Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2000-04-20
2002-11-12
Henderson, Christopher (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S332900
Reexamination Certificate
active
06479594
ABSTRACT:
The present invention pertains to sulfonated interpolymers of &agr;-olefin/vinyl or vinylidene aromatic monomers or hindered aliphatic or cycloaliphatic vinylidene monomers or a combination thereof; salts thereof; and blends thereof. The preferred sulfonated interpolymer is a sulfonated substantially random ethylene/styrene interpolymer.
Interpolymers of &agr;-olefin/vinyl or vinylidene aromatic monomer or hindered aliphatic or cycloaliphatic vinylidene monomer or a combination thereof are well known as described by Stevens et al. in EP 0 416 815 A2. Also well known are polyamide polymers and polymers and copolymers of &agr;-olefins.
It is often desirable to prepare blends of polymers so as to obtain a polymeric blend which provides properties or characteristics not available from either of the polymers alone. Such is true of blends of polyamides and polymers and copolymers of &agr;-olefins. However, such polymers are incompatible and a suitable compatibilizer must be employed before the blends can be utilized.
It has now been found that sulfonated interpolymers of &agr;-olefin/vinyl or vinylidene aromatic monomers or hindered aliphatic or cycloaliphatic vinylidene monomers or a combination thereof and salts thereof are suitable compatibilizers for blends of polyamides and polymers and copolymers of &agr;-olefins. The interpolymers containing the sulfonated salts provide improved mechanical properties at elevated temperatures as compared to the interpolymers prior to being sulfonated and subsequently converted to the salt.
SUMMARY OF THE INVENTION
One aspect of the present invention pertains to a surface sulfonated article prepared from a substantially random interpolymer comprising:
(1) from 1 to 65 mole percent of polymer units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) a combination of at least one vinyl or vinylidene aromatic monomer containing an aromatic ring Ar, and at least one hindered aliphatic or cycloaliphatic vinylidene monomer; and
(2) from 35 to 99 mole percent of polymer units derived from at least one aliphatic &agr;-olefin having from 2 to 20 carbon atoms; and
(3) from zero to 20 mole percent of polymer units derived from a diene containing from 4 to 20 carbon atoms; and
wherein from 0.001 to 30 mole percent of the polymer units contained in said interpolymer contains one or more groups represented by the formula —SO
3
−
M where M is hydrogen, NH
4
+
or a group 1, 2, 7, 11 or 12 metal in ionic form.
Another aspect of the present invention pertains to a substantially random interpolymer having a sulfonated aromatic or cycloaliphatic ring or a sulfonated polymer backbone or a combination thereof, wherein the interpolymer is made from monomer components comprising:
(1) from 1 to 65 mole percent of (a) at least one vinyl or vinylidene aromatic monomer, or (b) a combination of at least one vinyl or vinylidene aromatic monomer and at least one hindered aliphatic or cycloaliphatic vinylidene monomer; and
(2) from 35 to 99 mole percent of at least one aliphatic (&agr;-olefin having from 2 to 20 carbon atoms; and
(3) optionally, from zero to 20 mole percent of a diene containing from 4 to 2 carbon atoms; and
wherein from 0.1 to 65 mole percent of the aromatic or cycloaliphatic rings contained in said sulfonated interpolymer contains a group represented by the formula —SO
3
−
M where M is hydrogen, NH
4
+
or a group 1, 2, 7, 11 or 12 metal in ionic form.
Another aspect of the present invention pertains to a compatibilized blend of polymers comprising
(A) from 1 to 99 percent by weight of at least one polyamide;
(B) from 1 to 99 percent by weight of at least one olefin polymer free of mers derived from aromatic vinyl, aromatic vinylidene, hindered aliphatic vinylidene, cycloaliphatic vinylidene monomers or a combination thereof; and
(C) from 1 to 99 percent by weight of at least one ring sulfonated substantially random interpolymer made from monomer components comprising
(1) from 1 to 65 mole percent of (a) at least one vinyl or vinylidene aromatic monomer, or (b) a combination of at least one vinyl or vinylidene aromatic monomer and at least one hindered aliphatic or cycloaliphatic vinylidene monomer, and
(2) from 35 to 99 mole percent of at least one aliphatic &agr;-olefin having from 2 to 20 carbon atoms; and
(3) optionally, from zero to 20 mole percent of a diene containing from 4 to 20 carbon atoms; and
wherein from 0.05 to 30 mole percent of the aromatic or cycloaliphatic rings contained in said sulfonated interpolymer contains one or more groups represented by the formula —SO
3
−
M where M is hydrogen, NH
4
+
or a group 1, 2, 7, 11 or 12 metal in ionic form or combination thereof.
Another aspect of the present invention pertains to a modified interpolymer composition having an upper service temperature at least 5° C., preferably from 20° C. to 50° C., more preferably from 50° C. to 150° C. higher than the unmodified interpolymer, said unmodified interpolymer comprising
(A) from 1 to 65 mole percent of polymer units derived from at least one vinyl or vinylidene aromatic monomer; and
(B) from 35 to 99 mole percent of polymer units derived from at least one aliphatic &agr;-olefin having from 2 to 20 carbon atoms;
said modified polymer resulting from
(1) subjecting said unmodified interpolymer to sulfonation so as to provide the resultant sulfonated interpolymer with from 0.1 to 5 weight percent —SO
3
H groups; and
(2) reacting the sulfonated interpolymer of step (1) with a NH
4
+
or a Group 1, 2,7 or 12 metal compound capable of reacting with the product from step (1) to convert at least some, preferably from 1 to 100, more preferably from 50 to 100 mole percent, most preferably 100 mole percent of the pendant —SO
3
H groups to —SO
3
−
M groups wherein M is NH
4
+
or a Group 1, 2, 7, 11 or 12 metal in ionic form.
In the above compositions, the total number of monomer units in the polymers is 100 mole percent and the total polymer content of the blends is 100 percent by weight.
The blends of the present invention can comprise, consist essentially of, or consist of any two or more of such interpolymers, polymers or copolymers enumerated herein. Likewise, the interpolymers, polymers or copolymers include those made from monomer components which comprise, consist essentially of, or consist of any two or more of the enumerated polymerizable monomers.
DETAILED DESCRIPTION OF THE INVENTION
Any reference herein to metals of a particular group refers to the “Fnew” groups of the periodic table of the elements set forth in the
CRC Handbook of Chemistry and Physics,
71
st
ed.
The term “hydrocarbyl” means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or cycloaliphatic substituted aromatic groups. The aliphatic or cycloaliphatic groups are preferably saturated. Likewise, the term “hydrocarbyloxy” means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached.
The term “interpolymer” is used herein to indicate a polymer wherein at least two different monomers are polymerized to form the interpolymer. This includes copolymers, terpolymers, etc.
The term “mer(s)” means the polymerized unit of the polymer derived from the indicated monomer(s).
The term “plurality” as used herein means two or more.
When references are made herein to a polymer containing monomer(s) or monomer units derive from, it really means that the polymer contains monomer(s) residues resulting from polymerizing the indicated monomer(s) to make the polymer.
The term “substantially random” in the substantially random interpolymer comprising an &agr;-olefin and a vinyl or vinylidene aromatic monomer or hindered aliphatic vinylidene monomer as used herein means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in
POLYMER SEQUENCE DETERMINATION, Carbon
Cheung Yunwa W.
Hahn Stephen F.
Ho Thoi H.
Schmidt Gregory F.
Stevens James C.
Henderson Christopher
The Dow Chemical Company
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