Carboxylated polymers complexes

Abstract

The present invention deals with the composition, and application of novel carboxylated polymers. The complexes are made by a series of reactions which include reaction of an anhydride with an allyl alcohol alkoxylate, polymerization of the carboxylated allyl alkoxylate, then formation of a complex of the poly carboxylate with quaternary compounds.

Description

BACKGROUND OF THE INVENTION

2. 1. Field of the Invention

3. The present invention deals with the composition, and application of novel carboxylated polymers, and complexes thereof. The complexes useful as softening, anti-tangle, and conditioning agents for use in personal care applications due to their outstanding mildness. The properties of these novel compounds that makes them well suited for these applications is the fact that they are substantive to fibers, hair and skin and also very mild to the skin and eyes and provide protection from environmental factors like acid rain and other pollutions which come in contact with hair and skin. The use of the complex results in several additional desirable properties heretofore unattainable. This includes overcoming the problem of eye and skin irritation using traditional cationic conditioning agents.

4. 2. Arts and Practices

5. U.S. Pat. No. 5,162,472 to O'Lenick discloses free radical polymers which incorporate silicone into the backbone. While these materials have desirable properties, they do not form monolayers on the hair nor do they provide protection to the hair.

6. The formation of a high molecular weight polymeric complex results in less penetration of the skin by the compounds of the present invention and a very effective conditioner that remains on the surfact of the hair or skin where the conditioning agent is most effective.

7. The references cited herein are incorporated by reference to the extent applicable. Ratios and percentages are by weight and temperatures are Celsius unless otherwise stated.

THE INVENTION

Object of the Invention

8. It is the object of the current invention to provide a novel series of anionic free radical polymers and complexes thereof with cationic compounds. The formation of a high molecular weight polymeric complex results in less penetration of the skin by the compounds of the present invention and a very effective conditioner that remains on the surfact of the hair or skin where the conditioning agent is most effective.

9. It is another object of the current invention to provide a novel allyl alkoxy carboxylate used as an intermediate in the preparation of the compounds of the present invention.

10. It is still another objective of the current invention to provide personal care compositions which contain an effective conditioning amount of the compounds of the current invention. That effective conditioning concentration will vary from 0.1 to 20% of the composition. The compounds of the present invention have outstanding conditioning properties when applied to hair and skin.

SUMMARY OF THE INVENTION

11. The present invention is directed to free radical polymers which contain a carboxyl group as one of the functional groups polymerized. The compounds of the invention are prepared by the free radical polymerization of a novel allyl carboxy monomer.

12. The carboxy functional allyl monomer is polymerized and subsequently complexed with a variety of quaternary compounds to form the conditioning quats of the present invention.

13. The allyl alkoxy carboxylate used to make the compounds of the present invention conform to the following structure:

CH2═CH—CH2—O—(CH2CH2O)a—(CH2CH(CH3)O)b—(CH2CH2O)c—R1

14. wherein:

15. a, b and c are integers each independently ranging from 0 to 20;

16. R1 is selected from the group consisting of; 1

17. The compounds are made by the reaction of allyl alcohol alkoxylates, which are commercially available with succinic anhydride, maleic anhydride and phthalic anhydride. 2

18. wherein R1 is —C(O)—CH2—CH2—C(O)—OH.

19. The same reaction is conducted with maleic anhydride and phthalic anhydride to give the other compounds. 3

20. wherein R1 is —C(O)—CH2═CH2—C(O)—OH. 45

21. These allyl alkoxy carboxylates are key materials to synthesise the carboxy polymers that are used to make the ultimate complex. The carboxy polymers conform to the following structure; 6

22. wherein;

23. R2 is CH2CH2—CH2—O—(CH2CH2O)a—(CH2CH(CH3)O)b—(CH2CH2O)c—R1

24. e is an integer from 10 to 2,000.

25. The compounds of the current invention are prepared by the free radical reaction of the allyl alkoxy carboxylate containing monomer.

COMPLEX

26. The complex compound of the present invention conform to the following structure; 7

27. wherein;

28. R2 is CH2CH2—CH2—O—(CH2CH2O)a—(CH2CH(CH3)O)b—(CH2CH2O)c—R3

29. R3 is selected from the group consisting of; 8

30. and 9

31. e is an integer from 10 to 2,000.

