step b) the reaction of the remaining hydroxy groups and optionally of the remaining secondary amino groups with the at least one alkylene oxide is performed in the presence of a catalyst, wherein the catalyst is a base.

3. The polymer according to claim 1, wherein in component a1) in formulae (I.a) and/or (I.b) i) A is a methylene group, which is unsubstituted or carries one substituent selected from C.sub.1-C.sub.4-alkyl, and/or ii) R.sup.1, R.sup.1*, R.sup.2, R.sup.2*, R.sup.3, R.sup.3*, R.sup.4, R.sup.4*, R.sup.5, R.sup.5* and R.sup.6 are independently of one another selected from hydrogen and C.sub.1-C.sub.4-alkyl.

4. The polymer according to claim 1, wherein i) in component a2) the polyol is an aliphatic polyol, a cycloaliphatic polyol, or an arylaliphatic polyol, and/or ii) in component a3) the polyamine is selected from ethylenediamine, N,N-dimethylethylenediamine, N, N-diethylethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane or piperazine.

5. The polymer according to claim 1, wherein the sum of the amount of components a1), a2) and a3) is more than 90% in relation to the sum of the amount of all monomers employed in the condensation according to step a).

6. The polymer according to claim 1, wherein i) 50 to 100 wt. % of component a1), ii) 0 to 50 wt. % of component a2), and iii) 0 to 50 wt. % of component a3) are employed in relation to the sum of the amount of all monomers of step a).

7. The polymer according to claim 1, wherein at least 95 wt.-% of all monomers employed in step a) are selected from component a1).

8. The polymer according to claim 1, wherein in step b) the at least one alkylene oxide is selected from epoxyethane, epoxypropane, 1,2-epoxybutane, (butylene oxide) 2,3-epoxybutane, 1,2-epoxy-2-methylpropane, 1,2-epoxypentane, 2,3-epoxypentane, 1,2-epoxy-2-methylbutane, 2,3-epoxy-2-methylbutane, 1,2-epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane, 1,2-epoxyethylenebenzene, 1,2-epoxydecane (decene oxide), 1,2-epoxydodecane (dodecene oxide), 1,2-epoxytetradecane and/or 1,2-epoxyhexadecane.

9. The polymer according to claim 1, wherein in step b) the ratio of i) the alkylene oxide versus ii) the sum of the amount of the remaining hydroxy groups and optionally the remaining secondary amino groups is 0.1:1 to 0.7:1 [mol/mol].

10. The polymer according to claim 1, wherein in step b) the ratio of i) the alkylene oxide versus ii) the sum of the amount of the remaining hydroxy groups and optionally the remaining secondary amino groups is 0.4:1 to 0.7:1 [mol/mol], and the alkylene oxide is butylene oxide.

11. The polymer according to claim 1, wherein in step b) the ratio of i) the alkylene oxide versus ii) the sum of the amount of the remaining hydroxy groups and optionally the remaining secondary amino groups is 0.1:1 to 0.7:1 [mol/mol], and the alkylene oxide is dodecene oxide.

12. The polymer according to claim 1, wherein in step b) i) the polymer has a number average molecular weight of from 500 to 100 000 g/mol, wherein the number average molecular weight of the polymer is determined by size exclusion chromatography with hexafluoroisopropanol as eluent, and/or ii) the average degree of alkoxylation is in the range from >0 to <1.

13. A process for preparing the polymer according to claim 1, wherein the process comprises the steps a) and b): a) condensing at least one component a1), optionally at least one component a2) and/or optionally at least one component a3), which are defined as follows: a1) is at least one compound selected from N-(hydroxyalkyl)amines of formulae (I.a) and/or (I.b), ##STR00007## wherein A is independently selected from C.sub.1-C.sub.6-alkylene, R.sup.1, R.sup.1*, R.sup.2, R.sup.2*, R.sup.3, R.sup.3*, R.sup.4, R.sup.4*, R.sup.5, R.sup.5* and R.sup.6 are independently of one another selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted, and a2) is at least one compound selected from polyols of formula Y(OH).sub.n, wherein n is an integer from 2 to 4, and Y denotes a bivalent, trivalent or tetravalent aliphatic, cycloaliphatic or aromatic radical having 2 to 10 carbon atoms, and a3) is at least one compound selected from polyamines of formula
Y(NHR.sup.y).sub.m, wherein m is an integer from 2 to 4, Y denotes a bivalent, trivalent or tetravalent aliphatic, cycloaliphatic or aromatic radical having 2 to 10 carbon atoms, and R.sup.y has one of the meanings given for R.sup.6 or two radicals R.sup.y together may form a C.sub.1-C.sub.6-alkylene group, wherein the sum of the amount of components a1), a2) and a3) is more than 70 wt.-% in relation to the sum of the amount of all monomers employed in the condensation according to step a) to obtain a polyether having remaining hydroxyl groups and optionally remaining secondary amino groups, and b) reacting a part of the remaining hydroxy groups and optionally a part of the remaining secondary amino groups of the polyether obtained in step a) with at least one alkylene oxide, wherein the ratio of i) the alkylene oxide versus ii) the sum of the amount of the remaining hydroxyl groups and optionally the remaining secondary amino groups is >0:1 to <1:1 [mol/mol].

