Salt sensitive aqueous emulsions

Details Salt sensitive aqueous emulsions Salt sensitive aqueous emulsions

2000-03-31

2004-01-27

Reddick, Judy M. (Department: 1713)

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

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C524S548000, C524S549000, C524S555000, C524S556000, C524S558000, C524S559000, C524S808000, C524S812000, C524S814000, C524S815000, C524S816000, C524S817000, C524S833000, C524S819000, C524S820000, C524S823000, C524S824000, C524S832000

Reexamination Certificate

active

06683129

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to aqueous emulsions comprising a water-dispersible copolymer which is non-dispersible in aqueous solutions containing 0.5% or more of an inorganic salt, comprising acidic ethylenically unsaturated monomers and ethylenically unsaturated monomers. The acidic ethylenically unsaturated monomers and the ethylenically unsaturated monomers are defined herein. The present invention also pertains to emulsion polymerization methods for making the aqueous emulsions with or without a surfactant.
BACKGROUND OF THE INVENTION
Water-soluble polymers, soluble in tap water but insoluble in dilute salt solutions, are known in the art, however many of these water-soluble polymer compositions are not entirely satisfactory. Moreover, many water-soluble copolymers require alkali to remove the polymeric film which is often difficult and unsafe for the consumer. The present invention provides improved water-dispersible copolymer compositions without the disadvantages characteristic of previously known compositions.
SUMMARY OF THE INVENTION
In a first embodiment, the present invention is directed to an aqueous emulsion comprising a water-dispersible copolymer which is non-dispersible in aqueous solutions containing 0.5% or more of an inorganic salt, wherein the water-dispersible copolymer comprises in percentages by weight:
(A) from about 10% to about 90% of an acidic ethylenically unsaturated monomer; and
(B) from about 10% to about 90% of an ethylenically unsaturated monomer selected from the group of monomer formulas consisting of:
(i) CH
2
═C(R
1
)COR
2
;
(ii) R
3
OOC—CH═CH—COOR
4
;
(iii) CH
2
═C(R
5
)OCOR
6
;
(iv) CH
2
═C(COOR
7
)CH
2
COOR
8
;
(v) CH
3
CH═CHCOOR
9
;
(vi) R
10
C
6
H
4
CR
11
═CHR
11
; and
(vii) R
12
CH═CHR
13
;
 wherein R
1
is hydrogen or methyl and R
2
is —OZ′ or —N(Z″)(Z″), wherein Z′ is an alkyl group having from 1 to 7 carbon atoms, and Z″ is independently selected from the group consisting of hydrogen and alkyl groups having from 1 to 6 carbon atoms; R
3
and R
4
are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R
3
and R
4
are not both hydrogen; R
5
is hydrogen or methyl and R
6
is an alkyl group having from 1 to 7 carbon atoms; R
7
and R
8
are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R
7
and R
8
are not both hydrogen; R
9
is an alkyl group having from 1 to 7 carbon atoms; R
10
and R
11
are hydrogen; R
12
and R
13
are independently selected from the group consisting of hydrogen, —CN, —NHCHO, —NHCOCH
3
, and an alkyl group having from 1 to 7 carbon atoms; and the copolymer has a weight average molecular weight greater than about 25,000 and is present in an amount from about 20% to about 70%.
In a second embodiment, the present invention is directed to an aqueous emulsion comprising a water-dispersible copolymer which is non-dispersible in aqueous solutions containing 0.5% or more of an inorganic salt, wherein the water-dispersible copolymer comprises in percentages by weight:
(A) from about 10% to about 90% of an acidic ethylenically unsaturated monomer; and
(B) from about 10% to about 90% of an ethylenically unsaturated monomer selected from the group of monomer formulas consisting of:
(i) CH
2
═C(R′
1
)COR′
2
;
(ii) R′
3
OOC—CH═CH—COOR′
4
;
(iii) CH
2
═C(R′
5
)OCOR′
6
;
(iv) CH
2
═C(COOR′
7
)CH
2
COOR′
8
;
(v) CH
3
CH═CHCOOR′
9
;
(vi) R′
10
C
6
H
4
CR′
11
═CHR′
