Cyclic carbonates and their reactions with amines

Details Cyclic carbonates and their reactions with amines Cyclic carbonates and their reactions with amines

1999-12-13

2001-05-08

Gorr, Rachel (Department: 1711)

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

Synthetic resins

From reactant having a halogen atom or oxygen single bonded...

C544S383000, C546S245000, C548S351100, C560S132000, C560S157000

Reexamination Certificate

active

06228979

ABSTRACT:

FIELD OF THE INVENTION
Six-membered cyclic carbonates substituted with keto or carbohydro-carbyloxy groups in the 5 position are described. These cyclic carbonates are especially reactive with primary and cyclic secondary amines to form novel hydroxyurethanes which are useful as monomers and reactive diluents.
TECHNICAL BACKGROUND
Cyclic carbonates are known to react with amines, such as primary amines, to form hydroxytrethanes. However, these reactions tend to be relatively slow, so this reaction has not been employed much for commercial uses. If methods could be found to speed up such reactions, they would be more useful for commercial uses.
K. D. Weilandt, et al., Makromol. Chem. Phys., vol. 197, p. 3851-3856 (1996) report the preparation and polymerization (to a polycarbonate) of “2-methoxycarbonyl-2-methyltrimethylenecarbonate”. No mention is made of reaction with amines.
SUMMARY OF THE INVENTION
This invention concerns a process for the production of hydroxyurethanes by the reaction of a cyclic carbonate with a primary or cyclic secondary amine, wherein the improvement comprises, using as the cyclic carbonate a compound of the formula
wherein:
R
1
, R
2
, R
3
, R
4
and R
5
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
6
is hydrocarbyl, substituted hydrocarbyl or —OR
7
; and
R
7
is hydrocarbyl or substituted hydrocarbyl.
This invention also concerns a hydroxyurethane of the formula
wherein:
R
1
, R
2
, R
3
, R
4
and R
5
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
6
is hydrocarbyl, substituted hydrocarbyl or —OR
10
;
R
10
is hydrocarbyl or substituted hydrocarbyl;
m is 1,2,3or 4;
p is 1,2or 3;
R
7
is hydrocarbyl or substituted hydrocarbyl having m free valencies; and
R
8
and R
9
taken together from a ring, said ring having p free valences to secondary nitrogen atoms.
Also described herein is a compound of the formula
wherein:
R
1
, R
2
, R
3
, R
4
and R
5
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R
6
is hydrocarbyl, substituted hydrocarbyl or —OR
10
; and
R
10
is hydrocarbyl or substituted hydrocarbyl.
DETAILS OF THE INVENTION
The cyclic carbonates made and used herein are of the formula (I). Preferred cyclic carbonates have one or more of the following: R
1
, R
2
, R
3
and R
4
are hydrogen; and/or R
5
is alkyl containing 1 to 6 carbon atoms, more preferably methyl; and/or R
6
is alkyl containing 1 to 10 carbon atoms, more preferably methyl; and/or R
6
is —OR
10
wherein R
10
is hydrocarbyl, more preferably alkyl containing 1 to 10 carbon atoms, and especial preferably methyl.
In a another preferred form the group R
10
, which may be substituted hydrocarbyl, may contain one or more of the grouping
wherein all of these groups (and all others in this paragraph) are as defined above. In other words, such compounds contain 2 or more cyclic carbonate groups of the type described for (I), and are included within the definition of (I). Such compounds are useful as crosslinking agents for polymers which contain groups that may react with cyclic carbonates, such as primary amines (see below).
Compounds containing more than one such cyclic carbonate group may be made by the following route:
In Equations (1) and (3) a Bronsted acid is used as a catalyst, in Equation (2) a catalyst such as a tetraaloxytitanate can be used, and in Equation 4 a phosgene source, such as triphosgene is preferred. Compounds such as (XI) containing more than 2 cyclic carbonate groups may be made simply by using an appropriate polyol in place of HO(CH
2
)
z
OH, wherein z is an integer of 2 or more. It is preferred that R
10
contain 1, 2 or 3 of the groups (VII), more preferably 1 such group.
Herein hydrocarbyl means a univalent radical containing only carbon and hydrogen. If not otherwise specified it is preferred that a hydrocarbyl or substituted hydrocarbyl radical contain 1 to about 30 carbon atoms. By substituted hydrocarbyl is meant a hydrocarbyl radical containing one or more substituents (functional groups) that do not interfere with the desired reaction(s) or with the stability of the compound involved. Suitable substituents herein include ether, oxo (keto), ester, halogen, amide and carbamate.
