U.S. patent application number 10/025637 was filed with the patent office on 2002-08-15 for continuous polymerization process and products therefrom.
Invention is credited to Bowe, Michael Damian, Greenblatt, Gary David, Lange, Barry Clifford, Larson, Gary Robert, Merritt, Richard Foster, Petrovich, Lori Marie, Whitman, David William, Wilczynski, Robert.
Application Number | 20020111448 10/025637 |
Document ID | / |
Family ID | 22789301 |
Filed Date | 2002-08-15 |
United States Patent
Application |
20020111448 |
Kind Code |
A1 |
Greenblatt, Gary David ; et
al. |
August 15, 2002 |
Continuous polymerization process and products therefrom
Abstract
A continuous process for oligomers which do not contain, as
polymerized units, carboxylic acid-containing monomers and their
salts, including the steps of: (1) forming a reaction mixture,
substantially free of carboxylic acid-containing monomers and their
salts, containing: (i) 0.5 to 99.95% by weight of the reaction
mixture of at least one ethylenically unsaturated monomer; and (ii)
0.05 to 25% by weight, based on the weight of the ethylenically
unsaturated monomer, of at least one free-radical initiator; and
(2) continuously passing the reaction mixture through a heated zone
wherein the reaction mixture is maintained at a temperature of at
least 150.degree. C. and a pressure of at least 30 bars for from
0.1 seconds to 4 minutes to form terminally-unsaturated oligomers.
In addition, processes for forming oligomers of vinyl acetate and
oligomers of vinyl alcohol are disclosed. Mixtures of fully
saturated and terminally unsaturated oligomers are also
disclosed.
Inventors: |
Greenblatt, Gary David;
(Rydal, PA) ; Lange, Barry Clifford; (Lansdale,
PA) ; Bowe, Michael Damian; (Newtown, PA) ;
Merritt, Richard Foster; (Fort Washington, PA) ;
Wilczynski, Robert; (Yardley, PA) ; Larson, Gary
Robert; (Hatfield, PA) ; Petrovich, Lori Marie;
(Blue Bell, PA) ; Whitman, David William;
(Sumneytown, PA) |
Correspondence
Address: |
Gregory M. Hill
Rohm and Haas Company
100 Independence Mall West
Philadelphia
PA
19106
US
|
Family ID: |
22789301 |
Appl. No.: |
10/025637 |
Filed: |
December 19, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10025637 |
Dec 19, 2001 |
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09212038 |
Dec 15, 1998 |
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60042725 |
Apr 8, 1997 |
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60077059 |
Mar 6, 1998 |
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Current U.S.
Class: |
526/227 ;
526/328; 526/64; 526/88; 560/202 |
Current CPC
Class: |
C07C 67/347 20130101;
C08F 20/04 20130101; C08F 290/046 20130101; C08K 5/0016 20130101;
C08K 5/0025 20130101; C07C 67/347 20130101; C07C 2603/68 20170501;
C08F 220/281 20200201; C07C 43/196 20130101; C08F 2/02 20130101;
C08L 21/00 20130101; C08K 5/0016 20130101; C11D 3/3757 20130101;
C08L 21/00 20130101; C08L 101/00 20130101; C08L 101/00 20130101;
C08L 21/00 20130101; C07C 69/604 20130101; C08L 2666/04 20130101;
C08L 2666/02 20130101; C08F 2/18 20130101 |
Class at
Publication: |
526/227 ; 526/88;
526/328; 526/64; 560/202 |
International
Class: |
C08F 004/28 |
Claims
What is claimed is:
1. A process for forming oligomers, comprising the steps of: (1)
forming a reaction mixture, substantially free of solvent and
carboxylic acid-monomers and their salts, comprising: (i) 0.5 to
99.95% by weight, based on the weight of said reaction mixture, of
at least one ethylenically-unsaturated monomer; and (ii) 0.05 to
25% by weight, based on the weight of said
ethylenically-unsaturated monomer, of at least one free-radical
initiator; and (2) continuously passing said reaction mixture
through a heated zone wherein said reaction mixture is maintained
at a temperature of at least 150.degree. C. and a pressure of at
least 30 bars for from 0.1 seconds to 4 minutes to form
terminally-unsaturated oligomers.
2. A process for forming oligomers having a degree of
polymerization of at least 4, comprising the steps of: (1) forming
a reaction mixture, substantially free of carboxylic-containing
monomers and their salts, comprising: (i) 0.5 to 99.95% by weight,
based on the weight of said reaction mixture, of at least one
ethylenically-unsaturated monomer; and (ii) 0.05 to 25% by weight,
based on the weight of said ethylenically-unsaturated monomer, of
at least one free-radical initiator; and (2) continuously passing
said reaction mixture through a heated zone wherein said reaction
mixture is maintained at a temperature of at least 150.degree. C.
and a pressure of at least 30 bars for from 0.1 seconds to 4
minutes to form terminally-unsaturated oligomers.
3. The process of claims 1 or 2, wherein step (2) is conducted in a
tubular reactor having no moving parts.
