Blocky hydroxyethylcellulose, derivatives thereof, process of making, and uses thereof

• US 20060182703A1
• Filed: 02/14/2006
• Published: 08/17/2006
• Est. Priority Date: 02/17/2005
• Status: Active Grant

• Current Assignee: Hercules, LLC (Ashland Global Holdings, Inc.)
• Original Assignee: Hercules Incorporated (Ashland Global Holdings, Inc.)
• Inventors: Arisz, Petrus Wilhelmus Franciscus, Nguyen, Tuyen T., Lusvardi, Kate M.
• Granted Patent: US 8,709,390 B2
• Time in Patent Office: Days
• US Class Current: 424/70.130
• CPC Class Codes: A61K 8/731 Cellulose; Quaternized cellulose derivatives
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: A61Q 5/06 Preparations for styling the hair, e.g. by temporary shaping or colouring
• CPC Class Codes: A61Q 5/12 Preparations containing hair conditioners
• CPC Class Codes: C04B 2103/44 Thickening, gelling or viscosity increasing agents
• CPC Class Codes: C04B 2111/00672 Pointing or jointing materials
• CPC Class Codes: C04B 24/383 Cellulose or derivatives thereof
• CPC Class Codes: C04B 28/02 containing hydraulic cements other than calcium sulfates
• CPC Class Codes: C08B 11/08 with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
• CPC Class Codes: C08B 11/20 Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
• CPC Class Codes: C08B 15/00 Preparation of other cellulose derivatives or modified cellulose , e.g. complexes
• CPC Class Codes: C08L 1/08 Cellulose derivatives
• CPC Class Codes: C08L 1/284 with hydroxylated hydrocarbon radicals
• CPC Class Codes: C09D 101/284 with hydroxylated hydrocarbon radicals
• CPC Class Codes: C09D 11/08 based on natural resins
• CPC Class Codes: C09K 8/10 Cellulose or derivatives thereof
• CPC Class Codes: C09K 8/467 containing additives for specific purposes
• CPC Class Codes: C09K 8/514 of natural origin, e.g. polysaccharides, cellulose C09K8/512 takes precedence

Abstract

This invention relates to non-uniformly substituted (“blocky”) hydroxyethylcelluloses (HECs) and derivatives thereof that exhibit associative behavior in both neat solutions and in filled systems. The HECs and derivatives thereof exhibit unique and highly desirable rheology and are more efficient in thickening aqueous systems than prior art HEC products. These blocky HECs can be distinguished from prior art and commercial HEC products by having an unsubstituted anhydroglucose trimer ratio (U3R) greater than 0.21 and the hydroxethyl molar substitution greater than about 1.3 and less than about 5. This invention also relates to processes for making blocky HEC and uses thereof in functional systems.

Claims

1. A composition comprising hydroxyethylcellulose (HEC) having hydroxyethyl groups that are non-uniformly distributed on the cellulose backbone wherein the unsubstituted trimer ratio (U3R) is greater than 0.21 and the hydroxyethyl molar substitution is greater than about 1.3 and less than about 5.0.

2. The composition of claim 1, wherein the hydroxyethylcellulose is further modified with one or more substituents having chemical functionality selected from the group consisting of nonionic, anionic, and cationic and mixtures thereof.

3. The composition of claim 2, wherein the substituents are attached to the hydroxyethylcellulose backbone via an ether, ester, or urethane linkage moiety.

4. The composition of claim 2, wherein the substituents present have nonionic chemical functionality.

5. The composition of claim 4, wherein the substituents have the formula

—

R, or -A-R,

wherein

A is selected from the group consisting of

CH₂—

CH(OH),

CH₂—

CH(OH)—

CH₂,

(CH₂—

CH₂—

O)_n where n=1-100,

CH₂—

CH(OH)—

CH₂—

O—

(CH₂—

CH₂—

O)_n where n=1-100, and

CH(R)—

C(O)—

CH₂,

and

R is selected from the group consisting of

i) an acyclic or cyclic, saturated or unsaturated, branched or linear hydrocarbon moiety having 1 to 30 carbon atoms,

ii) an acyclic or cyclic, saturated or unsaturated, branched or linear heterohydrocarbon moiety having 1 to 30 carbon atoms and one of more oxygen, nitrogen, or silicone atoms,

iii) an acyclic or cyclic, saturated or unsaturated, branched or linear hydrocarbon moiety having 1 to 30 carbon atoms and one or more aromatic hydrocarbon groups,

iv) an acyclic or cyclic, saturated or unsaturated, branched or linear heterohydrocarbon moiety having 1 to 30 carbon atoms and one or more oxygen, nitrogen, or silicone atoms and one or more aromatic groups, and

v) an acyclic or cyclic, saturated or unsaturated, branched or linear, heterohydrocarbon moiety having 1 to 30 carbon atoms and one or more oxygen, nitrogen, or silicone atoms and one or more heteroaromatic groups containing one or more oxygen, nitrogen, or silicone groups.