The 6-membered cyclic carbonates described herein may be made by methods illustrated in the Examples, see for instance Examples 1 and 2. Similar cyclic carbonates containing other groups and/or substituents may be made by analogous methods.
These carbonates may be reacted with a primary amine or a secondary cyclic amine. By a primary amine herein is meant the usual meaning, a compound containing the —NH
2
group. It is preferred that this group be bound to an alkyl-type carbon atom, i.e., R
11
R
12
R
13
CNH
2
wherein R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl. In one preferred amine R
11
, R
12
and R
13
are each independently hydrogen or alkyl, and more preferably R
11
and R
12
are hydrogen and R
13
is alkyl or cycloalkyl. The primary amine may contain more than one —NH
2
group. When this occurs, and the amine fully reacts, a compound such as (II) and/or (III) may be produced in which m is 2, 3 or 4. In one preferred reaction the primary amine contains 2, 3 or 4, more preferably 2 primary amine groups, so that in (II) and (III) produced m will be 2, 3 or 4, or 2 respectively. When m is more than 1, the starting primary amine would have the formula R
7
(NH
2
)
m
, to give (II) and/or (III). Another preferred primary amine H
2
N(CH
2
)
q
NH
2
wherein q is 2 to about 12.
The amine may also be a cyclic secondary amine of the type
where the nitrogen is part of a ring. More than one secondary amine may be present in such a compound and the two amine nitrogen atoms need not be present in the same ring. The number of secondary cyclic amine groups present in the secondary cyclic amine corresponds to p in (IV) and (V) when the secondary cyclic amine is completely reacted. It is preferred that the secondary cyclic amine contain 2 or 3, more preferably 2, secondary cyclic amine groups. Thus it is also preferred in (IV) and (V) that p is 2 or 3, more preferably 2. Useful secondary cyclic amines include pyrrolidine, piperidene, and perhydropyrazine. Perhydropyraaine is a preferred secondary cyclic amine.
Amines containing both a primary amino group and a secondary cyclic amino group are also included within the definition of amines useful herein, and are considered primary amines and/or secondary cyclic amines.
It has surprisingly been found that the cyclic carbonates described herein react exceptionally rapidly with primary or secondary cyclic amines. This is an advantage in the preparation of hydroxyurethanes which can be made in less time and/or under milder conditions.
Temperature of the process is not critical, a preferred temperature range being about −20° C. to about 120° C., more preferably about 0° C. to about 60° C., and especially preferably about 10° C. to about 40° C. Ratios of reactants are not critical, but in order to most efficiently utilize the ingredients a molar ratio of about 1:1 for the cyclic carbonate and primary or secondary cyclic amine groups is preferred.
The reaction of cyclic carbonates with amines is a known reaction, see for instance British Patent 689,705, U.S. Pat. Nos. 3,072,613 and 4,882,391, and French Patent 1,096,204, all of which are hereby included by reference. In general all that is necessary for the reaction to occur is to bring the reactants into contact, as in solution, or if one or both of the amine and carbonate are liquids, without solvent for a period of time sufficient to carry out the reaction.
The hydroxyurethanes (II), (III), (IV) or (V), when m or p is 1 may be transesterified and polymerize to polyesters containing pendant urethane groups, which are useful for coatings. All of (II), (III), (IV) and (V) may be used in coating as reactive diluents, that is they may reduce the viscosity of a coating containing an already formed polymer, and then be incorporated into the coating solids by r

Affiliated with

Also associated with

Rating

Cyclic carbonates and their reactions with amines does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Cyclic carbonates and their reactions with amines, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Cyclic carbonates and their reactions with amines will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2525382