14. A derivate of the polymer according to claim 1, wherein the derivate is obtainable by quaternization, protonation, sulphation and/or phosphation of said polymer.

15. A process for preparing the derivate according to claim 14 further comprising step c), wherein step c) includes subjecting the polymer obtained in step b) to quaternization, protonation, sulphation and/or phosphation.

Description

II. PREPARATION EXAMPLES

[0218] In the following examples, /mol OH means per mol of free OH-groups in the polymer (polytriethanolamine in the following examples).

Example 1: Polytriethanolamine+0.3 Mol Butylene Oxide/Mol OH

1 a) Polytriethanolamine (Condensation According to Step a))

[0219] A four-neck flask equipped with stirrer, distillation bridge, gas inlet tube, and internal thermometer is charged with 1500 g triethanolamine and 20 g of a 50% by weight aqueous solution of H.sub.3PO.sub.2. The mixture is heated under nitrogen to 200 C. The reaction mixture is stirred at 200 C. over a period of 15.5 hours, during which the condensate formed in the reaction is removed by means of a moderate stream of N.sub.2 as stripping gas via the distillation bridge. Toward the end of the reaction time indicated, the temperature is lowered to 140 C. Residual low molecular weight products are removed under a pressure of 100 mbar. Then, the reaction mixture is cooled to ambient temperature, and polytriethanolamine (OH number: 585 mg KOH/g, amine number: 423 mg KOH/g, dynamic viscosity at 60 C.: 431 mPas, Mn=4450 g/mol, Mw=8200 g/mol) is obtained.

1 b) Reaction with 0.3 Mol Butylene Oxide/Mol OH (Alkoxylation According to Step b))

[0220] In a 1 l autoclave 206.3 g polytriethanolamine obtained in example 1 a) and 1.0 g potassium hydroxide (50% aqueous solution) are mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave is purged with nitrogen and heated to 140 C. 46.5 g butylene oxide is added within 0.5 h. To complete the reaction, the mixture is allowed to post-react for additional 10 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 252.0 g of a brown liquid is obtained (hydroxyl number: 495.6 mgKOH/g, amine number: 357.9 mgKOH/g).

Example 2: Polytriethanolamine+0.6 Mol Butylene Oxide/Mol OH

[0221] In a 1 l autoclave 153.6 g polytriethanolamine obtained in example 1 a) and 0.9 g potassium hydroxide (50% aqueous solution) are mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave is purged with nitrogen and heated to 140 C. 69.2 g butylene oxide is added within 1 h. To complete the reaction, the mixture is allowed to post-react for additional 10 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 223.0 g of a brown liquid is obtained (hydroxyl number: 444.9 mgKOH/g, amine number: 304.1 mgKOH/g).

Example 3: Polytriethanolamine+0.5 Mol Dodecene Oxide/Mol OH

[0222] In a 2 l autoclave 197.8 g polytriethanolamine obtained in example 1 a) and 0.8 g potassium hydroxide (50% aqueous solution) are mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave is purged with nitrogen and heated to 140 C. 189.6 g dodecene oxide is added within 2 h. To complete the reaction, the mixture is allowed to post-react for additional 20 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 390.0 g of a brown liquid is obtained.

Example 4: Polytriethanolamine+0.3 Mol Dodecene Oxide/Mol OH

[0223] In a 2 l autoclave 197.8 g polytriethanolamine obtained in example 1 a) and 0.6 g potassium hydroxide (50% aqueous solution) are mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave is purged with nitrogen and heated to 140 C. 113.7 g dodecene oxide is added within 1 h. To complete the reaction, the mixture is allowed to post-react for additional 20 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 299.0 g of a brown liquid is obtained (hydroxyl number: 411.3 mgKOH/g amine number: 277.2 mgKOH/g).

Example 5: Polytriethanolamine+0.2 Mol Dodecene Oxide/Mol OH

[0224] In a 2 l autoclave 229.5 g polytriethanolamine obtained in example 1 a) and 0.6 g potassium hydroxide (50% aqueous solution) are mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave is purged with nitrogen and heated to 140 C. 88.1 g dodecene oxide is added within 0.5 h. To complete the reaction, the mixture is allowed to post-react for additional 24 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 315.0 g of a brown liquid is obtained (hydroxyl number: 426.5 mgKOH/g)

Example 6: Polytriethanolamine+0.1 Mol Dodecene Oxide/Mol OH

[0225] In a 2 l autoclave 242.2 g polytriethanolamine obtained in example 1 a) and 0.6 g potassium hydroxide (50% aqueous solution) are mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave is purged with nitrogen and heated to 140 C. 46.5 g dodecene oxide is added within 0.5 h. To complete the reaction, the mixture is allowed to post-react for additional 24 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 287.9 g of a brown liquid is obtained.