PREFERRED EMBODIMENTS

32. In a preferred embodiment of the allyl alkoxy carboxylate R1 is —C(O)—CH2—CH2—C(O)—OH.

33. In a preferred embodiment of the allyl alkoxy carboxylate R1 is —C(O)—CH═CH—C(O)—OH.

34. In a preferred embodiment of the allyl alkoxy carboxylate 10

35. In a preferred embodiment of the allyl alkoxy carboxylate x, y, and z are each 0.

36. In a preferred embodiment of the allyl alkoxy carboxylate x ranges from 7 to 15 y is 0 and z is 0.

37. In a preferred embodiment of the carboxy polymer R1 is —C(O)—CH2—CH2—C(O)—OH.

38. In a preferred embodiment of the carboxy polymer R1 is —C(O)—CH═CH—C(O)—OH.

39. In a preferred embodiment of the carboxy polymer 11

40. In a preferred embodiment of the carboxy polymer x, y, and z are each 0.

41. In a preferred embodiment of the carboxy polymer x ranges from 7 to 15 y is 0 and z is 0.

42. In a preferred embodiment of the complex R3 is 12

43. In a preferred embodiment of the complex R3 is 13

44. In a preferred embodiment of the complex R3 is 14

45. In a preferred embodiment of the complex R4 is CH3.

46. In a preferred embodiment of the complex R4 is CH3.

EXAMPLES

47.

Raw Materials
These compounds conform to the following structure:
CH2═CH—CH2—O—(CH2CH2—O)x—(CH2CH(CH3)CH2—O)y—(CH2CH2—O)z—H
	Example Number	x	y	z
	1	0	0	0
	2	0	1	0
	3	4	0	0
	4	7	0	0
	5	10	0	0
	6	20	0	0
	7	4	7	10
	8	7	4	20
	9	10	20	4
	10	20	10	7
	11	20	20	20
	12	7	7	7

48. These materials are items of commerce available commercially from Siltech Corporation Toronto Ontario Canada, and Pelron Corporation Chicago Ill.

Preparation of Allyl Alkoxy Carboxylates

49. General Procedure

50. Carboxy allyl alkoxylates are prepared by the reaction of the allyl alcohol alkoxylates example 1-12 with one mole of anhydride. The reaction mass is heated to 80 to 100° C. and the theoretical amount of water is stripped off.

Succinic Anhydride Examples

51. To 103.0 grams of succinic anhydride is added to a clean glass vessel equipped with agitation and a thermometer. Next, the specified amount of the specified allyl alkoxylate Examples 1-12 is added. The reaction mass is heated to 80 to 100 C. and the theoretical amount of water distills off. The allyl carboxylic ester is used without additional purification.

Examples 13-32

52.

		Allyl Alkoxylate
		Grams	Example Number
	Example 13	58.0	1
	Example 14	102.0	2
	Example 15	234.0	3
		Allyl alkoxylate	Allyl alkoxylate
		Grams	Example Number
	Example 16	366.0	4
	Example 17	498.0	5
	Example 18	938.0	6
	Example 19	1087.0	7
	Example 20	1718.0	8
	Example 21	1912.1	9
	Example 22	1836.2	10
	Example 23	2998.3	11
	Example 24	1087.0	12

Maleic Anhydride Examples

53. To 101.0 grams of maleic anhydride is added to a clean glass vessel equipped with agitation and a thermometer. Next, the specified amount of the specified intermediate Examples 1-12 is added. The reaction mass is heated to 80 to 100 C. and the theoretical amount of water distills off. The allyl carboxylic ester is used without additional purification.

Examples 25-36

54.

	Allyl Alkoxylate	Allyl Alkoxylate
	Grams	Example Number
	Example 25	58.0	1
	Example 26	102.0	2
	Example 27	234.0	3
	Example 28	366.0	4
	Example 29	498.0	5
	Example 30	938.0	6
	Example 31	1087.0	7
	Example 32	1718.0	8
	Example 33	1912.1	9
	Example 34	1836.2	10
	Example 35	2998.3	11
	Example 36	1087.0	12

Examples 37-48

Phthalic Anhydride Examples

55. To 146.0 grams of phthalic anhydride is added to a clean glass vessel equipped with agitation and a thermometer. Next, the specified amount of the specified intermediate Examples 1-12 is added. The reaction mass is heated to 80 to 100 C. and the theoretical amount of water distills off. The allyl carboxylic ester is used without additional purification.