4. The process of claims 1 or 2, wherein said
ethylenically-unsaturated monomer is at least one monomer selected
from the group consisting of n-alkyl(meth)acrylates, branched
alkyl(meth)acrylates, cycloalkyl (meth)acrylates, straight chain or
branched haloalkyl(meth)acrylates, aromatic alkyl(meth)acrylates,
aromatic (meth)acrylates, hydroxyalkyl(meth)acrylates, heterocyclyl
(meth)acrylates, aminoalkyl (meth)acrylates, ether-containing
(meth)acrylates, silicon-containing (meth)acrylates,
(meth)acrylamides, epoxide-containing (meth)acrylates, unsaturated
alkyl(meth)acrylates, (meth)acrylate esters derived from
(poly)unsaturated vegetable oils, terminal alkenes, aralkenes,
heterocyclyl alkenes, dienes, vinyl halides, vinyl esters, vinyl
ketones, aldehyde-containing vinyl functionality, epoxyalkenes,
vinyl monomers, vinylsilanes, alkoxyvinylsilanes, unsaturated
diesters, and functional (meth)acrylates.
5. The process of claims 1 or 2, wherein said reaction mixture
comprises at least two different ethylenically-unsaturated
monomers.
6. The process of claims 1 or 2, wherein said reaction mixture
comprises at least three different ethylenically-unsaturated
monomers.
7. The process of claim 2, wherein said reaction mixture further
comprises 0% to 99.5% solvent.
8. The process of claim 7, wherein said solvent is at least one
solvent selected from the group consisting of tetrahydrofuran,
acetone, ethyl acetate, methyl alcohol, butyl alcohol, hexane,
heptane, benzene, toluene, xylene, carbon dioxide, water, and
mixtures thereof.
9. The process of claims 1 or 2, further comprising the step of:
(3) hydrogenating said terminally-unsaturated oligomers.
10. The process of claims 1 or 2 wherein said heated zone is
maintained at a temperature of from 200.degree. C. to 500.degree.
C.
11. The process of claims 1 or 2 wherein said heated zone is
maintained at a temperature of from 275.degree. C. to 450.degree.
C.
12. The process of claims 1 or 2 wherein said heated zone is
maintained at a pressure of from 70 bars to 350 bars.
13. The process of claims 1 or 2 wherein said heated zone is
maintained at a pressure of from 200 bars to 300 bars.
14. The process of claims 1 or 2 wherein said reaction mixture is
maintained in said heated zone for from 0.5 seconds to 2
minutes.
15. The process of claims 1 or 2 wherein said reaction mixture is
maintained in said heated zone for from 1 second to 1 minute.
16. A process for forming oligomers of vinyl acetate, comprising
the steps of: (1) forming a reaction mixture, substantially free of
carboxylic-containing monomers and their salts, comprising: (i) 0.5
to 99.95% by weight, based on the weight of said reaction mixture,
of vinyl acetate; and (ii) 0.05 to 25% by weight, based on the
weight of said vinyl acetate, of at least one free-radical
initiator; and (2) continuously passing said reaction mixture
through a heated zone wherein said reaction mixture is maintained
at a temperature of at least 150.degree. C. and a pressure of at
least 30 bars for from 0.1 seconds to 4 minutes to form oligomers
of vinyl acetate.
17. A process for forming oligomers of vinyl alcohol, comprising
the steps of: (1) forming a reaction mixture, substantially free of
carboxylic-containing monomers and their salts, comprising: (i) 0.5
to 99.95% by weight, based on the weight of said reaction mixture,
of vinyl acetate; and (ii) 0.05 to 25% by weight, based on the
weight of said vinyl acetate, of at least one free-radical
initiator; (2) continuously passing said reaction mixture through a
heated zone wherein said reaction mixture is maintained at a
temperature of at least 150.degree. C. and a pressure of at least
30 bars for from 0.1 seconds to 4 minutes to form oligomers of
vinyl acetate; and (3) hydrolyzing said oligomers of vinyl acetate
in the presence of a catalyst to form oligomers of vinyl
alcohol.
18. A process for forming oligomers of vinyl alcohol, comprising
the steps of: (1) forming a reaction mixture, substantially free of
carboxylic-containing monomers and their salts, comprising: (i) 0.5
to 99.95% by weight, based on the weight of said reaction mixture,
of vinyl acetate; and (ii) 0.05 to 25% by weight, based on the
weight of said vinyl acetate, of at least one free-radical
initiator; (2) continuously passing said reaction mixture through a
heated zone wherein said reaction mixture is maintained at a
temperature of at least 150.degree. C. and a pressure of at least
30 bars for from 0.1 seconds to 4 minutes to form oligomers of
vinyl acetate; and (3) transesterifying said oligomers of vinyl
acetate with an alcohol in the presence of a catalyst to form
oligomers of vinyl alcohol.
19. The process of claims 16-18 wherein step (2) is conducted in a
tubular reactor having no moving parts.
