Polyether/polyurethane association thickeners

Details Polyether/polyurethane association thickeners Polyether/polyurethane association thickeners

2003-04-02

2004-09-07

Gorr, Rachel (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From reactant having at least one -n=c=x group as well as...

C528S077000, C528S049000, C528S083000

Reexamination Certificate

active

06787628

ABSTRACT:

The present invention relates to polymers comprising polyether chains having a hydrophobic side chain which are linked by urethane and/or amide groups and their use as “Association Thickeners” in polar media such as paints and inks, including inks for non-contact printing processes such as Drop-on-Demand inkjet printing. Many of these polymers are believed to function according to “Micellar Bridging” theory.
The terms “Association Thickener” and “Micellar Bridging” theory are explained in U.S. Pat. No. 4,426,485 and refer to the manner in which the hydrophobic parts (hereinafter hydrophobe) of a water-soluble thickener are absorbed by a solute particle such as a latex particle to provide a network of low molecular weight thickener molecules giving good flow and levelling characteristics to water-borne coatings and latex systems under high shear conditions.
Association Thickeners are thickeners which function by Micellar Bridging theory and generally contain hydrophobes which are spaced either randomly or in clusters along a hydrophilic, especially water-soluble, polymer backbone. Polyester Association Thickeners have been proposed which are obtained by polymerising a polyethylene glycol chain attached to a moiety containing a hydrophobe but these can exhibit storage deficiencies when used in strongly alkaline latices and/or latices which contain primary amines. It has now been found that improved storage properties can be obtained where the repeat units are connected via urethane and/or amide groups.
According to the invention there is provided a polymer comprising the addition reaction product of a polyisocyanate having a functionality of from 2 to 10 and a succinyl polyether having a C
6-30
-alk(en)yl group and at least one group which is capable of reacting with the polyisocyanate.
The polyisocyanate may be aliphatic, cyclo-aliphatic or aromatic, including mixtures thereof. Examples of suitable polyisocyanates are 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-decamethylenediisocyanate, 1,4-cyclohexylenediisocyanate, 4,4
1
-methylenebis (isocyanatocyclohexane), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, m- and p-phenylenediisocyanate, 2,6-and 2,4-tolylenediisocyanate (TDI), xylenediisocyanate, 4-chloro-1,3-phenylenediisocyanate, 4,4
1
-biphenyleneisocyanate, 4,4
1
-methylenediphenylisocyanate(MDI), isophorone diisocyanate, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthylene diisocyanate; polymethylene polyphenylisocyanates sold under the brand name “PAPI” such as “PAPI 135” (equivalent weight of 133.5 and average isocyanate functionality of 2.7) and “PAPI 901” (equivalent weight of 133 and average isocyanate functionality of 2.3); aromatic triisocyanate adduct of trimethylolpropane and TDI sold under the trade name “Mondur CB-75” aliphatic tri-isocyanates such as the hydrolytic trimerisation product of 1,6-hexamethylenediisocyanate sold as “Desmodur N”; and C
36
-dimer acid diisocyanate sold as “DDI” as disclosed in J. Am. Oil Chem. Soc. 51,522 (1974).
Other polyfunctional polyisocyanates are those obtainable by the addition reaction of diisocyanates and polyols such as
or those obtainable from di-isocyanates by the biuret reaction, such as
OCN—(CH
2
)
6
—N—(CONH(CH
2
)
6
NCO)
2
or polyisocyanates obtainable by the cyclisation of di-isocyanates such as
Trade product: Desmodur HL (registered Trade Mark)
Trade product: Desmodur IL (registered Trade Mark)
Trade product: Polurene KC (registered Trade Mark)
Trade product: Polurene HR (registered Trade Mark)
Tolylene diisocyanate-isophorone diisocyanate-isocyanurate Company: SAPICI)
Trimeric isophoronediisocyanate (isocyanurate-T1890 of Chemische Werke Huls)
