Ether compounds and process for producing the same

Details Ether compounds and process for producing the same Ether compounds and process for producing the same

1999-03-11

2001-03-20

Killos, Paul J. (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acid esters

C560S198000

Reexamination Certificate

active

06204410

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a novel compound having an ether group, which can be cured by radical polymerization and a process for producing the same.
BACKGROUND ART
Thermosetting resins and photocurable resins are used as coating materials, paint materials, optical materials and adhesive materials. Curable compositions exhibiting a high curing rate that contain an acrylic acid ester or methacrylic acid ester as a principal component are widely used as thermosetting resins from the viewpoint that the operation efficiency and productivity can be enhanced. In particular, a bifunctional or higher-functional acrylic acid ester or methacrylic acid ester is employed for increasing the polymerization degree of cured resin to thereby increase the hardness of the surface of the cured resin.
However, in the curing of such a polyfunctional acrylic acid ester by radical polymerization, the polymerization is inhibited by oxygen to thereby produce uncured portion with the result that the problem of remaining tack is caused. Moreover, many of the acrylic acid esters exhibit high skin stimulation, so that, also, the problem of toxicity is encountered.
Vinyl ether compounds are known as being a photocurable compound whose skin stimulation is low. The vinyl ether compounds are cured by cationic polymerization, so that they are less susceptible to the polymerization inhibition by oxygen. However, the catalysts for use in the cationic polymerization have such drawbacks that they are deactivated by moisture or bases, they are expensive and the number of varieties thereof is small to thereby limit the number of really available catalysts and many thereof are highly toxic. Further, the radical polymerization of only one kind (single) vinyl ether does not proceed, so that, for example, the method of copolymerizing a vinyl ether and an acrylic material (monomer) is employed for effecting the radical polymerization. However, in this copolymerization, the copolymerizability cannot always be stated as being excellent and, even if the copolymerization by radical polymerization is performed, the production of product with satisfactorily high practicability is limited.
Recently, the use of a propenyl ether as a cationic polymerization material is drawing attention. Crivello et al. reported in J. Macromol. Sci. Part A, A31(9), 1105 (1994) that propenyl ethers exhibited high cationic polymerizability. The propenyl ether compounds have skeletal structures derived from phenols such as bisphenol.
Further, U.S. Pat. No. 4,864,054 reported that an aromatic propenyl ether compound could be used in various applications through the cationic polymerization thereof. This aromatic propenyl ether compound is one having a skeletal structure derived from a phenol such as bisphenol A or hydroquinone or from an ester such as a terephthalic acid ester or an isophthalic acid ester.
However, when the radical polymerization is intended, the problem is encountered such that the radical polymerizability of this propenyl ether alone is as low as that of the above vinyl ether.
The radical polymerization method has advantages in that, as compared with other polymerization methods, the curing time is generally relatively short, the molecular weight can be large, a large variety of radical polymerization initiators are available and their use is easy. Therefore, the radical polymerization method is an industrially useful polymerization method. However, a compound having a propenyl ether group or an allyl ether group whose sole radical polymerization is practicable is little known.
(1) Canadian Patent Specification No. 575985 describes esters prepared from a saturated or an unsaturated polycarboxylic acid and a &bgr;-(2-propenoxy)alkanol of the formula RCH═CH—CH
2
—O—CH(R′)CH(R″)—OH or CH