6. The composition of claim 5, wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, alkyl aryl, aryl alkyl, alkenyl aryl, aryl alkenyl, and mixtures thereof, having when possible, from 1 to 30 carbon atoms.

7. The composition of claim 2, wherein the substituents present have anionic chemical functionality.

8. The composition of claim 7, wherein the anionic chemical functionality is selected from the group consisting of carboxylate, sulfate, sulfonate, phosphate, phosphonate and mixtures thereof.

9. The composition of claim 7, wherein the substituents are selected from the group consisting of carboxymethyl, sulfoethyl, phosphonomethyl, and mixtures thereof.

10. The composition of claim 2, wherein the substituents present have cationic chemical functionality.

11. The composition of claim 10, wherein the substituents have the formula R¹R²R³R⁴N+(A⁻

)

wherein

R¹ is —

CH₂—

CHOH—

CH₂—

or —

CH₂—

CH₂—

,

R², R³, R⁴ each independently is selected from the group consisting of an alkyl or aryl alkyl group having 1 to 20 carbon atoms, and

A- is a halide, sulfate, phosphate, or tetrafluoroborate.

12. The composition of claim 11, wherein the substituents are selected from the group consisting of 2-hydroxpropyltrimethylammonium chloride, 2-hydroxypropyldodecyldimethylammonium chloride, 2-hydroxypropylcocoalkyldimethylammonium chloride 2-hydroxypropyloctadecyidimethylammonium chloride and mixtures thereof.

13. The composition of claim 10, wherein the cationic group is derived from the grafting reaction of the HEC composition with diallyldimethylammonium chloride.

14. The composition of claim 2, wherein the modified hydroxyethylcellulose is selected from the group consisting of methyl hydroxyethylcellulose, ethyl hydroxyethylcellulose, octyl hydroxyethylcellulose, cetyl hydroxyethylcellullose, cetoxy-2-hydroxypropyl hydroxyethylcellulose, butoxy-2-hydroxypropyl hydroxyethylcellulose, butoxy-2-hydroxypropyl cetyl hydroxyethylcellulose, butoxy-2-hydroxypropyl cetoxy-2-hydroxyethylcellulose, carboxymethyl hydroxyethylcellulose, carboxymethyl ethyl hydroxyethylcellulose, carboxymethyl octyl hydroxyethylcellulose, carboxymethyl cetyl hydroxyethylcellulose, carboxymethyl cetoxy-2-hydroxypropylcellulose, carboxymethyl butoxy-2-hydroxyethylcellulose, sulfoethyl hydroxyethyicellulose, sulfoethyl ethyl hydroxyethylcellulose, sulfoethyl cetyl hydroxyethylcellulose, sulfoethyl cetoxy-2-hydroxypropylcellulose, 2-hydroxypropyltrimethylammonium chloride hydroxyethylcellulose, 2-hydroxypropyltrimethylammonium chloride ethyl hydroxyethylcellulose, 2-hydroxypropyltrimethylammonium chloride butoxy-2-hydroxypropyl hydroxyethylcellulose, 2-hydroxypropyltrimethylammonium chloride octyl hydroxyethylcellulose 2-hydroxypropyltrimethylammonium chloride cetyl hydroxyethylcellulose, 2-hydroxypropyltrimethylammonium chloride cetoxy-2-hydroxypropyl hydroxyethylcellulose, 2-hydroxypropyllauryldimethylammonium chloride hydroxyethylcellulose,

2-hydroxypropyltrimethylammonium chloride 2-hydroxypropyllauryldimethylammonium chloride hydroxyethylcellulose,

diallyldimethylammonium chloride hydroxyethylcellulose graft copolymer, and diallyldimethylammoniumchloride cetyl hydroxyethylcellulose graft copolymer.

15. The composition of claim 1, wherein the unsubstituted trimer ratio (U3R) is greater than 0.235.

16. The composition of claim 1, wherein the hydroxyethyl molar substitution is greater that about 1.3 and less than about 4.0.

