Hyperbranched polymers

Abstract

There is disclosed certain hyperbranched polyester amides with end groups selected from: esters or amides of betaine-type end groups useful in various end uses such as a flocculent.

Claims

1. A hyperbranched polyester amide, wherein the hyperbranched polyester amide comprises at least one end group thereon represented by Formula 1: ##STR00002## wherein the arrow denotes a point of attachment to the hyperbranched polyester amide from the Formula 1 group; R.sub.0 denotes optionally substituted C.sub.1-20hydrocarbo, and Y denotes NR.sub.a or O where R.sub.a is H or optionally substituted C.sub.1-20hydrocarbo, and wherein when Formula 1 is a zwitterion, one or more of the groups R.sub.0, R.sub.1 and R.sub.2 comprise a suitable amount of negative charge to balance the nitrogen cation, p is 0 and X.sup. is absent; or wherein groups R.sub.0, R.sub.1 and R.sub.2 are neutral groups, then X.sup. represents an anion and p is a suitable integer to balance the nitrogen cation; and R.sub.1 and R.sub.2 independently denote optionally substituted C.sub.1-20hydrocarbo groups or together with the nitrogen to which they are attached form in whole or in part a cyclic moiety comprising up to 20 C atoms and optionally one or more hetero atoms.

2. The hyperbranched polyester amide as claimed in claim 1, wherein R.sub.0 is a C.sub.1-20hydrocarbo substituted by one or more hetero atom.

3. The hyperbranched polyester amide as claimed in claim 1, which has a cloud point of at least 50 C.

4. The hyperbranched polyester amide as claimed in claim 1, wherein the hyperbranched polyester amide has a cloud point of at least 75 C., and the at least one end group thereon comprises at least one zwitterion that has an anionic carboxylate ester attached to a positively charged nitrogen atom.

5. The hyperbranched polyester amide as claimed in claim 1, wherein the hyperbranched polyester amide has a cloud point of at least 80 C., and wherein the at least one end group is represented by Formula 1a: ##STR00003## wherein R.sub.1 and R.sub.2 independently denote optionally substituted C.sub.1-6hydrocarbo groups.

6. The hyperbranched polyester amide as claimed in claim 1, wherein in R.sub.1 and R.sub.2 independently denote C.sub.1-4hydrocarbyl groups.

7. The hyperbranched polyester amide as claimed in claim 6, wherein in R.sub.1 and R.sub.2 independently denote methyl.

8. The hyperbranched polyester amide as claimed in claim 1, wherein the hyperbranched polyester amide comprises cationic functional groups thereon and at least one carboxylate counter anion obtained from at least one organic carboxylic acid or salt thereof.

9. The hyperbranched polyester amide as claimed in claim 8, wherein the at least one carboxylate counter anion is obtained from citric acid or an acid salt thereof.

10. The hyperbranched polyester amide as claimed in claim 1, which comprises a core obtained from hexahydrophthalic anhydride.

11. The hyperbranched polyester amide as claimed in claim 1, which has a cloud point of at least 100 C. in BRINE.

12. The hyperbranched polyester amide as claimed in claim 1, which comprises a core obtained from at least one hexahydrophthalic anhydride, at least one cationic end group and at least one citrate counter anion, and wherein the hyperbranched polyester amide has a cloud point of at least 100 C. in BRINE.

13. The hyperbranched polyester amide as claimed in claim 1, wherein p is 1 if X has a single negative charge.

14. A flocculent composition which comprises the hyperbranched polyester amide as claimed in claim 1 and a diluent.

15. A method of flocculating a material dispersed in an aqueous medium comprising the steps of: (a) providing an aqueous dispersion of a material dispersed in an aqueous medium, and (b) adding to the aqueous dispersion a sufficient amount of the hyperbranched polyester amide as claimed in claim 1 so as to flocculate the material dispersed in the aqueous medium.

Description

EXAMPLES

(1) The present invention will now be described in detail with reference to the following non limiting examples which are by way of illustration only. The below examples comprise preparation of the polyester amides according to the invention in solvent.

