Polymerizable compounds and use thereof

Details Polymerizable compounds and use thereof Polymerizable compounds and use thereof

2001-03-29

2003-03-18

Seidleck, James J. (Department: 1711)

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

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S287000, C525S255000, C525S538000, C526S277000, C528S286000, C528S287000, C528S398000

Reexamination Certificate

active

06534597

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to polymerizable compounds, some of which are surfactants, and to uses thereof, e.g. as an emulsifier in emulsion polymerization, and to latices produced by emulsion polymerization utilizing the polymerizable compounds.
BACKGROUND OF THE INVENTION
The use of latices, produced by emulsion polymerization, in the production of paints or coatings for substrates is well know in the art. However, adhesion of such paints or coatings to the substrates is generally adversely affected by the presence of emulsifiers required in the emulsion polymerization process. For example, such emulsifiers affect adhesion and particularly wet adhesion in numerous ways. The emulsifiers tend to migrate to the surface during the drying process and collect at the interface of the paint or coating and the substrate forming a layer that is of greater sensitivity to moisture and reduces adhesion. Additionally, many such emulsifiers are generally incompatible with the other coating or paint components and tend to segregate, carry water and cause haze formation. It is therefore desirable that there be available polymerizable monomers that enable one to eliminate or decrease the amount of such emulsifiers required in the emulsion polymerization process.
SUMMARY OF THE INVENTION
This invention provides a process for the production of high monoester content polyalkylene oxide (meth)acrylate polymerizable phosphate esters, and processes to produce emulsion polymers of such polymerizable monomers and the resulting emulsion polymer products. The polymerizable polyalkylene oxide (meth)acrylate polymerizable phosphate esters produced by the process of this invention have a high mono/di-ester content, i.e., 80/20 or greater, and produce emulsion polymers of greatly improved properties compared to emulsion polymers produced from phosphate esters of lower mono/di-ester content.
The method comprises reacting exclusively a stoichiometrically effective amount of phosphoric anhydride with phosphoric acid to produce a phosphation reagent having an effective equivalent polyphosphoric acid weight percent of from about 118 to 125, and reacting the phosphonation reagent with an alcohol medium of the formula R
1
—C(O)—R
2
—O—H, wherein R
1
and R
2
are as defined herein after, to produce a resulting ester composition wherein in the resulting ester compositions, the mono-ester to di-ester weight ratio is greater than 80:20 and the weight percent of the residual of said alcohol and phosphoric acid are individually each less than 6%, and the polymerizable compounds in the ester composition have the formula
R
1
—C(O)—R
2
—OPO
3
H
2
wherein:
R
1
is an optionally substituted vinyl radical, preferably CH
2
═CH—, CH
2
═C(CH
3
)—, or cis-CH(COOH)═CH—, and
R
2
is a divalent polyoxyalkylene radical having at least two oxyalkylene units, preferably about 2 to about 50 oxyalkylene units, more typically about 2 to about 20 oxyalkylene units, e.g. (O—CH
2
CH
2
)
n
or (O—CH
2
CH(CH
3
))
n
wherein n is from about 2 to about 50.
The invention further comprises a method of making an emulsion polymer comprising copolymerizing by emulsion polymerization a polymerizable surfactant, or a salt thereof, having the formula:
R
1
—C(O)—R
2
—X
wherein:
R
1
is an optionally substituted vinyl radical, preferably CH
2
═CH—, CH
2
═C(CH
3
)—, or cis-CH(COOH)═CH—,
R
2
is a divalent polyoxyalkylene radical having at least two oxypropylene units, preferably about 2 to about 50 oxypropylene units, more typically about 2 to about 20 oxypropylene units, optional oxyethylene units in a block or random pattern, and a molar ratio oxypropylene units to oxyethylene units of at least about 2:1, preferably at least about 3:1, typically at least about 4:1 and more typically at least about 5:1, and
X is a phosphate —OPO
