Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
2000-07-20
2001-07-03
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
Reexamination Certificate
active
06255438
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to phenolic compounds and polymers derived therefrom. The invention also relates to methods for making phenolic compounds and polymers derived therefrom.
Phenolic compounds are used in the synthesis of a wide variety of chemical products, particularly in the production of plastics and other bulk specialty products. Phenolic compounds bearing at least two reactive functional groups, at least one of which is a phenolic moiety, are commonly used to prepare polymers, particularly condensation polymers. One example is the polymerization of bis(phenols) with phosgene to prepare polycarbonates. In some cases mixtures of monomers, each bearing at least two nucleophilic groups, are used in a polymerization process with a separate monomer bearing two electrophilic groups to tailor properties of the resulting polymer. An example is the preparation of a polyestercarbonate through reaction of phosgene with a mixture of a “hard-block” monomer such as bisphenol-A and a “soft-block” monomer such as an aliphatic alpha-omega dicarboxylic acid, for example dodecanedioic acid. Such polyestercarbonates (for example, LEXAN of General Electric Plastics) typically retain the high impact strength which is the hallmark of polycarbonate resin while offering superior melt and flow characteristics relative to the corresponding polycarbonate made without soft-block monomer.
Soft-block monomers such as aliphatic alpha-omega dicarboxylic acids are typically produced by conversion processes based upon the use of non-renewable petrochemical feedstock. These multi-step chemical conversion processes typically produce unwanted hazardous byproducts which result in yield losses and must be destroyed before they are released to the environment. Disposal of a hazardous waste stream greatly adds to the cost of production. In addition, the organic chemical synthesis of long-chain diacids is limited by the starting materials used, and each chemical synthesis process can produce only one species of diacid. Soft-block monomers such as aliphatic alpha-omega dicarboxylic acids may also be prepared by biological fermentation as described in U.S. Pat. No. 6,066,480. However, fermentation processes often have less than optimum productivity and space-volume rates for economic production.
New types of phenolic compounds which may serve, for example, as monomers in condensation polymerization processes are constantly being sought. In particular, new types of phenolic compounds are needed which bear at least two functional groups, at least one of which is a phenolic moiety, which can serve as soft-block monomers in condensation polymerization. Also, new methods for the production of phenolic compounds are needed which have economic advantage over more commonly known methods such as synthesis from smaller hydrocarbon fragments.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed in one of its aspects to phenolic compounds which may be derived from naturally occurring essential oils such as citronella oil. Such oils are generally inexpensive and non-toxic, and have the advantage of being renewable resources. Thus, in one of its aspects the present invention is directed to phenolic compounds bearing at least two functional groups, at least one of which is a phenolic moiety. In this aspect the invention comprises phenolic compounds of the formula I:
wherein R
1
and R
2
independently at each occurrence represent alkyl or aralkyl; the free valence bond linking the aryl ring to the alpha-carbon atom independently at each occurrence is either ortho or para to the phenolic group; R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, and R
10
independently at each occurrence represent hydrogen, alkyl or aralkyl; R
11
independently at each occurrence represents alkyl or halogen; n independently at each occurrence is 0-3; x, y, and z independently at each occurrence are 0-4, wherein the sum of each x+y+z grouping is at least 1;
and either k is one and G represents CH
2
OH, CHO, CO
2
H, COCl, CO
2
R
12
, CO
2
M or
wherein R
12
is alkyl, aralkyl, alkaryl, or aryl; M is a cation; R
11
and n are as previously defined. and the free valence bond in formula II is either ortho or para to the phenolic group;
or k is two and G represents a linking moiety, wherein the linking moiety is either a carbonate linkage as in formula III:
a mono-ether linkage CH
2
]
2
O as in formula IV:
a di-ether linkage CH
2
O]
2
R
13
as in formula V:
a mono-ester linkage (C═O)OCH
2
as in formula VI:
a di-ester linkage (C═O)O]
2
R
14
as in formula VII:
or a di-ester linkage CH
2
O(C═O)]
2
R
15
as in formula VIII:
wherein R
13
, R
14
, and R
15
are alkyl, aralkyl, alkaryl, or aryl.