Comparative Example 7: Polytriethanolamine+20 Mol Ethylene Oxide/Mol OH

[0226] In a 2 l autoclave 66.0 g polytriethanolamine obtained in example 1 a) and 2.7 g potassium hydroxide (50% aqueous solution) are mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave is purged with nitrogen and heated to 140 C. 605.6 g ethylene oxide is added within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 10 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 653.6 g of a light brown solid is obtained (hydroxyl number: 65.Math.4 mgKOH/g)

Example 8: Polytriethanolamine+0.2 Mol Dodecene Oxide/Mol OH

[0227] In a 2 l autoclave 167.1 g polytriethanolamine (hydroxyl number: 448.1 mgKOH/g) obtained as described in example 1 a) and 0.4 g potassium tert. butoxide are mixed and stirred under vacuum (<10 mbar) at 120 C. for 0.5 h. The autoclave is purged with nitrogen and heated to 140 C. 49.1 g dodecene oxide is added within 0.5 h. To complete the reaction, the mixture is allowed to post-react for additional 20 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 216.6 g of a brown liquid is obtained.

Comparative Example 9: Polytriethanolamine+1.5 Mol Dodecene Oxide/Mol OH

[0228] In a 5 l autoclave 400.0 g polytriethanolamine (hydroxyl number: 584.6 mgKOH/g) obtained as described in example 1 a) and 7.8 g potassium tert. butoxide are mixed and stirred under vacuum (<10 mbar) at 120 C. for 0.5 h. The autoclave is purged with nitrogen and heated to 140 C. 1150.0 g dodecene oxide is added within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 80 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. 1558.0 g of a yellow liquid is obtained. The conversion of dodecene epoxide (99%) is determined by epoxide titration: epoxy value 113.3 mgKOH/g, amine number: 110.5 mgKOH/g. Epoxy value is determined:according to DIN1877 (July 2000)

Example 10: Evaluation of Cleaning Performance

Preparation of Burnt-on Grease:

[0229] Commercially available vegetable oils are mixed together with albumin (commercially available from Sigma Aldrich) in a ratio of 80 to 20 (w/w) and a heat resistant red dye is added. The mixture is homogenously distributed on an enamel plate and the plate is baked at 165 C. for 2.5-3 hours.

Test Procedure:

[0230] The prepared enamel plates are placed into a wet abrasion scrub tester (Sheen Instruments). Four Sponges are placed into the scrub tester and are treated with 25 mL of a test solution of 10% w/w of a detergent composition as detailed below in table 1 together with 90% w/w water. Hardness of the test solutions is adjusted to 2.5 mM of Ca.sup.2+/Mg.sup.2+ (ratio 3:1) and the pH to 9.0. A photo is taken after every wipe. The amount of residual grease on the enamel plate is quantified via image analysis of the photo.

[0231] The following hand dishwashing detergent compositions are made (table 1):

TABLE-US-00001 TABLE 1 Reference Ingredients composition A Composition B AES 21.41 21.41 C12/14 dimethyl 4.86 4.86 amineoxide Nonionic surfactant 0.43 0.43 PPG 2000 0.40 0.40 Ethanol 2.36 2.36 NaCl 0.80 0.80 Phenoxyethanol 0.15 0.15 PEI polymer 0.25 0.25 Additive 5.0 Dye, perfume and preservative NaOH/HCl to pH 9 (10% in demin water) Water to 100% Numbers in weight % of the formula [0232] AES: C13-15 ethoxylated sulfate with 0.6 average ethoxylation. Nonionic surfactant is a C9-C11 E08. [0233] PPG 2000: polypropylene glycol (Molecular Weight 2000) [0234] PEI polymer: alkoxylated polyethyleneimine polymer with a number average molecularweight of about 14,000 g/mol

[0235] Cleaning performance for solutions with additive (composition B as defined in table 1) are reported after 10 wipes in percentage vs. the cleaning observed for the solution without additive (reference composition A as defined in table 1). The results are shown in tables 2 and 3. Only results within the same cleaning test are compared.

TABLE-US-00002 TABLE 2 (cleaning test 1): cleaning index/[% vs. Reference composition A] Additive according to table 1 after 10 wipes example 1b) 172 example 2 162 comparitive example 7 92

TABLE-US-00003 TABLE 3 (cleaning test 2): cleaning index/[% vs. reference] Additive after 10 wipes example 5 182 example 4 184 comparitive example 7 114

TABLE-US-00004 TABLE 4 (cleaning test 4): cleaning index/[% vs. Reference composition A] Additive according to table 1 after 10 wipes example 5 207 comparitive example 9 99

[0236] Use of comparative example 9 as additive resulted in a turbid test solution whereas for example 5 a clear solution was obtained.

[0237] The results, as presented in table 2, 3 and 4 prove the performance of dishwashing compositions comprising an additive according to example 1 to 6 and 8 according to the present invention in a cleaning test to be superior over dishwashing compositions without an additive (composition A). Further, dishwashing compositions containing an polymer as additive, not according to the invention (comparative examples 7 and 9 in table 2, 3 and 4 show inferior results in the same test. This demonstrates the properties of the selected chemical structure of the inventive polymer, if used as additive, to be causal for the observed improved cleaning performance of the dishwashing composition.