	Allyl alkoxylate	Allyl alkoxylate
	Grams	Example Number
	Example 37	58.0	1
	Example 38	102.0	2
	Example 39	234.0	3
	Example 40	366.0	4
	Example 41	498.0	5
	Example 42	938.0	6
	Example 43	1087.0	7
	Example 44	1718.0	8
	Example 45	1912.1	9
	Example 46	1836.2	10
	Example 47	2998.3	11
	Example 48	1087.0	12

Preparation of Carboxy Polymers

Examples 49-84

56. General Polymerization Procedure

57. The polymerization of the allyl carboxy compound is achieved by utilizing free radical catalyst in a low oxygen containing solvent, most commonly water. The water is deionized and sparged with nitrogen to remove dissolved oxygen contained therein immediately prior to use. Then, the specified amount of the treated de-ionized water is added to a suitable glass vessel. Most commonly, 50 to 80% of the total weight of the batch is water. The specified amount of the specified monomers are then added under agitation. Nitrogen is continuously sparged and the temperature is raised to about 50 C. Once the temperature has reached 50 and the nitrogen has been bubbled through the reaction mass for thirty minutes, a free radical initiator is added. Many peracids, like t-butyl-perbenzoate, t-butyl-hydroperoxide and inorganic free radical initiators like stannic chloride can be used. The preferred initiator is azobisisobutylnitrile. The reaction is exothermic and cooling is used to keep the temperature below 90 C.

58. The molecular weight is monitored by viscosity and both increase as the reaction continues.

Example 49

59. To the 5,000 grams of deionized water, which has just been spargred with nitrogen for 30 minutes, is added the specified amount 5,000 grams of the specified allyl carboxy monomer Ex # 13 under good agitation and nitrogen sparge. The temperature is raised to about 50 C. Once the temperature has reached 50 and the nitrogen has been bubbled through the reaction mass for thirty minutes, 0.05% by weight of batch of azobisisobutylnitrile. The catalyst may be optimally added in smaller increments of one quarter of the total needed waiting 30 minutes between additions. The viscosity will raise as the polymerization occurs. The temperature raises to about 90 C. and is cooled with cooling water as needed to prevent the temperature from reaching 90 C. The molecular weight is controlled by viscosity. When the desired visocity is achieved, air is bubbled through the vessel to quench the polymer. The desired polymer is used as prepared.

Examples 50-84

60. Example 49 is repeated only substituting the allyl carboxy monomer for example 13 used in example 49.

		Final Viscosity
Example	Allyl Carboxy Example	(centipose)
50	14	100
51	15	500
52	16	1000
53	17	2000
54	18	500
55	19	700
56	20	1200
57	21	5000
58	22	500
59	23	50
60	24	1250
61	25	1375
62	26	5000
63	27	8250
64	28	1000
65	29	500
66	30	800
67	31	2500
68	32	5000
69	33	7000
70	34	9000
71	35	100
72	36	500
73	37	900
74	38	1250
75	39	1450
76	40	780
77	41	6000
78	42	8000
79	43	7500
80	44	1500
81	45	280
82	46	1350
83	47	4000
84	48	1000

Polymeric Complexes

61. Cationic Component

Stearalkonium Chloride

62. Stearalkonium Chloride is an item of commerce available from a variety of sources. One such source is Henkel Corporation in Hoboken N.J..

63. Stearylalkonium chloride is also known as n,n-dimethyl, n-stearyl, n benzyl ammonium chloride and conforms to the following structure: 15

64. Stearyl trimethyl ammonium chloride

65. Stearyl trimethyl ammonium chloride is an item of commerce available from a variety of sources. One such source is Henkel Corporation in Hoboken N.J..

66. Stearyl trimethyl ammonium chloride is also known as n,n, n-trimethyl,n-stearyl ammonium chloride and conforms to the following structure: 16

Preparation of Complex

Example 85

67. The polymers of the present invention (examples 51-84) are typically prepared solutions ranging in concentrations of between 10 and 55% solids. The examples given use a 50% solid product.

68. To 410.0 grams of the 50% solution of polymer example 50 is added 500 grams of water. The resulting solution is heated to 80 C. In a separate container the quaternary compound is heated to 80 C. The molten quat is added to the hot polymer solution under good agitation. The pH is adjusted to 7.0 using NaOH 50%. The result is a clear homogenous complex of quaternary and carboxy polymer.

