# Patent

## Title
(Meth)acrylate amide acetals

## Abstract

The present invention, in one aspect, is a composition comprising (meth)acrylate amide acetals. Acetals of the present invention are useful as components in coatings for automotive and architectural structures. Coatings comprising components of the present invention cure rapidly with low VOC emissions. In another aspect, the present invention provides a process for making (meth)acrylate amide acetals described herein.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application 60/615,362, filed Sep. 30, 2004.


FIELD OF THE INVENTION
The present invention relates to (meth)acrylate amide acetals which are readily prepared from the reaction of hydroxy amide acetals with methacryloyl chloride or via ester exchange reaction with methyl (meth)acrylate. This provides the monomers for eventual preparation of polymeric amide acetals.
BACKGROUND OF THE INVENTION
Amide acetals have been used for example in copolymerization with polyisocyanates as disclosed in U.S. Pat. No. 4,721,767. Cross-linked amide acetal based coating compositions dry and cure rapidly without the potential problems created by VOC emissions. Such coatings can be very useful, for example, in the automotive coatings industry.
Co-owned and co-pending US Patent Publication 2005-007461 describes polymeric compositions containing amide acetal groups, which are crosslinked by hydrolyzing the amide acetal groups, and subsequently reacting the hydroxyl groups and/or the amine functions that are formed to crosslink the composition.
Co-owned and co-pending U.S. patent application Ser. No. 10/960,656 describes a catalytic process for making amide acetals from nitriles and diethanolamines.
CA 132: 280540, an anonymous disclosure, alluded to the potential preparation of hydroxy amide acetals from epoxides and oxazolines but did not include how to make these, nor provide any experimental results.
SUMMARY OF THE INVENTION
The present invention relates to (meth)acrylate amide acetal compositions of the formula




wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino;

R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group;
R52 is hydrogen or methyl; and
n is 1-10.
It further relates to the process to form (meth)acrylate amide acetals, said process comprising reacting a hydroxy amide acetal of the formula




wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino;

R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and
n is 1-10;
with an ester of the formula

CH2═C(R)—C(O)—OR′

where R is hydrogen or methyl and R′ is C1-C20 alkyl.

The invention further relates to a process for forming a (meth)acrylate amide acetals, said process comprising reacting a hydroxy amide acetal of the formula




wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino;

R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and
n is 1-10;
with an acid halide, such as

CH2═C(R)—C(O)—X

where X is a halogen selected from the group consisting of Cl, and Br; R is hydrogen or methyl; said reaction performed in the presence of a base selected from the group consisting of triethylamine and pyridine.

The present invention further relates to a process for forming a (meth)acrylate amide acetal, said process comprising reacting a hydroxy amide acetal of the formula




wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino;

R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and
n is 1-10;
with an (meth)acrylic anhydride of the formula

CH2═C(R)—C(O)—O—C(O)—C(R)═CH2

where each R is independently methyl or ethyl, said reaction performed in the presence of a base selected from the group consisting of triethylamine and pyridine.

The present invention further relates to products formed by the disclosed processes.
DETAILS OF THE INVENTION
The present invention relates to a process for the preparation of (meth)acrylate amide acetals. Amide acetals have the general formula




General processes for producing amide acetals are disclosed in co-owned and co-pending U.S. Patent Publication 2005-007461 and U.S. patent application Ser. No. 10/960,656). As disclosed in these applications, amide acetals can also be represented by the formula





wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino; and R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and

where n is 1-10. It is more typical that R42-R49 each independently represent hydrogen and C1-C10 alkyl groups.

The amide acetal as shown above is used to produce (meth)acrylate amide acetals by any of several methods, including transesterification and reaction with an acid halide in the presence of a base. With transesterification, the amide acetal would react with an ester such as

CH2═C(R)—C(O)—OR′

where R is hydrogen or methyl and R′ is C1-C20 alkyl. Reaction with an acid halide, such as

CH2═C(R)—C(O)—X

or a (meth)acrylate anhydride

CH2═C(R)—C(O)—O—C(O)—C(R)═CH2

where each R is independently hydrogen or methyl and X is a halogen such as Cl or Br, in the presence of a base (e.g., triethylamine, pyridine) also gives the desired end-product. The formula for these (meth)acrylate amide acetals is





where R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and R52 is either hydrogen or methyl.

Generally, for the transesterification method, an excess of the methyl or ethyl (meth)acrylate is mixed with the hydroxy amide acetal together with a catalytic amount of a base, such as titanium (IV) butoxide. The reaction mixture is heated and the liberated methanol or ethanol is removed. Vacuum distillation affords the desired product.
Generally, for the acid halide or anhydride method, the hydroxy amide acetal and a base, such as pyridine or triethylamine, are mixed with an organic solvent such as tetrahyrofuran or dichloromethane. The resulting solution is cooled to 0° C. under nitrogen. The acid halide or (meth)acrylate anhydride is then slowly added. After completion of the reaction the salts are removed via filtration and vacuum distillation affords the desired material.
The materials made by the process described find use in a variety of end-uses, including but not limited to components in coatings for automotive and architectural structures.
These and other features and advantages of the present invention will be more readily understood, by those of ordinary skill in the art, from a reading of the following detailed description. It is to be appreciated those certain features of the invention, which are, for clarity, described above and below in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. In addition, references in the singular may also include the plural (for example, “a” and “an” may refer to one, or one or more) unless the context specifically states otherwise.
The use of numerical values in the various ranges specified in this application, unless expressly indicated otherwise, are stated as approximations as though the minimum and maximum values within the stated ranges were both preceded by the word “about.” In this manner slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Also, the disclosure of these ranges is intended as a continuous range including every value between the minimum and maximum values.
Unless otherwise stated, all chemicals and reagents were used as received from Aldrich Chemical Co., Milwaukee, Wis.


