Polymerized modified particles and methods of making the same

Details Polymerized modified particles and methods of making the same Polymerized modified particles and methods of making the same

2000-05-04

2002-04-16

Yoon, Tae H. (Department: 1714)

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

Synthetic resins

Processes of preparing a desired or intentional composition...

C523S202000, C523S205000, C524S495000, C524S570000, C524S571000, C524S575000, C524S575500, C106S031130, C106S031600, C152S151000

Reexamination Certificate

active

06372820

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to particles, such as carbon black, having an attached or associated metal or metal containing group which permits the formation of polymer on the particle. The present invention further relates to methods of preparing and using such modified particles.
The role of carbon black as a thermal stabilizer in polymeric systems is discussed by W. L. Hawkins, R. H. Hansen, W. Matreyek, F. H. Winslow;
J. Applied Polymer Science
, vol. 1, pages 37-42, 1959; J. T. Cruver, K. W. Rollmann:
J. Applied Polymer Science
, vol. 8, pages 1169-83, 1964, and by G. Ivan, M. Giurgina:
Revue Roumaine de Chemie
, vol. 29, number 8, pages 639-646, 1984. In each discussion the mechanism is through phenolic and quinone oxygen groups on the carbon black surface behaving either as radical traps or peroxide decomposers. One skilled in the art, however, would consider these sites unavailable as initiating sites for polymerization processes.
Belmont et al. (J. A. Belmont, J. M. Funt: International Rubber Conference, Essen, Germany, Jun. 24-27, 1991) identified the presence of peroxide groups, typically in the range of 0.1 to 0.4 micromoles/sq meter, on the carbon black surface. However, the majority (greater than 80%) of the peroxide groups are thermally stable to heat treatment at 200° C. and hence cannot be considered to be potential initiating sites for radical polymerization.
Tsubokawa et al. (K. Fujiki, N. Tsubokawa, Y. Sone:
Polymer J.
, vol. 22, number 8; pages 661-70, 1990, and N. Tsubokawa:
Prog. Polymer Science
, vol. 17, pages 417-70, 1992) discuss growing polymers from an activated carbon black surface by first attaching a reactive group via the oxygen groups on the carbon black surface. Typical examples include the use of glycidyl methacrylate where the glycidyl group reacts with phenolic hydroxyl groups on the carbon black surface providing a vinyl functionality; the reaction of 4,4′ azo bis-(4-cyanovaleric acid) whereby the acid group reacts with phenolic hydroxyl groups and subsequent heating decomposes the azo group to generate an alkyl radical; and the reaction of the phenolic hydroxyl groups with butyl lithium which can then be used as an initiation site for anionic polymerization.
All of these approaches require the presence of oxygen groups on the carbon black surface. Since the level of reactive hydroxyl and carboxylic acid groups, relative to the above approaches, present on a typical furnace or thermal carbon black is typically 0.01 to 0.1 micromoles/sq meter, the number of potential initiation sites is quite low.
Further, subsequent polymerization from these activated sites will most likely occur in the normal manner for free radical polymerization with the chains being irreversibly terminated by chain combination reactions, combination with unreacted oxygen groups on the carbon black surface, and/or the addition of chain stoppers. In all cases the polymerization cannot be reinitiated. Accordingly, there is a need to provide particles with attached stable free radicals which overcome the above-described limitations.
SUMMARY OF THE INVENTION
In accordance with the purposes of the present invention, the present invention relates to a modified particle which includes a particle having an attached group having the formula:
—A—R
1
—X
+
—M
−
  (I)
or
—A—R
1
—X
−
—M
+
  (II),
or
—A—R
1
—X—M  (III)
wherein A represents an aromatic group or an alkyl group and preferably includes at least one functional group on the aromatic or alkyl group; R
1
represents a bond, an arylene group, an alkylene group,
wherein R
4
is an alkyl or alkylene group or an aryl or arylene group; M represents a metal or metal containing group; and X represents a polymer formed from at least one polymerizable vinyl or diene containing monomer.
The present invention further relates to a modified particle or aggregate wherein the particle or aggregate is a carbon-metal containing species multiphase aggregate, a carbon-silicon containing species multiphase aggregate, a metal oxide, or a metal hydroxide. Attached to the particle or aggregate is a group having the formula:
—CoupA—[A—X
+
—M
−
]
n
  (IV)
or
—CoupA—[A—X
−
—M
+
]
n
  (V),
or
—CoupA—[A—X—M]
n
  (VI)
wherein CoupA represents a Si-containing group, a Ti-containing group, a Cr-containing group, or a Zr-containing group; A is defined above; M is defined above; X is defined above; and n is an integer of from 1 to 3.
The present invention further relates to a modified particle having an attached group of the formula:
—A—R
1
—X—CH═CH2→(M)(L)
x
  (VII),
wherein A, R
1
, and M are defined above, and L represents a neutral ligand group and x represents the number of coordination sites of M and is at least 1. L can be of the same or different when x is greater than 1. The arrow in the formula represents the association or chelation of the metal or metal containing group (with or without the ligand) on the vinyl or diene containing group.
The present invention also relates to another modified particle having an attached polymer. The particle is a carbon-metal containing species multiphase aggregate, a carbon-silicon containing species multiphase aggregate, a metal oxide, or a metal hydroxide. Attached to the particle is a group having the formula:
—CoupA—[R
1
—X—CH═CH
2
→(M)(L)
x
]
n
  (VIII),
wherein CoupA, R
1
, X, M, L, x, and the arrow (→) are defined above, and n is an integer of from 1 to 3.
The present invention, in addition, relates to a method for preparing and using these various modified particles. The method can include reacting a particle having an attached alkyl and/or aromatic group with an ionic or non-ionic metal containing group which is capable of polymerizing one or more types of monomer units which have one or more vinyl containing groups to form a reaction product, like particles having groups represented by formulas (I)-(VI). The particle having an attached alkyl and/or aromatic group will generally have a functional group as well in order to react with the metal or metal containing group. The reaction product can then be subsequently modified, such as by modifying the polymer and/or removing the metal or metal containing group.
Another method of making a modified particle can involve modifying a particle having attached a group having the formula:
—A—R
1
—M  (IX),
or
— — —CoupA— — —R
1
—M  (X)
wherein A; CoupA; R
1
; and M are defined above. M in these formulas can be non-ionic or ionic. When M is ionic in these formulas, though not shown, M would include an appropriate counter-ion. The method involves reacting a) a particle having attached an aromatic group or an alkyl group with a group containing a functional group capable of reaction with a metal or metal containing compound in such a manner that a covalent, ionic, or coordinate bond between the particle and metal or metal containing group is formed.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention, as claimed.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention relates to several modified particles which can be subsequently used in a polymerization to attach one or more polymers onto the modified particles. The modified particle prior to polymerization includes a modified particle which is a particle having attached a group having the formula:
—A—R
1
—M  (IX)
wherein A represents an aromatic group or an alkyl group which is attached to the particle; R
1
represents a bond, an arylene group, an alkylene group,
wherein R
4
is an alkyl or alkylene group or an aryl or arylene group; and M represents at least one metal or metal containing group. In this formula, M is anionic, cationic, or non-ionic. When M is ionic (e.g., cationic or ani

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