11
; and
(vii) R′
12
CH═CHR′
13
;
 wherein R′
1
is hydrogen or methyl, and R′
2
is selected from the group consisting of —OZ′, —N(Z″)(Z″), and —OZ′″OH, wherein Z′ is an alkyl group having from 8 to 18 carbon atoms; Z″ is independently selected from the group consisting of alkyl groups having from 7 to 10 carbon atoms, dimethylamino alkyl groups having from 1 to 5 carbon atoms, and hydroxyalkyl groups having from 1 to 5 carbon atoms; and Z′″ is an alkyl group having from 1 to 4 carbon atoms; R′
3
and R′
4
are independently an alkyl group having from 8 to 18 carbon atoms; R′
5
is hydrogen or methyl and R′
6
is an alkyl group having from 8 to 18 carbon atoms; R′
7
and R′
8
are independently an alkyl group having from 8 to 18 carbon atoms; R′
9
is an alkyl group having from 8 to 18 carbon atoms; R′
10
and R′
11
are independently an alkyl group having from 1 to 2 carbon atoms; R′
12
and R′
13
are independently selected from the group consisting of 2-pyrrolidinone, N-caprolactam, 2-pyridine, 3-pyridine, 4-pyridine, and an alkyl group having from 7 to 18 carbon atoms, with the proviso that R
12
and R
13
are not at the same time 2-pyrrolidinone, N-caprolactam, 2-pyridine, 3-pyridine, or 4-pyridine; and the copolymer has a weight average molecular weight greater than about 25,000 and is present in an amount from about 20% to about 70%.
In a third embodiment, the present invention is directed to an aqueous emulsion comprising a water-dispersible copolymer which is non-dispersible in aqueous solutions containing 0.5% or more of an inorganic salt, wherein the water-dispersible copolymer comprises in percentages by weight:
(A) from about 10% to about 80% of an acidic ethylenically unsaturated monomer, with the proviso that the acidic ethylenically unsaturated monomer is not acrylic acid;
(B) from about 10% to about 80% of an ethylenically unsaturated monomer selected from the group of monomer formulas consisting of:
(i) CH
2
═C(R
1
)COR
2
;
(ii) R
3
OOC—CH═CH—COOR
4
;
(iii) CH
2
═C(R
5
)OCOR
6
;
(iv) CH
2
═C(COOR
7
)CH
2
COOR
8
;
(v) CH
3
CH═CHCOOR
9
;
(vi) R
10
C
6
H
4
CR
11
═CHR
11
; and
(vii) R
12
CH═CHR
13
;
 wherein R
1
is hydrogen or methyl and R
2
is —OZ′ or —N(Z″)(Z″), wherein Z′ is an alkyl group having from 1 to 7 carbon atoms, and Z″ is independently selected from the group consisting of hydrogen and alkyl groups having from 1 to 6 carbon atoms; R
3
and R
4
are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R
3
and R
4
are not both hydrogen; R
5
is hydrogen or methyl and R
6
is an alkyl group having from 1 to 7 carbon atoms; R
7
and R
8
are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R
7
and R
8
are not both hydrogen; R
9
is an alkyl group having from 1 to 7 carbon atoms; R
10
and R
11
are hydrogen; and R
12
and R
13
are independently selected from the group consisting of hydrogen, —CN, —NHCHO, and an alkyl group having from 1 to 7 carbon atoms; and
(C) from about 10% to about 80% of an ethylenically unsaturated monomer selected from the group of monomer formulas consisting of:
(i) CH
2
═C(R′
1
)COR′
2
;
(ii) R′
3
OOC—CH═CH—COOR′
4
;
(iii) CH
2
═C(R′
5
)OCOR′
6
;
(iv) CH
2
═C(COOR′
7
)CH
2
COOR′
8
;
(v) CH
3
CH═CHCOOR′
9
;
(vi) R′
10
C
6
H
4
CR′
11
═CHR′
11
; and
(vii) R′
12
CH═CHR′
13
;
 wherein R′
1
is hydrogen or methyl, and R′
2
is selected from the group consisting of —OZ′, —N(Z″)(Z″), and —OZ′″OH, wherein Z′ is an alkyl group having from 8 to 18 carbon atoms; Z″ is independently selected from the group consisting of alkyl groups having from 7 to 10 carbon atoms, dimethylamino alkyl groups having from 1 to 5 carbon atoms, and hydroxyalkyl groups having from 1 to 5 carbon atoms; and Z′″ is an alkyl group having from 1 to 4 carbon atoms; R′
3
and R′
4
are independently an alkyl group having from 8 to 18 carbon atoms; R′
5
is hydrogen or methyl and R′
6
is an alkyl group having from 8 to 18 carbon atoms; R′
7
an

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