3
H
2
group, wherein in the ester the mono-phosphate ester to di-phosphate ester weight ratio is greater than 80:20
with at least one other polymerizable monomer.
DETAILED DESCRIPTION OF THE INVENTION
In one aspect, this invention relates to a method of making polymerizable phosphate ester compounds having the formula:
R
1
—C(O)—R
2
—OPO
3
H
2
wherein:
R
1
is an optionally substituted vinyl radical, preferably CH
2
═CH—, CH
2
═C(CH
3
)—, or cis-CH(COOH)═CH—, and
R
2
is a divalent polyoxyalkylene radical having at least two oxyalkylene units, preferably about 2 to about 50 oxyalkylene units, more typically about 2 to about 20 oxyalkylene units, e.g. (O—CH
2
CH
2
)
n
or (O—CH
2
CH(CH
3
))
n
wherein n is from about 2 to about 50, wherein in the ester the mono-phosphate ester to di-phosphate ester weight ratio is greater than 80:20.
The polyoxyalkylene unit can be derived from a variety of epoxyalkane compounds including ethylene oxide, propylene oxide, butylene oxide, styrene oxide, other alkyl, cycloalkyl or aryl substituted alkyl oxides or alkyl or aryl glycidyl ethers. It may additionally include hydrocarbon chain segments such as might be derived from ring opening of caprolactone by 2-hydroxyethyl methacrylate.
The method comprises the steps of:
a) preparing a slurry or paste reagent composition by intimately blending and exclusively reacting, at from about room temperature to about 80° C. or the ultimate phosphation reaction temperature, an effective amount of phosphoric anhydride with from about 75 weight percent to about 117 weight percent phosphoric acid, said reagent composition having an effective equivalent polyphosphoric acid weight percent of from about 118 to about 125; and
b) reacting said reagent composition with at least one alcohol of the formula R
1
—C(O)—R
2
—O—H, typically for a reaction time of from about 4 to about 12 hours;
wherein in the resulting ester compositions, the mono-ester to di-ester weight ratio is greater than 80:20 and the weight percent of the residual of said alcohol and phosphoric acid are individually each less than 6%.
In another aspect, this invention relates to a method of making polymerizable compounds having the formula:
R
1
—C(O)—R
2
—OPO
3
H
2
wherein:
R
1
is an optionally substituted vinyl radical, preferably CH
2
═CH—, CH
2
═C(CH
3
)—, or cis-CH(COOH)═CH—, and
R
2
is a divalent polyoxyalkylene radical having at least two oxyalkylene units, preferably about 2 to about 50 oxyalkylene units, more typically about 2 to about 20 oxyalkylene units, e.g. (O—CH
2
CH
2
)
n
or (O—CH
2
CH(CH
3
))
n
wherein n is from about 2 to about 50;
said method comprising the steps of:
A) preparing a phosphoric acid-alcohol reactant solution by
i) dissolving
a) from about 75 weight % to about 117 weight % phosphoric acid in
b) at least one alcohol medium of the formula R
1
—C(O)—R
2
—O—H, wherein R
1
and R
2
are as defined above, under essentially non-reactive temperature conditions;
B) then
ii) intimately blending a stoichiometrically effective amount of phosphoric anhydride into said reactant solution and
iii) reacting exclusively the phosphoric acid in said reactant solution with the stoichiometrically effective amount of phosphoric anhydride to produce in-situ a phosphation reagent having an effective equivalent polyphosphoric acid weight percent of from about 118 to 125; and
C) reacting the phosphation reagent so produced with the alcohol medium, typically at from about 75° C. to about 100° C. for a reaction time of from about 4 to about 12 hours,
wherein in the resulting ester compositions, the mono-ester to di-ester weight ratio is greater than 80:20 and the weight percent of the residual of said alcohol and phosphoric acid are individually each less than 6%.
Latices, water based dispersions of polymers obtained by emulsion polymerization, are widely used in various applications such as paints, adhesives, paper coatings, and carpet backing. Although some applications do not require it, the major property of the latex is its ability to bind various substrates. Thus, adhesion is a key factor, and one of the most difficult aspects is the wet adhesion. The latter is strongly affected by the presence of surfact

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