Preparation 1A

(2) A 6 L glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a Dean Stark distilling trap filled with methylcyclohexane and a nitrogen connection. The reactor is charged with 1037.4 g of diisopropanol amine, 1459.2 g of N,N-bis(NN-dimethylaminopropyl) amine and 2268.3 g of hexahydrophthalic anhydride. A gentle nitrogen flow is applied to the glass reactor. The reaction mixture is stirred at 500 rpm and heated to 120 C. This temperature is maintained for 30 minutes. The temperature is increased to 180 C. and the azeotropic distillation starts. Heating is maintained until the residual carboxylic acid content <10 mgKOH/g (titrimetical analysis). The reaction mixture is cooled down to 130 C. and the methylcyclohexane is distilled off by means of vacuum distillation at this temperature. The product obtained is used in the next step.

(3) The product has been characterised as follows: Acid value=9.3 mgKOH/g (titrimetrical analysis), Amine value=183.6 mgKOH/g (titrimetrical analysis), Molecular weight Mw=5200 g/mol.

Preparation 1B

(4) A 3 L glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a condenser and a nitrogen connection. The reactor is charged with 450.0 g of the product obtained in preparation 1A and 550.0 g of ethylene glycol. A gentle nitrogen flow is applied to the glass reactor. The mixture is stirred and heated to 80 C. to obtain a solution. 143.9 g of methylchloroacetate is added over a period of one hour. 119.7 g of ethylene glycol is added to the mixture and the mixture is heated to 100 C. This temperature is maintained until the amount of unreacted methylchloroacetate is <50 ppm (determined by H.sup.1-NMR). The product is diluted with 56.2 g ethylene glycol to obtain the desired solid contents.

(5) The product has been characterised as follows: Solid contents=44.5 w % (halogen drier @ 160). Viscosity=1220 mPa.Math.s (23 C.). Example 1.

Preparation 1C

(6) A 3 L glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a condenser and a nitrogen connection. The reactor is charged with 500.0 g of the product obtained in preparation 1A and 611.1 g of ethylene glycol. A gentle nitrogen flow is applied to the glass reactor. The mixture is stirred and heated to 80 C. to obtain a solution. 124.3 g of methylchloroacetate is added over a period of one hour. 92.9 g of ethylene glycol is added to the mixture and the mixture is heated to 100 C. This temperature is maintained until the amount of unreacted methylchloroacetate is <50 ppm (determined by H.sup.1-NMR). The product is diluted with 59.0 g ethylene glycol to obtain the desired solid contents.

(7) The product has been characterised as follows: Solid contents=46.0 w % (halogen drier @ 160). Viscosity=1430 mPa.Math.s (23 C.). Example 2

Preparation 1D

(8) In a 1 L PE jar, 625.0 g of the product obtained in preparation 1C is mixed with 43.4 g of citric acid and 67.0 g of ethylene glycol. The mixture is shaken until it is homogeneous.

(9) The product has been characterised as follows: Solid contents=45.0 w % (calculated). Viscosity=1425 mPa.Math.s (23 C.). Example 3.

Preparation 1E

(10) In a 1 L PE jar, 595.0 g of the product obtained in preparation 1C is mixed with 63.6 g of choline dihydrogencitrate and 90.9 g of ethylene glycol. The mixture is shaken until it is homogeneous.

(11) The product has been characterised as follows: Solid contents=45.0 w % (calculated). Viscosity=1005 mPa.Math.s (23 C.). Example 4.

Preparation 2A

(12) A 3 L glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a distillation head and a vacuum and nitrogen connection. The reactor is charged with 207.1 g diisopropanol amine and 437.0 g of N,N-bis(NN-dimethylaminopropyl) amine. The reactor is heated to 40 C. and 892.5 g of dodecenyl succinic anhydride is added. The mixture is heated to 160 C. and this temperature is maintained for 1 hour. Then, the pressure is gradually reduced to a final pressure of <10 mbar to remove reaction water. Heating and vacuum were maintained until the residual carboxylic acid content is <8 mgKOH/g (titrimetrical analysis) to obtain a product used in the next step.