Further examples of polyisocyanates available as commercial products include Desmodur VL (polyisocyanate based on diphenylmethane diisocyanate (MDI) from Bayer), Desmodur A 4370 (polyisocyanate based on isophorone diisocyanate (IPDI) from Bayer), Polurene KD (polyisocyanate based on toluene diisocyanate (TDI) from SAPICI), Uronal RA.50 (polyisocyanate based on TDI from Galstaff), Polurene A (polyisocyanate based on TDI-trimethylol propane (TMP) from SAPICI), Polurene MC (polyisocyanate based on TMP-IPDI from SAPICI), Polurene MD.70 (polyisocyanate based on TMP-TDI-MDI from SAPICI.
Many of the polyisocyanates are commercially available as mixtures. The term “average functionality” means the statistical average number of free isocyanate groups in the polyisocyanate and is the ratio of average molecular weight of the polyisocyanate and the isocyanate equivalent weight taking into account the number of isocyanate groups.
Preferably, the polyisocyanate has a functionality of from 2 to 6.
The succinyl polyether is obtainable by reacting a polyether having at least one amino or hydroxy group with a C
6-30
-alk(en)ylsuccinic anhydride.
The polyether is preferably derivable from ethylene oxide, propylene oxide or butylene oxide or it may be derivable from polymerised tetrahydrofuran, including mixtures thereof. It is, however, preferred that the polyether is derivable from ethylene oxide and/or propyleneoxide. Polyethers derivable from ethylene oxide are much preferred. The number of recurring alkyleneoxy groups in the succinyl polyether is preferably from 4 to 800, more preferably from 4 to 500 and especially from 4 to 300.
The polyether may be a polyalkyleneglycol, a polyalkyleneglycol mono alkyl ether, a polyalkyleneglycol mono amine, a polyalkyleneglycol mono alkyl ether mono amine or a polyalkyleneglycol diamine.
When the polyether is a mono alkyl ether, the alkyl group preferably contains not greater than 30 carbon atoms, more preferably not greater than 20 carbon atoms, even more preferably not greater than 10 carbon atoms and especially not greater than 6 carbon atoms. The alkyl group may be linear or branched. Useful thickeners have been obtained when the polyether is a mono methyl ether.
It is much preferred that the polyether is difunctional. Examples of difunctional polyethers are polyalkyleneglycols, more preferably polyalkyleneglycol mono amines and especially polyalkyleneglycol diamines.
Examples of polyalkyleneglycols are polyethyleneglycols such as PEG 200, PEG 1500, PEG 2000, PEG 3000, PEG 4000, PEG 6000, PEG 8000, PEG 10000, PEG 12000 and PEG 35000, wherein the numbers indicate the approximate number average molecular weight.
Examples of mixed chain polyalkyleneglycols are the EO/PO/EO block copolymers such as those which are commercially available as Synperonic polymers from Uniqema and the PO/EO/PO block co polymers which are available as Pluronic polymers from BASF.
Examples of polyalkylene glycol mono alkyl ethers are MeO PEG 350, 550, 750, 2000 and 5000 (ex Aldrich) and
n
BuO PPG 340, 1000, 1200, 2500, and 4000 (ex Aldrich).
Other examples of polyalkyleneglycol mono alkyl ethers are Brij 35 (EO (23) end-capped by dodecanol), Brij 97 (EO(10) end-capped by oleyl alcohol), Brij 78 (EO(20) end-capped by stearyl alcohol) and Brij 700 (EO(100) end-capped by stearyl alcohol). The Brij surfactants are available from ICI Inc.
Examples of polyalkyleneglycol mono alkyl mono amines are the so called Jeffamine M series of polyethers available from Huntsman Corporation. Specific examples are Jeffamine M-1000 (MeO EO (19) PO (3) amine), M-600 (MeO EO (1) PO (9) amine), M-2070 (MeO EO (32) PO (10)amine), M-2005 (MeO EO (6) PO(39) and M-3003 (MeO EO (49) PO (8) amine). MeO represents a methoxy terminated polyether, EO represents repeat ethylene oxide units and PO represents repeat propyleneoxide units and the numbers in parentheses represent the approximate number of repeat units.
Examples of polyalkyleneglycol diamines are the so-called Jeffamine D-series of polyether diamines which are amine terminated polypropyleneglycols of formula
Specified examples are Jeffamine D-230 (x=2-3), D-400(x=5-6), D-2000 (x=33 average) and D-4000 (x=68 average).
Other examples of polyalkyleneglycol diamines are the Jeffamine ED-series of polyether diamines which are bas

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