2
═C(R)—CH
2
—O—CH(R′)CH(R″)—OH (wherein each of R, R′ and R″ is selected from among hydrogen and alkyls, the alkyls preferably being those which do not contain more than three carbon atoms, for example, methyl, ethyl or propyl).
Specifically, the specification discloses, as preferred esters, di-(&bgr;-propenoxyethyl) maleate, di(&bgr;-propenoxyethyl) fumarate (CH
2
═CH—CH
2
—O—(CH
2
)
2
—OCO—CH═CH—COO—(CH
2
)
2
—O—CH
2
—CH═CH
2
) and di-(&bgr;-propenoxyethyl) itaconate (CH
2
═CH—CH
2
—O—(CH
2
)
2
—OCO—CH(═CH
2
)CH
2
—COO—(CH
2
)
2
—O—CH
2
—CH═CH
2
). Further, the specification teaches that the copolymerization reaction of the above monomers is accelerated by the presence of a peroxide such as dibenzoyl peroxide or diacetyl peroxide.
However, the specification fails to present any specific description as to esters including an alkylene group having at least 3 carbon atoms or a cycloalkylene group having at least 5 carbon atoms in the moiety “CH(R′)—CH(R″)—” of the above formula.
(2) Japanese Patent Publication No. 55(1980)39533 discloses a process for producing an &ohgr;-vinyloxyalkyl carboxylate in which an unsaturated carboxylic acid and an &ohgr;-halogenoalkyl vinyl ether are condensed with each other.
(3) Further, Japanese Patent Laid-open Publication No. 57(1982)-165409 discloses a thermosetting composition containing a thermosetting catalyst, which comprises:
(A) an aromatic polyvinyl ether compound selected from among (i) polyvinyl compounds of the formula R[QR
1
OC(R
2
)═C(R
3
)
2
]
n
(wherein Q: —O—, —COO—, etc., R: polyvalent aromatic organic group, R
1
: alkylene group having 1 to 8 carbon atoms, each of R
2
and R
3
: H or alkyl group having 1 to 8 carbon atoms, and n: 2 to 10) and (ii) reaction product of the above polyvinyl compound with an active hydrogen compound selected from a specified group including polycarboxylic acids, phenols, etc., and
(B) (a) an aryl onium salt selected from a specified group and (b) an organic oxidant or an aromatic polyvinyl ether soluble copper compound.
(4) Still further, Japanese Patent No. 2,744,849 describes a process for producing a polyester having vinyl ether terminals, which comprises the steps of:
(a) reacting a polyol with a polybasic acid ester having vinyl ether terminals in the presence of a transesterification catalyst to thereby produce an oligomer of the polyol and the polybasic acid ester which has vinyl ether terminals and a by-product of hydroxymonovinyl ether, and
(b) separating the hydroxymonovinyl ether during the reaction of the step (a).
Compounds of the formula Y-[COOX]
m
(wherein Y: alkyl group, etc., X: alkyl having 1 to 6 carbon atoms, etc., and m is 2 to 6) in which Y may be —(CH
2
)
n
— are described as the above polybasic acid ester. The reaction of the formula:
XOCO—Y—COOX (i)+R′CH═CR″OZ-OH (ii)→
R′CH═CR″OZ—OCO—Y—COO—ZOR″C═HCR′(iii)+2XOH↑
(wherein each of R′ and R″: H or lower alkyl group having 1 to 10 carbon atoms and Z: alkylene group or cycloalkylene group) and the chain extension reaction between vinyl ether terminated ester (iii) and polyol (HO-A-OH) are described as examples of the vinyl ether terminal forming reactions of ester.
However, in the patent specification, there is no description regarding compounds wherein Y represents —CH═CH or —(CH
2
)—C(═CH
2
)—, and there is no description teaching or suggesting the radical polymerization of vinyl ether terminated ester (iii).
(5) Still further, claim
1
of Published Japanese Translation of PCT Patent Application No. 5(1993)-506838 describes an optical fiber coating composition comprising a product obtained by reacting together (a) a vinyl ether urethane oligomer composed of a product obtained by reacting together (i) a hydroxyl terminated polyester or hydroxyl terminated polyether, (ii) a diisocyanate or a polyisocyanate having at least two functional groups and (iii) a hydroxymonovinyl ether, (b) a vinyl ether terminated ester monomer and (c) a vinyl ether terminated monomer derived from a specified alcohol. A-(—COOZOCR
4
═CHR
3
)
n
(wherein n: 1 to 4, A: alkylene group, etc., Z: alkyl

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