(13) The product has been characterised as follows: Acid value=5.5 mgKOH/g (titrimetrical analysis), Amine value=158.6 mgKOH/g (titrimetrical analysis), Molecular weight Mw=3500 g/mol.

Preparation 2B

(14) A 500 mL glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a condenser and a nitrogen connection. The reactor is charged with 150.0 g of the product obtained in preparation 2A and 183.3 g of ethylene glycol. A gentle nitrogen flow is applied to the glass reactor. The mixture is stirred and heated to 80 C. to obtain a solution. 41.4 g of methylchloroacetate is added over a period of one hour. 32.5 g of ethylene glycol is added to the mixture and the mixture is heated to 100 C. This temperature is maintained until the amount of unreacted methylchloroacetate is <50 ppm (H.sup.1-NMR). The product is diluted with 18.1 g ethylene glycol to obtain the desired solid contents.

(15) The product has been characterised as follows: Solid contents=41.0 w % (halogen drier @ 160). Example 5.

Preparation 3A

(16) A 6 L glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a Dean Stark distilling trap filled with methylcyclohexane and a nitrogen connection. The reactor is charged with 967.5 g of diisopropanol amine, 1597.5 g of N,N-bis(NN-dimethylaminopropyl) amine and 2190.9 g of hexahydrophthalic anhydride. A gentle nitrogen flow is applied to the glass reactor. The reaction mixture is stirred at 500 rpm and heated to 120 C. This temperature is maintained for 30 minutes. The temperature is increased to 180 C. and the azeotropic distillation starts. Heating and distallation is maintained until the residual carboxylic acid content <10 mgKOH/g (titrimetical analysis). The reaction mixture is cooled down to 130 C. and the methylcyclohexane is distilled off by means of vacuum distillation at this temperature. The product obtained is used in the next step.

(17) The product has been characterised as follows: Acid value=7.8 mgKOH/g (titrimetrical analysis), Amine value=197.7 mgKOH/g (titrimetrical analysis), Molecular weight Mw=2900 g/mol.

Preparation 3B

(18) A 3 L glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a condenser and a nitrogen connection. The reactor is charged with 500.0 g of the product obtained in preparation 3A and 541.7 g of ethylene glycol. A gentle nitrogen flow is applied to the glass reactor. The mixture is stirred and heated to 80 C. to obtain a solution. 133.6 g of methylchloroacetate is added over a period of one hour. 92.2 g of ethylene glycol is added to the mixture and the mixture is heated to 100 C. This temperature is maintained until the amount of unreacted methylchloroacetate is <50 ppm (determined by H.sup.1-NMR). The product is diluted with 56.2 g ethylene glycol to obtain the desired solid contents.

(19) The product has been characterised as follows: Solid contents=53.1 wt % (halogen drier @ 160). Viscosity=3470 mPa.Math.s (23 C.). Example 6.

Preparation 4A

(20) A 3 L double walled glass reactor, which can be heated by circulating hot oil, is fitted with a mechanical stirrer, a connection connected to a vacuum pump and a nitrogen connection. A gentle nitrogen flow is applied to the glass reactor. The reactor is warmed to 80 C. and charged with 131.6 g of diisopropanol amine, 185.0 g of N,N-bis(NN-dimethylaminopropyl) amine. 220.0 g of hexahydrophthalic anhydride is slowly added over a period of 25 minutes. The reaction mixture is stirred at approximately 300 rpm. This temperature is maintained at 80 C. for 10 minutes and 263.4 of polyethylene glycol biscarboxymethylene ether with average molecular weight of 600 is added. The temperature is increased to 170 C. and the pressure is gradually reduced to 50 mbar over a period 9 hrs. Heating and vacuum is maintained until the residual carboxylic acid content <10 mgKOH/g (titrimetical analysis). The product obtained is used in the next step.

(21) The product has been characterised as follows: Acid value=10.2 mgKOH/g (titrimetrical analysis), Amine value=115.3 mgKOH/g (titrimetrical analysis), Molecular weight Mw=7000 g/mol.