EXAMPLES
Example 1
2-Methyl-acrylic acid 5-(2,6-dimethyl-tetrahydro-oxazolo[2,3-b]oxazol-7a-yl)-pentyl ester




In an oven dried 100 mL round-bottom flask equipped with a pressure equalizing addition funnel and a reflux condenser were added 5-(2,6-Dimethyl-tetrahydro-oxazolo[2,3-b]oxazol-7a-yl)-pentan-1-ol (22.9 g, 0.01 mol) followed by chloroform 50 mL and triethylamine 12.12 g, 0.12 mol). The reaction content was cooled to 0° C. under nitrogen. While stirring a solution of methacryloyl chloride (11.44 g, 0.11 mol) in chloroform was added slowly. After completion of the acid chloride the reaction was stirred one hour at 0° C., then allowed to warmed to room temperature and then stirred over night at room temperature. The triethylamine salt was filter off through Celite® (World Minerals, Santa Barbara, Calif.), the filtrate concentrate at reduced pressure. NMR (proton) showed this material to be the desired material contaminated with triethyl amine salt. This material was then washed with hexanes (2×125 ml), the hexanes washes combined concentrated giving 13.74 g of product.
Example 2
2-Methyl-acrylic acid 2,6-dimethyl-tetrahydro-oxazolo[2,3-b]oxazol-7a-ylmethyl  ester




In an oven dried 300 mL round-bottom flask equipped with a reflux condenser were added 2,6-Dimethyl-tetrahydro-oxazolo[2,3-b]oxazol-7a-yl-methanol (789 g, 0.45 mol), methyl methacrylate (180.0 g, 1.80 mol), Prostab® 5415 (3.00 g, Ciba Specialty Chemicals, Basel, Switzerland) and titanium (iv) n-butoxide (6.00 g, 0.024 mol). The reaction content was heated to 110° C. for  ̃8 hours GC analyses indicated  ̃44% conversion. The reflux condenser was replaced with an oven dried distillation head and the distillate boiling between 60-70° C. collected. The distillation head was replaced with a reflux condenser and the reaction content heated to 120° C. for  ̃4 hours, at the end of which GC analyses indicated the conversion to be  ̃75%. Again the reflux condenser was replaced with a distillation head and the distillated boiling between 60-70° C. collected for  ̃8 hours, at the end of which GC analyses indicated the conversion to be  ̃90%. The reaction content was cooled to room temperature and the unreacted methyl methacrylate removed under vacuum and then the remaining reaction content vaccuum fractionally distilled affording four fractions:
















Head Temp
Pot Temp
Vacuum
Weight



Fraction
(° C.)
(° C.)
(torr)
(g)
Comments




















1
85
122
1.5




2
85-94
120
1.4


3
94-96
122
1.3
8.55
some product


4
 96-105
122-140
1.3-1.1
58.45
Almost all







product







(GC~92%)

## Claims

1. An (meth)acrylate amide acetal composition of the formula




wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino;
R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and
R52 is hydrogen or methyl; and
n is 1-10.

2. The (meth)acrylate amide acetal of claim 1, wherein R42-R49 each independently represent hydrogen and C1-C10 alkyl groups.

3. A process for forming a (meth)acrylate amide acetal, said process comprising reacting a hydroxy amide acetal of the formula




wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino;
R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and
n is 1-10;

with an ester of the formula


CH2═C(R)—C(O)—OR′


where R is hydrogen or methyl, and R′ is C1-C20 alkyl; in the presence of a catalytic amount of base.

4. The process of claim 3, wherein R42-R49 each independently represent hydrogen and C1-C10 alkyl groups.

5. A process for forming a (meth)acrylate amide acetal, said process comprising reacting a hydroxy amide acetal of the formula




wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino;
R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and
n is 1-10;

with an acid halide, such as


CH2═C(R)—C(O)—X


where X is a halogen selected from the group consisting of Cl and Br; R is hydrogen or methyl; said reaction performed in the presence of a base selected from the group consisting of triethylamine and pyridine.

6. The process of claim 5, wherein R42-R49 each independently represent hydrogen and C1-C10 alkyl groups.

7. A process for forming a (meth)acrylate amide acetal, said process comprising reacting a hydroxy amide acetal of the formula




wherein R42-R49 independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group, said alkyl, alkenyl, alkynyl, aryl, or aralkyl may each have one or more substituents selected from the groups consisting of halo, alkoxy, imino, and dialkylamino;
R41 is (CR50R51)n, wherein R50 and R51 are each independently represent a hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C2-C20 alkyl ester, or C7-C20 aralkyl group; and
n is 1-10;

with a (meth)acrylic anhydride of the formula


CH2═C(R)—C(O)—O—C(O)—C(R)═CH2


where each R is independently hydrogen or methyl, said reaction performed in the presence of a base selected from the group consisting of triethylamine and pyridine.

8. The process of claim 6, wherein R42-R49 each independently represent hydrogen and C1-C10 alkyl groups.

9. A product of the process of any of claims 3-8.