20. A mixture, comprising: (1) about 50 to 90% by weight, based on
the weight of the mixture, of a first oligomer having terminal
unsaturation of Formula (I): 17(I) where at least one of E.sup.1
and E.sup.2 is an endgroup of the formula: 18and when only one of
said E.sup.1 and E.sup.2 is an endgroup of Formula (II) then said
other of said E.sup.1 and E.sup.2 is selected independently from H,
19and where A, A.sup.1 and A.sup.2=independently selected from --H;
C.sub.1-C.sub.50 straight-chain or branched alkyl, optionally
substituted with a Y group; C.sub.2-C.sub.50 straight-chain or
branched alkenyl containing 1-5 double bonds, optionally
substituted with 1-2 Y groups; C.sub.5-C.sub.8 cycloalkyl,
C.sub.5-C.sub.8 cycloalkenyl; phenyl, (CH.sub.2).sub.m-phenyl- , 1-
or 2-naphthyl; --(C.dbd.O)H; --C(OR.sup.1).sub.2H;
--(C.dbd.O)R.sup.1, --(C.dbd.O)CF.sub.3;
--C(OR.sup.1).sub.2R.sup.1; --(C.dbd.O)OR, --O(C.dbd.O)R.sup.1;
--(C.dbd.O)Cl; --O(C.dbd.O)OR.sup.1; --OR; --(C.dbd.O)NH.sub.2,
--(C.dbd.O)NHR.sup.1, --(C.dbd.O)N(R.sup.1).su- b.2,
--NH(C.dbd.O)R.sup.1, --NH(C.dbd.O)H,
--(C.dbd.O)NH(CH.sub.2).sub.m(N- H.sub.3).sup.(+)(X).sup.(-),
--(C.dbd.O)NH(CH.sub.2).sub.m(NR.sup.1).sub.2- ;
--Si(OR.sup.1).sub.3, --Si(OR.sup.1).sub.2R.sup.1,
--Si(OR.sup.1)(R.sup.1).sub.2, --Si(R.sup.1).sub.3; --F, --Cl,
--Br, --I; --C.ident.N; oxiranyl; --NH(C.dbd.O)NH.sub.2,
--NH(C.dbd.O)NHR.sup.1, --NH(C.dbd.O)N(R.sup.1).sub.2;
20--CH.sub.2C.sub.nF.sub.2n+1, --CH.sub.2CH.sub.2C.sub.nF.sub.2n+1,
--CH(CF.sub.3).sub.2, --CH.sub.2C.sub.nF.sub.2nH,
--CH.sub.2CH.sub.2C.sub.nF.sub.2nH; --P(.dbd.O)(OR.sup.1).sub.3;
--S(.dbd.O).sub.2(OR.sup.1); --S(.dbd.O).sub.2R.sup.1; A.sup.3,
A.sup.4=independently selected from --H, --F, --Cl, --Br, R.sup.1;
G.sup.1, G.sup.2=independently selected from --H, --CH.sub.3,
--(CH.sub.2).sub.mCO.sub.2R.sup.1, --F, --Cl, --Br, --I; M.sup.1,
M.sup.2+independently selected from --H, --C.ident.N,
--(C.dbd.O)OR.sup.1, --F, --Cl, --Br, --I; Q=C.sub.1-C.sub.8
straight-chain or branched alkyl, --OR.sup.3, residue from radical
decomposition of azo initiators (azonitrile, azoamidine, cyclic
azoamidine, azoamide, azoalkyl classes) such as
--C(R.sup.4).sub.2C.ident- .N; R=C.sub.1-C.sub.50 straight-chain or
branched alkyl, C.sub.2-C.sub.50 straight-chain or branched alkenyl
containing 1-5 double bonds; C.sub.5-C.sub.8 cycloalkyl,
C.sub.5-C.sub.8 cycloalkenyl; phenyl, (CH.sub.2).sub.m-phenyl, 1-
or 2-naphthyl, -4-benzoylphenyl (where any phenyl group may be
substituted with up to 2 R.sup.2), anthracenyl, anthracenylmethyl;
--(CH.sub.2).sub.mO(C.dbd.O)R.sup.1,
--(CH.sub.2).sub.m(C.dbd.O)OR.sup.1;
--(CH.sub.2).sub.m(C.dbd.O)R.sup.1;
--(CH.sub.2).sub.m(C.dbd.O)NH.sub.2,
--(CH.sub.2).sub.m(C.dbd.O)NHR.sup.- 1,
--(CH.sub.2).sub.m(C.dbd.O)NH(R.sup.1).sub.2;
--(CH.sub.2).sub.mN(R.su- p.1).sub.2,
--(CH.sub.2).sub.mNH.sub.3.sup.(+)X.sup.(-);
--(CH.sub.2).sub.mOR.sup.1, --(CH.sub.2CH.sub.2O).sub.mR.sup.1,
--(CH.sub.2CH(CH.sub.3)O).sub.mR.sup.1, -2-tetrahydrofuranyl;
--(CH.sub.2).sub.mN.dbd.C.dbd.O; --CH.sub.2C.sub.nF.sub.2n+1,
--CH.sub.2CH.sub.2C.sub.nF.sub.2n+1, --CH(CF.sub.3).sub.2,
--CH.sub.2C.sub.nF.sub.2nH, --CH.sub.2CH.sub.2C.sub.nF.sub.2nH;
(CH.sub.2).sub.m 21 linear alkanes containing 1-5 epoxy groups
derived from (poly)unsaturated vegetable oils;
