Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2002-10-23
2003-09-30
Dentz, Bernard (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C526S269000
Reexamination Certificate
active
06627762
ABSTRACT:
BACKGROUND OF THE INVENTION
(Meth)acrylate ester compounds having cyclic propylene carbonate groups are described in Decker, C., et al,
Makromol. Chem, Rapid Commun
, 11, 159-167 (1990); Decker, C., et al, Cpt. 2 of Vol. III “Radiation Curing in Polymer Science and Technology,” Fouassier et al, eds, Elsevier Applied Science, NY (1993); Jansen, et al, Polymer Preprints, 42(2), 769 (2001); U.S. Pat. No. 5,621,119; U.S. Pat. No. 6,001,535; European Patent No. EP 0 001 088; European Pat. No. EP 0 667 560; and International Patent Publication No. WO 02/42383. Such compounds have advantages in radiation curing compositions, for instance, for their high cure rates and improved hardness and flexibility properties.
A variety of different linking structures between the (meth)acrylate ester group and the cyclic propylene carbonate groups are described in the documents listed above. However, it has not previously been proposed to prepare such compounds with acetal or hemiacetal ester moieties in the linking structure.
SUMMARY OF THE INVENTION
The present invention is directed to novel acetal or hemiacetal ester linked propylene carbonate functional (meth)acrylic esters, and to methods for their synthesis.
The inventive compounds are characterized by the formula:
where
R
1
is H or methyl,
R
2
is H or alkyl,
each R
3
, independently, is a C
2
-C
4
alkylene,
n is 0-4,
n′ is 1-4,
x is one or more,
y is one or more,
x+y=z, and
A is a z-valent organic group linked to the group(s) on the left thereof through a carbon atom thereof and linked to the group(s) on the right thereof through an ether or ester oxygen atom, or, provided that x and y are both 1, is a direct bond.
The inventive compounds may be readily synthesized by reaction of certain alk-1-enyl alkylene cyclocarbonate ethers and known (meth)acrylic carboxylic acids or hydroxy functional (meth)acrylic esters. In addition to providing compounds having a single (meth)acrylate and a plurality of cyclic propylene carbonate groups, the method is readily adaptable to preparation of compounds having a each of these functionalities, but with one or the other, or both, being present in a plurality.
DETAILED DESCRIPTION OF THE INVENTION
All published documents, including all U.S. patent documents, mentioned anywhere in this application are hereby expressly incorporated herein by reference in their entirety. Any copending patent applications, mentioned anywhere in this application are also hereby expressly incorporated herein by reference in their entirety.
A. Monomer Compounds
Alk-1-enyl alkylene cyclocarbonate ethers of the formula:
where R
2
, R
3
, n and n′ are as previously defined, are known, for instance from WO 92/04383. Such alk-1-eneyl ethers may be reacted with (meth)acrylic carboxylic acids or hydroxy functional (meth)acrylic esters to produce the compounds of the invention.
In formula I above, the z-valent organic group A may be for instance an alkylene group, such as ethylene, propylene and butylene; a group of the formula —(R
3
O)
n″
—, where R
3
is as previously defined and n″ is as defined for n; an alkyleneacetyloxy group. The group A may also be a residue of any other partially (meth)acrylated polyol, for instance the glycerol residue of glyceryl monoacrylate or of glyceryl diacrylate.
Examples of suitable R
2
groups include H, and methyl, ethyl, n-propyl, isopropyl, butyl, cyclohexyl, hexyl, phenyl, octyl, 2-ethylhexyl, decyl, lauryl, cetyl and octadecyl. In some embodiments R
2
may be H or an alkyl group of 1-10 carbon atoms, especially H (i.e. a vinyl ether), or methyl (i.e. a propenyl ether).
Examples of R
3
groups include ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene and 1,2-butylene.
Specific useful ether compounds which may be employed in such synthesis reactions are prop-1-enyl propylene carbonate (PEPC), and the vinyloxyethyl ether of propylene carbonate.