Preparation 4B

(22) A 1 L glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a condenser and a nitrogen connection. The reactor is charged with 91.5 g of the product obtained in preparation 4A and 111.8 g of ethylene glycol. A gentle nitrogen flow is applied to the glass reactor. The mixture is stirred and heated to 100 C. to obtain a solution. 12.6 g of methylchloroacetate is added. An additional 22.5 g of ethylene glycol is added to the mixture and the mixture is stirred at 100 C. This temperature is maintained until the amount of unreacted methylchloroacetate is <50 ppm (determined by H.sup.1-NMR). The product is diluted with 10.4 g ethylene glycol to obtain the desired solid contents.

(23) The product has been characterised as follows: Solid contents=45.8 wt % (halogen drier @ 160). Viscosity=512 mPa.Math.s (23 C., 2.5 rpm). Example 7.

Preparation 5A

(24) A 1 L double walled glass reactor, which can be heated by a heating mantle, is fitted with a mechanical stirrer, a connection connected to a vacuum pump and a nitrogen connection. A gentle nitrogen flow is applied to the glass reactor. The reactor is charged with 142.5 g hexahydrophthalic anhydride and 297.2 g of polyethyleneglycol monomethyl ether with average molecular weight of 750 g/mol. The reaction mixture is stirred at 500 rpm and heated to 80 C. This temperature is maintained for 30 minutes. Than the reactor is charged with 7.5 g of morpholine and stirred for 10 minutes. 52.8 g of diisopropanolamine and 34.4 g of 1-methylpiperazine is added. The temperature is increased to 120 C. stirred for 1 hour. Than the temperature is increased to 170 C. which is maintained for 1 hour. The pressure is gradually reduced with approximately 50 mbar each 5 minutes until full vacuum is reached. This is maintained until the residual carboxylic acid content <10 mgKOH/g (titrimetical analysis). The product obtained is used in the next step.

(25) The product has been characterised as follows: Acid value=8.4 mgKOH/g (titrimetrical analysis), Amine value=36.8 mgKOH/g (titrimetrical analysis), Molecular weight Mw=3800 g/mol.

Preparation 5B

(26) A 370 mL glass reactor, which can be heated by a hot water bath, is fitted with a gneticl stirrer. The reactor is charged with 200 g of a 50 wt % solution of the product obtained in 5A in 2-butoxyethanol and 6.4 g methyl chloroacetate is added. The mixture is stirred at 80 C. for 20 hours to obtain the final product of example 8.

(27) Comparative A:

(28) A double walled glass reactor, which can be heated by means of thermal oil, fitted with a mechanical stirrer, a distillation head, a vacuum and nitrogen connection, is charged with 192.5 g of succinic anhydride. The reactor was heated to 125 C. When the succinic anhydride has melted 307.5 g of diisopropanol amine was added. The reaction mixture was stirred for 1 hour and then the temperature was raised to 160 C. Over a period of 4 hours the pressure was gradually reduce to a final pressure of <10 mbar to distil off reaction water. Heating and vacuum were maintained until the residual carboxylic acid content was <0.2 meq/g (tritrimetrical analysis). Molecular weight Mn=1200. AV=5.2 mgKOH/g

(29) Comparative B

(30) A double walled glass reactor, which can be heated by means of thermal oil, fitted with a mechanical stirrer, a distillation head, a vacuum and nitrogen connection, is charged with 245.5 g of hexahydrophthalic anhydride. The reactor was heated to 80 C. When the anhydride has melted 254.5 g of diisopropanol amine was added. The reaction mixture was stirred for 1 hour and then the temperature was raised to 160 C. Over a period of 4 hours the pressure was gradually reduce to a final pressure of <10 mbar to distil off reaction water. Heating and vacuum were maintained until the residual carboxylic acid content was <0.2 meq/g (tritrimetrical analysis). Molecular weight Mn=1500. AV=6.4 mgKOH/g.

(31) TABLE-US-00002 Cloud point ( C.) Compound from example DMW BRINE 1 >100 >100 2 >100 >100 3 >100 >100 4 >100 >100 5 >100 >100 6 >100 >100 7 nd 67 8 91 37 Comp A 84 14 Comp B Insoluble Insoluble