--(CH.sub.2).sub.pOH, --(CH.sub.2CH.sub.2O).sub.mH
--[CH.sub.2CH--(CH.sub.3)O].sub.mH;
--(CH.sub.2).sub.mSi(OR.sup.1).sub.3,
(CH.sub.2).sub.mSi(R.sup.1)(OR.sup.- 1).sub.2,
--(CH.sub.2).sub.mSi(R.sup.1).sub.2 OR.sup.1,
--(CH.sub.2).sub.mSi(R.sup.1).sub.3; 22
--(CH.sub.2).sub.mO(C.dbd.O)CH.s- ub.2(C.dbd.O)R.sup.1;
R.sup.1=independently selected from C.sub.1-C.sub.8 straight chain
or branched alkyl where (R.sup.1).sub.2 may constitute a
C.sub.5-C.sub.8 cycloalkyl group; phenyl, --CH.sub.2phenyl;
R.sup.2=C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, --CHO,
--(C.dbd.O)OR1, --N(R.sup.1).sub.2, --NO.sub.2,
--(C.dbd.O)N(R.sup.1).sub.2, --CF.sub.3, --(C.dbd.O)R.sup.1; --F,
--Cl, --Br, --I; R.sup.3=--H, C.sub.1-C.sub.8 straight chain or
branched alkyl, --R.sup.1(C.dbd.O), -R.sup.1(C.dbd.O)O;
R.sup.4=C.sub.1-C.sub.18 straight-chain alkyl, C.sub.5-C.sub.8
cycloalkyl wherein the two adjacent R.sup.4 groups may together
form a 5-8 membered ring, C.sub.1-C.sub.4 alkoxy-substituted
straight-chain or branched C.sub.1-C.sub.8 alkyl groups;
X.sup.(-)=--F.sup.(-), --Cl.sup.(-), --Br.sup.(-), --I.sup.(-),
HSO.sub.4.sup.(-), --H.sub.2PO.sub.3.sup.(-); Y=--OH, --F, --Cl,
--Br, --I, --NH.sub.2, --N(R.sup.1).sub.2; m=1-8 n=1-18 p=2-8
x=0-49 y=0-49 z=0-49 x+y+z.ltoreq.49; and (2) about 10 to 50% by
weight, based on the weight of the mixture, of a second oligomer of
Formula (I), 23(I) where E.sup.1 and E.sup.2=independently selected
from H, 24A, A.sup.1 and A.sup.2 =independently selected from --H;
C.sub.1-C.sub.50 straight-chain or branched alkyl, optionally
substituted with a Y group; C.sub.2-C.sub.50 straight-chain or
branched alkenyl containing 1-5 double bonds, optionally
substituted with 1-2 Y groups; C.sub.5-C.sub.8 cycloalkyl,
C.sub.5-C.sub.8 cycloalkenyl; phenyl, (CH.sub.2).sub.m-phenyl, 1-
or 2-naphthyl; --(C.dbd.O)H; --C(OR.sup.1).sub.2H;
--(C.dbd.O)R.sup.1, --(C.dbd.O)CF.sub.3;
--C(OR.sup.1).sub.2R.sup.1; --(C.dbd.O)OR, --O(C.dbd.O)R.sup.1;
----(C.dbd.O)Cl; --O(C.dbd.O)OR.sup.1; --OR; --(C.dbd.O)NH.sub.2,
--(C.dbd.O)NHR.sup.1, --(C.dbd.O)N(R.sup.1).sub.2,
--NH(C.dbd.O)R.sup.1, --NH(C.dbd.O)H,
--(C.dbd.O)NH(CH.sup.2).sub.m(NH.sub.3).sup.(+)(X).sup.(-- ),
--(C.dbd.O)NH(CH.sub.2).sub.m(NR.sup.1).sub.2;
--Si(OR.sup.1).sub.3, --Si(OR.sup.1).sub.2R.sup.1,
--Si(OR.sup.1)(R.sup.1).sub.2, --Si(R.sup.1).sub.3; --F, --Cl,
--Br, --I; --C.ident.N; oxiranyl; --NH(C.dbd.O)NH.sub.2,
--NH(C.dbd.O)NHR.sup.1, --NH(C.dbd.O)N(R.sup.1).su- b.2;
25--CH.sub.2C.sub.nF.sub.2n+1, --CH.sub.2CH.sub.2C.sub.nF.sub.2n+1,
--CH(CF.sub.3).sub.2, --CH.sub.2C.sub.nF.sub.2nH, --CH.sub.2
CH.sub.2C.sub.nF.sub.2nH; --P(.dbd.O)(OR.sup.1).sub.3;
--S(.dbd.O).sub.2(OR.sup.1); --S(.dbd.O).sub.2R.sup.1; A.sup.3,
A.sup.4=independently selected from --H, --F, --Cl, --Br, R.sup.1;
G.sup.1, G.sup.2=independently selected from --H, --CH.sub.3,
--(CH.sub.2).sub.mCO.sub.2R.sup.1, --F, --Cl, --Br, --I; M.sup.1,
M.sup.2=independently selected from --H, --CN, --(C.dbd.O)OR.sup.1,
--F, --Cl, --Br, --I; Q=C.sub.1-C.sub.8 straight-chain or branched
alkyl, --OR.sup.3, residue from radical decomposition of azo
initiators (azonitrile, azoamidine, cyclic azoamidine, azoamide,
azoalkyl classes) such as --C(R.sup.4).sub.2C.ident.N;
R=C.sub.1-C.sub.50 straight-chain or branched alkyl,