Useful (meth)acrylic carboxylic acids which may be employed in such synthesis reactions include acrylic acid, methacrylic acid, B-carboxyethyl acrylate and B-carboxyethyl methacrylate.
Useful (meth)acrylic hydroxy esters which may be employed in such synthesis reactions are partially (meth)acrylated diols and polyols. Examples of such compounds include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl monomethacrylate, glyceryl monoacrylate, glyceryl dimethacrylate, glyceryl diacrylate, trimethylol propane monomethacrylate, trimethylol propane monomethacrylate, trimethylol diacrylate, trimethylol propane dimethacrylate; pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol mono(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol di(meth)acrylate, sorbitol mono(meth)acrylate, hydroxy functional saccharide (meth)acrylates, diethylene glycol mono(meth)acrylate, poly(ethylene glycol) mono(meth)acrylate, dipropylene glycol mono(meth)acrylate; poly(propylene glycol) mono(meth)acrylate, and the like.
The reaction of the alk-1-enyl alkylene cyclocarbonate ethers with the (meth)acrylic carboxylic acids and/or (meth)acrylic hydroxy esters is a simple thermally driven addition across the alk-1-enyl double bond. Addition of a hydroxyalkyl (meth)acrylate to a compound of formula II above, produces an acetal linked propylene carbonate functional (meth)acrylic ester, whereas addition of a (meth)acrylic acid compound produces a hemiacetal linked propylene carbonate functional (meth)acrylic ester. The addition reactions are run at elevated temperature, suitably a temperature range 20-120° C., preferably below 100° C. and above 50° C., and especially at about 70-90° C. for a time of 1-12 hours. Advantageously, the hydroxy ester or carboxylic acid is added to the compound of formula II incrementally. Typically a stabilizer is added to prevent premature polymerization. In certain cases it may be advantageous to employ an acidic catalyst such as para-toluene sulfonic acid or phosphoric acid to increase the reaction rates or to drive the reaction to completion.
In general, a suitable work-up procedure involves washing or treating the crude reaction mixture with sodium bicarbonate solution to remove residual acids (reagent and catalyst) if present, followed by washing with water to remove ionic impurities, drying with a suitable desiccant and filtering to remove insoluble particulate contaminants. In certain cases it may be desirable to vacuum strip the crude product and in some cases to distill or precipitate the monomers from blends of solvents and non-solvents. In other cases, chromatographic separation may be appropriate, particularly where isolation of highly purified material is required.
In an alternate synthesis, alk-1-enyl alkyleneepoxy ether compounds, for instance vinyl glycidyl ether or 1-propenyl glycidyl ether, may be first reacted with a hydroxyalkyl (meth)acrylate or a (meth)acrylic acid compound, to produce an acetal linked epoxy functional (meth)acrylic ester or a hemiacetal linked epoxy functional (meth)acrylic ester, respectively. Such products may then be reacted with carbon dioxide to form the desired propylene carbonate compound of the invention.
The inventive compounds are illustrated by the following:
Reaction product of propylene ether of propylene carbonate (PEPC) and acrylic acid:
Reaction product of vinyloxyethyl ether of propylene carbonate and acrylic acid
Reaction product of PEPC and &bgr;-carboxyethyl acrylate:
Reaction product of vinyloxyethyl ether of propylene carbonate and 2-hydroxyethyl acrylate:
Reaction product of PEPC and 2-hydroxyethyl acrylate:
Reaction product of PEPC and glycerol dimethacrylate:
Reaction product of PEPC and glycerol monomethacrylate:
and
Reaction product of 3-(2-vinyloxyethoxy)propylene-1,2-carbonate and acrylic acid:
The acetal-linked propylene carbonate functional (meth)acrylic ester compounds of the invention may be used as reactive diluents in conventional polymer-forming compositions based on free-radically polymeriza
Morrill Susanne D.
Woods John G.
Bauman Steven C.
Dentz Bernard
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