17. A slurry process for making the hydroxyethylcellulose composition of claim 1 comprising

A) mixing and reacting cellulose, water and a base reagent in an organic solvent for a sufficient time and at a sufficient temperature in order to form a first base reagent cellulose mixture, wherein the water to anhydroglucose (AGU) molar ratio is in the range of about 5 to 35 and (a) the base reagent to AGU molar ratio is greater than about 1.6 or (b) the base reagent to AGU molar ratio is less than about 0.4,

B) (i) when (a) is used from Step A, then sufficient acid is added in order to reduce the base reagent concentration to a base reagent to AGU molar ratio of no less than about 0.6 to form a second base reagent cellulose mixture, or

(ii) when (b) is used from Step A, then sufficient ethylene oxide is added and reacted at a sufficient temperature and for a sufficient time to form a HEC product with a hydroxyethyl molar substitution of less than 1.3, followed by additional base reagent to adjust the base reagent to AGU molar ratio to greater than about 1.0 to form a base reagent HEC mixture, and

C) then adding to the second base reagent cellulose mixture from B(i) or to the base reagent HEC cellulose mixture from B(ii) a sufficient amount of ethylene oxide and reacting at a sufficient temperature and for a sufficient time in order to form the final HEC composition.

18. The slurry process of claim 17, wherein the organic solvent is selected from the group consisting of ethanol, isopropanol, tert-butanol, acetone, methyl ethyl ketone, and dimethoxyethane and mixtures thereof.

19. The slurry process of claim 17, wherein the base is an alkali selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, and mixtures thereof.

20. The slurry process of claim 17, wherein the cellulose is selected from the group consisting of cotton linters, wood pulps, and mixtures thereof.

21. The slurry process of claim 17, wherein the HEC composition is further reacted with at least one other derivatizing reagent to form a modified hydroxyethylcellulose composition.

22. The slurry process of claim 21, wherein the derivatizing reagent is selected from the group consisting of nonionic, cationic, anionic organic compounds and mixtures thereof.

23. The slurry process of claim 22 wherein the organic compounds are selected from the group consisting of halides, epoxides, glycidyl ethers, carboxylic acids, isocyanates, and mixtures thereof.

24. The slurry process of claim 17 or 21, wherein the HEC or modified HEC composition is further reacted with a viscosity reducing agent.

25. The slurry process of claim 24, wherein the viscosity reducing agent is selected from the group consisting of peroxides, persulfates, peracids, cellulolytic enzymes, salts of halide oxo acids, oxygen, and ozone.

26. A composition comprising a) a functional system selected from the group consisting of personal care compositions, household care compositions, pharmaceutical compositions, building and construction compositions, emulsion polymerization compositions, oil field servicing fluid compositions, civil engineering servicing fluid compositions, paper coating compositions, paper making compositions, architectural coating compositions, industrial coating compositions, printing ink compositions, adhesive compositions, and mineral processing and recovery compositions and b) a hydroxyethylcellulose (HEC) of claim 1 or modified hydroxyethylcellulose of claim 2.

27. The composition of claim 26, wherein the functional system is an aqueous based architectural or industrial coating composition.

28. The coating composition of claim 27 further comprising a binder selected from the group consisting of a latex, an alkyd resin, a urethane resin, a silicone resin and an epoxy resin.

29. The composition of claim 26, wherein the functional system is a building or construction material composition selected from the group consisting of concrete, tile cements and adhesives, plasters, stuccos, mortars, underwater concrete, joint compound or cement, crack fillers, floor screeds, and adhesive mortars.

30. The composition of claim 29, wherein the building or construction material composition is a joint compound or cement.

31. The composition of claim 30, wherein the joint compound or cement contains less than about 0.5% clay.

32. The composition of claim 26, wherein the functional system is a personal care composition.

33. The composition of claim 32, wherein the personal care composition is selected from the group consisting of skin care, hair care, oral care, nail care, and personal hygiene products.

34. The composition of claim 26, wherein the functional system is a household care composition.

35. The composition of claim 34, wherein the household care composition is selected from the group consisting of fabric care, laundry detergent, hard surface cleaner, industrial institutional liquid soaps, and dish detergents.

36. The composition of claim 26, wherein the functional system is an oil field servicing fluid composition.

37. The composition of claim 36 wherein the oil field servicing fluid composition is selected from the group consisting of drilling fluid, completion or workover fluid, fracturing fluids, and oil well cementing fluids.

38. The composition of claim 26, wherein the functional system is a paper coating composition.

39. The composition of claim 26, wherein the functional system is a paper making composition.

40. The composition of claim 26, wherein the functional system is a pharmaceutical composition.

41. The composition of claim 40, wherein the pharmaceutical composition is selected from the form consisting of tablet, capsule, and granules.

42. The composition of claim 40, wherein the component b is used as an excipient.