C.sub.2-C.sub.50 straight-chain or branched alkenyl containing 1-5
double bonds; C.sub.5-C.sub.8 cycloalkyl, C.sub.5-C.sub.8
cycloalkenyl; phenyl, (CH.sub.2).sub.m-phenyl, 1- or 2-naphthyl,
-4-benzoylphenyl (where any phenyl group may be substituted with up
to 2 R.sup.2), anthracenyl, anthracenylmethyl;
--(CH.sub.2).sub.mO(C.dbd.O)R.- sup.1,
--(CH.sub.2).sub.m(C.dbd.O)OR.sup.1; --(CH.sub.2).sub.m(C.dbd.O)R.-
sup.1; --(CH.sub.2).sub.m(C.dbd.O)NH.sub.2,
--(CH.sub.2).sub.m(C.dbd.O)NH- R.sup.1,
--(CH.sub.2).sub.m(C.dbd.O)NH(R.sup.1).sub.2;
--(CH.sub.2).sub.mN(R.sup.1).sub.2,
--(CH.sub.2).sub.mNH.sub.3.sup.(+)X.s- up.(-);
--(CH.sub.2).sub.mOR.sup.1, --(CH.sub.2CH.sub.2O).sub.mR.sup.1,
--(CH.sub.2CH(CH.sub.3)O).sub.mR.sup.1, -2-tetrahydrofuranyl;
--(CH.sub.2).sub.mN.dbd.C.dbd.O; CH.sub.2C.sub.nF.sub.2n+1,
--CH.sub.2CH.sub.2C.sub.nF.sub.2n+1, --CH(CF.sub.3).sub.2,
--CH.sub.2C.sub.nF.sub.2nH, --CH.sub.2CH.sub.2C.sub.nF.sub.2nH;
--(CH.sub.2).sub.m 26 linear alkanes containing 1-5 epoxy groups
derived from (poly)unsaturated vegetable oils;
--(CH.sub.2).sub.pOH, --(CH.sub.2CH.sub.2O).sub.mH,
--[CH.sub.2CH(CH.sub.3)O].sub.mH;
--(CH.sub.2).sub.mSi(OR.sup.1).sub.3,
--(CH.sub.2).sub.mSi(R.sup.1)(OR.su- p.1).sub.2,
--(CH.sub.2).sub.mSi(R.sup.1).sub.2,OR.sup.1,
--(CH.sub.2).sub.mSi(R.sup.1).sub.3; 27
--(CH.sub.2).sub.mO(C.dbd.O)CH.s- ub.2(C.dbd.O)R.sup.1;
R.sup.1=independently selected from C.sub.1-C.sub.8 straight chain
or branched alkyl where (R.sup.1).sub.2 may constitute a
C.sub.5-C.sub.8 cycloalkyl group; phenyl, --CH.sub.2phenyl;
R.sup.2=C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, --CHO,
--(C.dbd.O)OR1, --N(R.sup.1).sub.2, --NO.sub.2,
--(C.dbd.O)N(R.sup.1).sub.2, --CF.sub.3, --(C.dbd.O)R.sup.1; --F,
--Cl, --Br, --I; R.sup.3=--H, C.sub.1-C.sub.8 straight chain or
branched alkyl, --R.sup.1(C.dbd.O), --R.sup.1(C.dbd.O)O;
R.sup.4=C.sub.1-C.sub.18 straight-chain alkyl, C.sub.5-C.sub.8
cycloalkyl wherein the two adjacent R.sup.4 groups may together
form a 5-8 membered ring, C.sub.1-C.sub.4 alkoxy-substituted
straight-chain or branched C.sub.1-C.sub.8 alkyl groups;
X.sup.(-)=--F.sup.(--), --Cl.sup.(-), --Br.sup.(-), --I.sup.(-),
--HSO.sub.4.sup.(-), --H.sub.2PO.sub.3.sup.(-); Y=--OH, --F, --Cl,
--Br, --I, --NH.sub.2, --N(R.sup.1).sub.2; m=1-8 n=1-18 p=2-8
x=0-49 y=0-49 z=0-49 x+y+z.ltoreq.49.
21. The mixture of claim 20 wherein said oligomers are formed from
at least one ethylenically-unsaturated monomer selected from the
group consisting of n-alkyl(meth)acrylates, branched
alkyl(meth)acrylates, cycloalkyl (meth)acrylates, straight chain or
branched haloalkyl(meth)acrylates, aromatic alkyl(meth)acrylates,
aromatic (meth)acrylates, hydroxyalkyl(meth)acrylates, heterocyclyl
(meth)acrylates, aminoalkyl (meth)acrylates, ether-containing
(meth)acrylates, silicon-containing (meth)acrylates,
(meth)acrylamides, epoxide-containing (meth)acrylates, unsaturated
alkyl(meth)acrylates, (meth)acrylate esters derived from
(poly)unsaturated vegetable oils, terminal alkenes, aralkenes,
heterocyclyl alkenes, dienes, vinyl halides, vinyl esters, vinyl
ketones, aldehyde-containing vinyl functionality, epoxyalkenes,
vinyl monomers vinylsilanes, alkoxyvinylsilanes, unsaturated
diesters, and functional (meth)acrylates.
