Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2002-01-15
2004-05-18
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S332000, C528S335000
Reexamination Certificate
active
06737500
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a method for making polvaspartic esters.
BACKGROUND OF THE INVENTION
Two-component coating compositions having a polyisocyanate component and an isocyanate-reactive component (a polyhydroxyl component) are known. These compositions are suitable for the preparation of high quality coatings that may be rendered rigid, elastic, resistant to abrasion and to solvents and, above, all, resistant to weathering. Polyaspartic esters have been used as isocyanate-reactive components in such two-component compositions. A polyaspartic ester can be used individually, with a polyisocyanate, or possibly in combination with polyols or polyamines. Alternatively, polyaspartic esters can be used with blocked polyamines such as ketimines, aldimines or oxizolidines.
Methods for making polyaspartic esters are known. It is known, for instance, that during the Michael Addition Reaction of an ester of fumaric or maleic acid and the primary amine, for instance, the ester of maleic or fumaric acid isomerizes to dialkyl fumarate in the presence of amines, according to the following chemical reaction:
The dialkyl fumarate is then converted to a polyaspartic ester. Mixtures of polyaspartic esters based on cyclic and acyclic amines have proven to be valuable isocyanate-reactive components of polyurea compositions that have found utility in the formulation of high solids coatings where solvent content is very low or zero. These formulations are used in architectural and automotive refinish applications. Known methods for preparing polyaspartic ester mixtures typically involve preparing polyaspartic esters based on acyclic and cyclic amines separately and then combining each polyaspartic ester mixture. Polyaspartic esters based on acyclic amines, which contain amines attached to primary carbons, generally react with an isocyanate faster than polyaspartic esters based on cyclic amines that have an amine group attached to a secondary ring carbon. In addition, polyaspartic esters based on acyclic amines have a lower viscosity than polyaspartic esters based on cyclic amines. It is often desirable to blend these types of amines to achieve formulations with different viscosities and with intermediate reaction speeds.
U.S. Pat. No. 5,236,741 and U.S. Pat. No. 5,623,045 each disclose a single step process for the production of polyaspartic esters. Each process reacts an ester of maleic or fumaric acid with a primary polyamine such that preferably one olefinic double bond is present for each primary amino group. The patents teach that excess starting materials is removed by distillation after the reaction. Neither patent discusses how much time it takes for the reaction of the ester of maleic or fumaric acid to complete, i.e., to obtain a yield of about 100% of the polyaspartic ester. Neither patent addresses the issue of developing a process that makes a 100% yield of a mixture of (1) a polyaspartic ester based on a cyclic amine and (2) a polyaspartic ester based on an acyclic amine in a matter of days.
Unfortunately, such methods have prevented manufacturers of polyaspartic esters from delivering shipments to customers as quickly as would be desired. I have discovered that by following the teachings of the above-described known methods and using a 1:1 stoichiometric ratio, it takes several months to obtain full, or near-full, conversion of the reaction of a cyclic amine and an ester of maleic or fumaric acid. For instance, the use of bis (4-aminocyclohexyl)methane requires the polyaspartic ester to be stored in excess of six weeks to achieve 95% reaction and from six to twelve months to achieve complete reaction; and the use of bis (3-methyl-4-aminocyclohexyl)methane [commercially known as Laromin C-260] requires the polyaspartic ester to be stored in excess of eight weeks to achieve 95% reaction and from twelve to eighteen months to achieve 100% reaction. Removing excess ester of maleic or fumaric acid, as suggested by U.S. Pat. Nos. 5,236,741 and 5,623,045, is a time-consuming expensive procedure.
The problem of long waiting times has not been able to be resolved by making large amounts of the mixtures in advance because it is extremely difficult to predict customers' needs for the mixtures. Further, expensive storage, and inventory costs have discouraged the making and the storing of large amounts of the mixtures. As such, it is not uncommon for a customer to have to wait several months to receive an order of mixtures of polyaspartic esters.
It would be advantageous to develop an improved method for making mixtures of polyaspartic esters based on cyclic amines and polyaspartic esters based on acyclic amines that overcomes the above-named disadvantages.
SUMMARY OF THE INVENTION
The invention relates to a method for making a polyaspartic ester mixture in-situ comprising the sequential steps of (a) reacting a cyclic amine with an excess amount of an ester of fumaric or maleic acid to form a mixture containing first polyaspartic ester component and excess unreacted ester of fumaric or maleic acid, and (b) adding an acyclic amine to the mixture resulting from step (a) and reacting the acyclic amine with the excess ester of fumaric or maleic acid to form a second polyaspartic ester component. The invention is also directed to the in-situ mixture of polyaspartic ester esters formed during the method, prior to termination of the process, that contains the first polyaspartic ester component and the second polyaspartic ester component. The method makes it possible for customers to receive mixtures of the polyaspartic esters in a fraction of the time it has ordinarily taken. These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.
DETAILED DESCRIPTION OF THE INVENTION
As used in this application, the term “cyclic amine” refers to an amine that has at least one primary amine group attached to a cyclic group, e.g., an amine attached to a secondary ring carbon. The term “acyclic amine” refers to an amine that does not have a primary amine group attached to a cyclic.
The invention is based on the discovery that mixtures of polyaspartic esters based on cyclic amines and polyaspartic esters based on acyclic amines can be prepared in-situ, (under certain conditions) in a fraction of the time it ordinarily takes to make them. It is critical that the cyclic amine first react with an excess ester of maleic or fumaric acid. As discussed below, if the sequence of the steps varies, e.g., if the steps are reversed or if the cyclic and acyclic amines are added simultaneously, the reaction proceeds substantially slower and is outside the scope of the present invention.
The first and second ester components are selected from esters of maleic acid and fumaric acid. Esters of maleic acid and fumaric acid include suitable dialkyl maleates or dialkyl fumarates. Suitable dialkyl maleates include, diethyl maleate, dipropyl maleate, dibutyl maleate, methyl propyl maleate, ethyl propyl maleate, and the like. Suitable dialkyl fumigates include, diethyl fumurate, dipropyl fumurate, dibutyl fumurate, methyl propyl fumurate, ethyl propyl fumurate, and the like. Generally, dimethyl maleate or dimethyl fumurate is not used in an appreciable amount because it has been discovered that these esters cause the precipitation of long needle-like crystals that no longer participate in the Michael Addition Reaction and that cause the reaction to stop altogether. It is believed that cinnamate esters do not react under the same reaction conditions as esters of maleic acid or fumaric acid.
The amine component is generally selected from difunctional or trifunctional cyclic and acyclic amines that can accomplish the objects of the invention. Suitable amines can be selected from the following. Suitable acyclic difunctional amines include but are not limited to ethylene diamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-dimethylhexane, 2,2,4- and/or 2,4,4-trimethyl-1,6-diaminoh
Bayer Polymers LLC
Gil Joseph C.
Matz Gary F.
Roy Thomas W.
Truong Duc
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