In another embodiment the present invention comprises a method for making phenolic compounds which comprises combining in the presence of an acidic material
A) a precursor compound of the formula IX:
wherein R
1
and R
2
independently at each occurrence represent alkyl or aralkyl; R
3
, R
5
, R
6
, R
7
, R
8
, R
9
, and R
10
independently at each occurrence represent hydrogen, alkyl, or aralkyl; x, y, and z independently at each occurrence are 0-4, wherein the sum of each x+y+z grouping is at least 1;
and either k is one and Q is CH
2
Br, CH
2
Cl, CH
2
OH, CHO, CO
2
H, COCl, CO
2
R
12
, CO
2
M, R
16
C═CR
17
R
18
, or
wherein the free valence bond linking the aryl ring to the alpha-carbon atom is either ortho or para to the phenolic group; R
11
independently at each occurrence represents alkyl or halogen; n is 0-3; R
12
is alkyl, aralkyl, alkaryl, or aryl; M is a cation; and R
16
, R
17
, and R
18
are each independently hydrogen, alkyl, or aralkyl;
or k is two and Q represents a linking moiety, wherein the linking moiety is either
vii) a carbonate linkage CH
2
O]
2
(C═O) as in formula X:
viii) a mono-ether linkage CH
2
]
2
O as in formula XI:
ix) a di-ether linkage CH
2
O]
2
R
13
as in formula XII:
x) a mono-ester linkage (C═O)OCH
2
as in formula XIII:
xi) a di-ester linkage (C═O)O]
2
R
14
as in formula XIV:
xii) a di-ester linkage CH
2
O(C═O)]
2
R
15
as in formula XV:
wherein R
13
, R
14
, and R
15
are alkyl, aralkyl, alkaryl, or aryl; and
B) a phenolic reactant of formula XVI containing at least one unsubstituted ortho or para position
wherein R
11
independently at each occurrence represents alkyl or halogen; and n is0-3.
In other embodiments the present invention comprises polymers made from the phenolic compounds of formula I and methods for making the polymers.
DETAILED DESCRIPTION OF THE INVENTION
The terms “radicals”, “groups”, and “moieties” are often used interchangeably hereinafter. Within the context of the present invention the term “alkyl” is intended to designate both normal alkyl, branched alkyl, and cycloalkyl radicals. Normal and branched alkyl radicals are preferably those comprising from 1 to about 22 carbon atoms, and include as illustrative non-limiting examples methyl, ethyl, propyl, isopropyl, butyl, tertiary-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, isooctyl, and nonyl. Cycloalkyl radicals represented are preferably those comprising from 3 to about 12 ring carbon atoms. Some illustrative non-limiting examples of these cycloalkyl radicals include cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl, and bicycloalkyl radicals such as [2.2.1]bicycloheptyl. Aralkyl radicals comprise aryl-substituted alkyl radicals comprising from 7 to about 22 carbon atoms; these include, but are not limited to, benzyl, phenylbutyl, phenylpropyl, and phenylethyl. Alkaryl radicals comprise alkyl-substituted aryl radicals comprising from 7 to about 24 carbon atoms; these include, but are not limited to, tolyl, xylyl, ethylphenyl, propylphenyl, and nonylphenyl. Aryl radicals comprise aromatic radicals with about 6-12 ring carbon atoms; these include, but are not limited to, phenyl, naphthyl, and biphenyl. Halogen radicals used in the various embodiments of the prese
Davis Gary Charles
Snowden Anthony Carroll
Whitney John Morgan
Boykin Terressa M.
Brown S. Bruce
General Electric Company
Johnson Noreen C.
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