22. A composition, consisting essentially of: (a) at least one
oligomer of the formula: 28(I) where A, A.sup.1 and
A.sup.2=independently selected from --H; C.sub.1-C.sub.50
straight-chain or branched alkyl, optionally substituted with a Y
group; C.sub.2-C.sub.50 straight-chain or branched alkenyl
containing 1-5 double bonds, optionally substituted with 1-2 Y
groups; C.sub.5-C.sub.8 cycloalkyl, C.sub.5-C.sub.8 cycloalkenyl;
phenyl, (CH.sub.2).sub.m-phenyl, 1- or 2-naphthyl; --(C.dbd.O)H;
--C(OR.sup.1).sub.2H; --(C.dbd.O)R.sup.1, --(C.dbd.O)CF.sub.3;
--C(OR.sup.1).sub.2R.sup.1; --(C.dbd.O)OR, --O(C.dbd.O)R.sup.1;
--(C.dbd.O)Cl; --O(C.dbd.O)OR.sup.1; --OR; --(C.dbd.O)NH.sub.2,
--(C.dbd.O)NHR.sup.1, --(C.dbd.O)N(R.sup.1).sub.2,
--NH(C.dbd.O)R.sup.1, --NH(C.dbd.O)H,
--(C.dbd.O)NH(CH.sub.2).sub.m(NH.sub.3).sup.(+)(X).sup.(-- ),
--(C.dbd.O)NH(CH.sub.2).sub.m(NR.sup.1).sub.2; --Si(OR ).sub.3,
--Si(OR.sup.1).sub.2R.sup.1, --Si(OR.sup.1)(R.sup.1).sub.2,
--Si(R.sup.1).sub.3; --F, --Cl, --Br, --I; --C.ident.N; oxiranyl;
--NH(C.dbd.O)NH.sub.2, --NH(C.dbd.O)NHR.sup.1,
--NH(C.dbd.O)N(R.sup.1).su- b.2; 29--CH.sub.2C.sub.nF.sub.2n+1,
--CH.sub.2CH.sub.2C.sub.nF.sub.2n+1, --CH(CF.sub.3).sub.2,
--CH.sub.2C.sub.nF.sub.2nH, --CH.sub.2CH.sub.2C.sub- .nF.sub.2nH;
--P(.dbd.O)(OR.sup.1).sub.3; --S(.dbd.O).sub.2(OR.sup.1);
--S(.dbd.O).sub.2R.sup.1; A.sup.3, A.sup.4=independently selected
from --H, --F, --Cl, --Br, R.sup.1; E.sup.1, E.sup.2=independently
selected from --H, 30G.sup.1,G.sup.2=independently selected from
--H, --CH.sup.3, --(CH.sub.2).sub.mCO.sub.2R.sup.1, --F, --Cl,
--Br, --I; M.sup.1, M.sup.2=independently selected from --H,
--C.ident.N, --(C.dbd.O)OR.sup.1, --F, --Cl, --Br, --I;
Q=C.sub.1-C.sub.8 straight-chain or branched alkyl, --OR.sup.3,
residue from radical decomposition of azo initiators (azonitrile,
azoamidine, cyclic azoamidine, azoamide, azoalkyl classes) such as
--C(R.sup.4).sub.2C.ident- .N; R=C.sub.1-C.sub.50 straight-chain or
branched alkyl, C.sub.2-C.sub.50 straight-chain or branched alkenyl
containing 1-5 double bonds; C.sub.5-C.sub.8 cycloalkyl,
C.sub.5-C.sub.8 cycloalkenyl; phenyl, (CH.sub.2).sub.m-phenyl, 1-
or 2-naphthyl, -4-benzoylphenyl (where any phenyl group may be
substituted with up to 2 R.sup.2), anthracenyl, anthracenylmethyl;
--(CH.sub.2).sub.mO(C.dbd.O)R.sup.1,
--(CH.sub.2).sub.m(C.dbd.O)OR.sup.1;
--(CH.sub.2).sub.m(C.dbd.O)R.sup.1;
--(CH.sub.2).sub.m(C.dbd.O)NH.sub.2,
--(CH.sub.2).sub.m(C.dbd.O)NHR.sup.- 1,
--(CH.sub.2).sub.m(C.dbd.O)NH(R.sup.1).sub.2;
--(CH.sub.2).sub.mN(R.sup- .1).sub.2,
--(CH.sub.2).sub.mNH.sub.3.sup.(+)X).sup.(-);
--(CH.sub.2).sub.mOR.sup.1, --(CH.sub.2CH.sub.2O).sub.mR.sup.1,
--(CH.sub.2CH(CH.sub.3)O).sub.mR.sup.1, -2-tetrahydrofuranyl;
--(CH.sub.2).sub.mN.dbd.C.dbd.O; --CH.sub.2C.sub.nF.sub.2n+1,
--CH.sub.2CH.sub.2C.sub.nF.sub.2n+1, --CH(CF.sub.3).sub.2,
--CH.sub.2C.sub.nF.sub.2nH, --CH.sub.2CH.sub.2C.sub.nF.sub.2nH;
--(CH.sub.2).sub.m 31 linear alkanes containing 1-5 epoxy groups
derived from (poly)unsaturated vegetable oils;
--(CH.sub.2).sub.pOH, --(CH.sub.2CH.sub.2O).sub.mH,
[CH.sub.2CH(CH.sub.3)O].sub.mH;
--(CH.sub.2).sub.mSi(OR.sup.1).sub.3,
--(CH.sub.2).sub.mSi(R.sup.1)(OR.su- p.1).sub.2,
--(CH.sub.2).sub.mSi(R.sup.1).sub.2OR.sup.1,
--(CH.sub.2).sub.mSi(R.sup.1).sub.3; 32
--(CH.sub.2).sub.mO(C.dbd.O)CH.s- ub.2(C.dbd.O)R.sup.1;
R.sup.1=independently selected from C.sub.1-C.sub.8 straight chain
or branched alkyl where (R.sup.1).sub.2 may constitute a
C.sub.5-C.sub.8 cycloalkyl group; phenyl, --CH.sub.2phenyl; R.sup.2
C.sub.1-C.sub.6 straight chain or branched alkyl, C.sub.1-C.sub.6
straight chain or branched alkoxy, --CHO, --(C.dbd.O)OR1,
--N(R.sup.1).sub.2, --NO.sub.2, --(C.dbd.O)N(R.sup.1).sub.2,
--CF.sub.3, --(C.dbd.O)R.sup.1; --F, --Cl, --Br, --I; R.sup.3=--H,
C.sub.1-C.sub.8 straight chain or branched alkyl,
--R.sup.1(C.dbd.O), --R.sup.1(C.dbd.O)O; R.sup.4=C.sub.1-C.sub.18
straight-chain alkyl, C.sub.5-C.sub.8 cycloalkyl wherein the two