Examples 86-119

69. Example 85 is repeated, only this time the specified number of grams of the specified polymer example replaces the polymer used in example 85. 500 grams of water is added. The resulting solution is heated to 80 C. In a separate container the quaternary compound is heated to 80 C. The molten quat is added to the hot polymer solution under good agitation. The pH is adjusted to 7.0 using NaOH 50%. The result is a clear homogenous complex of quaternary and carboxy polymer.

Example	Grams	Example	type	Grams
86	674.0	51	stearalkonium	424.0
			chloride
87	572.0	52	stearalkonium	424.0
			chloride
88	704.0	53	stearalkonium	424.0
			chloride
89	2082.0	54	stearalkonium	424.0
			chloride
90	1293.0	55	stearalkonium	424.0
			chloride
91	3642.0	56	stearalkonium	424.0
			chloride
92	2118.0	57	stearalkonium	424.0
			chloride
93	3878.0	58	stearalkonium	424.0
			chloride
94	6202.6	59	stearalkonium	424.0
			chloride
95	2380.0	60	stearalkonium	424.0
			chloride
96	318.0	61	stearalkonium	424.0
			chloride
97	406.0	62	stearalkonium	424.0
			chloride
98	670.0	63	stearalkonium	424.0
			chloride
99	934.0	64	stearalkonium	424.0
			chloride
100	1198.0	65	stearalkonium	424.0
			chloride
101	2978.0	66	stearalkonium	424.0
			chloride
102	2376.0	67	stearyltrimethyl	348.0
			ammonium chloride
103	1920.0	68	stearyltrimethyl	348.0
			ammonium chloride
104	4026.0	69	stearyltrimethyl	348.0
			ammonium chloride
105	3874.0	70	stearyltrimethyl	348.0
			ammonium chloride
106	6198.0	71	stearyltrimethyl	348.0
			ammonium chloride
107	2466.0	72	stearyltrimethyl	348.0
			ammonium chloride
108	408.0	73	stearyltrimethyl	348.0
			ammonium chloride
109	496.0	74	stearyltrimethyl	348.0
			ammonium chloride
110	760.0	75	stearyltrimethyl	348.0
			ammonium chloride
111	1024.0	76	stearyltrimethyl	348.0
			ammonium chloride
112	1288.0	77	stearyltrimethyl	348.0
			ammonium chloride
113	2168.0	78	stearyltrimethyl	348.0
			ammonium chloride
114	2466.0	79	stearyltrimethyl	348.0
			ammonium chloride
115	3728.0	80	stearyltrimethyl	348.0
			ammonium chloride
116	4116.0	81	stearyltrimethyl	348.0
			ammonium chloride
117	3965.0	82	stearyltrimethyl	348.0
			ammonium chloride
118	3144.3	83	stearyltrimethyl	348.0
			ammonium chloride
119	1233.0	84	stearyltrimethyl	348.0
			ammonium chloride

Applications Examples

70. The polymers of the present invention are very substantive conditioners to the hair and are surprisingly mild to the skin and eyes. Eye irritation is a major concern in the formulation of personal care products, particularly when working with quats. Primary eye irritation was tested using the protocol outlined in FHSLA 16 CFR 1500.42. The products were tested at 25% actives. The results were as follows:

	Compound	Score	Description
	Stearyl trimethyl	106.0	Severely Irritating
	ammonium chloride
	Example 102	8.3	Minimally Irritating
	Example 115	6.2	Minimally Irritating
	Stearalkonium Chloride	116.5	Severely Irritating
	Example 87	11.3	Minimally
			Irritating
	Example 89	6.0	Minimally
			Irritating

71. As the data clearly shows, the irritation potential of the complex is dramatically reduced, when compared to the starting quat.

Claims

1. A complex conforming to the following structure: 17

2. A complex of claim 1 wherein R3 is 19

3. A complex of claim 1 wherein R3 is 20

4. A complex of claim 1 wherein R3 is 21

5. A complex of claim 2 wherein R4 is CH3.

6. A complex of claim 3 wherein R4 is CH3.

7. A complex of claim 4 wherein R4 is CH3.

8. A complex of claim 1 wherein R4 is 22