adjacent R.sup.4 groups may together form a 5-8 membered ring,
C.sub.1-C.sub.4 alkoxy-substituted straight-chain or branched
C.sub.1-C.sub.8 alkyl groups; X.sup.(-)=--F.sup.(--), --Cl.sup.(-),
--Br.sup.(-), --I.sup.(-),--HSO.sub.4.sup.(-),
--H.sub.2PO.sub.3.sup.(-); Y=--OH, --F, --Cl, --Br, --I,
--NH.sub.2, --N(R.sup.1).sub.2; m=1-8 n=1-18 p=2-8 x=0-49 y=0-49
z=0-49 x+y+z.ltoreq.49; (b) at least one surfactant; and (c) water.
Description
[0001] This invention relates to a continuous polymerization
process and products therefrom. In particular, this invention
relates to a high temperature, high pressure, continuous
polymerization process to produce oligomers. More particularly,
this invention relates to a high temperature, high pressure,
continuous polymerization process to produce terminally unsaturated
and fully saturated oligomers. "Oligomers," as used herein and in
the appended claims, refers to polymers having a degree of
polymerization ("dP") of less than 50.
[0002] The art has long sought an inexpensive, efficient and
environmentally sound way to produce low molecular weight polymers.
However, production of these low molecular weight polymers has
proven to be difficult.
[0003] One method of achieving low molecular weight polymers is
through the use of efficient chain transfer agents, but this
approach has several drawbacks. First, this approach incorporates
the structure of the chain transfer agent into the polymer chain.
This can be undesirable since that structure will have an
increasing effect on the properties of the polymer as molecular
weight decreases. Furthermore, the chain transfer agents commonly
employed are mercaptans. These materials are expensive and have
objectionable odors associated with their presence. Other common
chain transfer agents are hypophosphites, bisulfites and alcohols.
These also add to the cost of the process, impart functionality to
the polymer, may introduce salts into the product, and may
necessitate a product separation step.
[0004] Another way of lowering the molecular weight of the polymers
is by increasing the amount of initiator. This approach adds
considerably to the cost of production and may result in polymer
chain degradation, crosslinking, and high levels of unreacted
initiator remaining in the product. In addition, high levels of
initiator may also result in high levels of salt by-products in the
polymer mixture which are known to be detrimental to performance in
many applications. The same is true for chain stopping agents, such
as sodium metabisulfite. Among the preferred free-radical
initiators for aqueous polymerization is hydrogen peroxide. It is
relatively inexpensive, has low toxicity, and does not produce
detrimental salt by-products. However, hydrogen peroxide does not
generally decompose efficiently at conventional polymerization
temperatures and large amounts must normally be used to generate
enough radicals to carry out a polymerization.
[0005] High levels of metal ions, alone or together with high
levels of initiator, have also been tried as a means for
controlling molecular weight. Such an approach is unsuitable for
some products that cannot tolerate metal ion contaminants in the
polymer product, such as pharmaceutical, medical and electronic
applications. In addition, depending on the metal ions used, the
product may be discolored due to the presence of the metal
ions.
[0006] U.S. Pat. No. 4,680,352 and U.S. Pat. No. 4,694,054 disclose
processes for preparing low molecular weight terminally-unsaturated
oligomers employing metal chelate chain transfer agents to control
molecular weight. These processes suffer from the same problems as
those processes employing high level of metal ions, as described
above. In addition, because the methods employing the metal chelate
chain transfer agents undergo .beta.-scission reactions, they are
limited to producing oligomers having homomethacrylate
backbones.
[0007] In the European Polymer Journal, Volume 8, pages 321-328
(1972), Feit describes a multistep synthesis technique for
preparing terminally-unsaturated oligomers and co-oligomers of
vinyl monomers having electronegative groups. The process described
therein requires a base-catalyzed addition of an acetic acid ester
derivative to an activated olefin, followed by hydrolysis of one
ester group, followed by a Mannich reaction to introduce a terminal
double bond. This three step process is repeated to prepare a
terminally-unsaturated oligomer with one additional mer. This
process suffers the drawback of being fairly complex, expensive and
time-consuming.
[0008] U.S. Pat. No. 5,710,227 discloses a high temperature,
continuous polymerization process for preparing terminally
unsaturated oligomers which are formed from acrylic acid and its
salts, and acrylic acid and its salts with other ethylenically
unsaturated monomers. The high temperature, continuous
polymerization process solves many of the problems associated with
previously known methods for preparing terminally-unsaturated
oligomers formed from acrylic acid. However, the neat form of many
of the acrylic acid products are solid and, thus, require the
addition of a solvent to handle and use the products.
[0009] U.S. Pat. No. 4,356,288 discloses the preparation of
terminally-unsaturated oligomers formed from esters of acrylic acid
having a degree of polymerization of about 6-30 by an anionic
polymerization reaction carried out in the presence of a catalytic
amount of an alkoxide anion. The method is relatively complex.
Because the method is inhibited by the presence of moisture
(lowering yield and uniformity of the final product), it is not a
viable commercial process.
[0010] In Chemical Engineering at Supercritical Fluid Conditions,
pages 515-533 (1983), Metzger et al. disclose the dimerization and
trimerization of methyl acrylate in benzene at a pressure of 200
bars and temperatures of 340-420.degree. C. in a flow reactor with
a residence time of 5 minutes.
[0011] The present invention seeks to overcome the problems
associated with the previously known methods for preparing
oligomers by providing a polymerization process that is not limited
to forming oligomers having only a homomethacrylate backbone or a
carboxylic acid-containing monomer residue backbone and that does
not require water or other solvent in the manufacture or use of the
oligomer. The present invention also provides an oligomer free of
metal, salt and surfactant contaminants, that, due to its purity
and composition, is not water sensitive or discolored and is liquid
when provided neat.
STATEMENT OF THE INVENTION
[0012] The invention is directed to a continuous process for
preparing terminally-unsaturated and fully saturated oligomers
which do not contain, as polymerized units, carboxylic
acid-containing monomers, including the steps of:
[0013] (1) forming a reaction mixture, substantially free of
carboxylic-acid monomers and their salts, containing:
[0014] (i) 0.5 to 99.95% by weight of the reaction mixture of at
least one ethylenically unsaturated monomer; and
[0015] (ii) 0.05 to 25% by weight, based on the weight of the
monomer, of at least one free-radical initiator; and
[0016] (2) continuously passing the reaction mixture through a
heated zone wherein the reaction mixture is maintained at a
temperature of at least 150.degree. C. and a pressure of at least
30 bars for from 0.1 seconds to 4 minutes to form
terminally-unsaturated oligomers.
[0017] In addition, the invention is directed to a process for
preparing fully saturated oligomers including the further step of
hydrogenating the terminally unsaturated oligomer. The invention is
also directed to processes for forming oligomers of vinyl acetate
and oligomers of vinyl alcohol.
[0018] The process of the invention is useful for preparing
oligomers of the formula: 1
[0019] (I)
[0020] where
[0021] A, A.sup.1 and A.sup.2=independently selected from --H;
[0022] C.sub.1-C.sub.50 straight-chain or branched alkyl,
optionally substituted with a Y group;
[0023] C.sub.2-C.sub.50 straight-chain or branched alkenyl
containing 1-5 double bonds, optionally substituted with 1-2 Y
groups;
[0024] C.sub.5-C.sub.8 cycloalkyl, C.sub.5-C.sub.8
cycloalkenyl;
[0025] phenyl, (CH.sub.2).sub.m-phenyl, 1- or 2-naphthyl;
[0026] --(C.dbd.O)H;
[0027] --C(OR.sup.1).sub.2H;
[0028] --(C.dbd.O)R.sup.1, --(C.dbd.O)CF.sub.3;
[0029] --C(OR.sup.1).sub.2R.sup.1;
[0030] --(C.dbd.O)OR, --O(C.dbd.O)R.sup.1;
[0031] --(C.dbd.O)Cl;
[0032] --O(C.dbd.O)OR.sup.1;
[0033] --OR;
[0034] --(C.dbd.O)NH.sub.2, --(C.dbd.O)NHR.sup.1,
--(C.dbd.O)N(R.sup.1).su- b.2, --NH(C.dbd.O)R.sup.1,
--NH(C.dbd.O)H, --(C.dbd.O)NH(CH.sub.2).sub.m(N-
H.sub.3).sup.(+)(X).sup.(-),
--(C.dbd.O)NH(CH.sub.2).sub.m(NR.sup.1).sub.2- ;
[0035] --Si(OR.sup.1).sub.3, --Si(OR.sup.1).sub.2R.sup.1,
--Si(OR.sup.1)(R.sup.1).sub.2, --Si(R.sup.1).sub.3;
[0036] --F, --Cl, --Br, --I;
[0037] --C.ident.N;
[0038] oxiranyl;
[0039] --NH(C.dbd.O)NH.sub.2, --NH(C.dbd.O)NHR.sup.1,
--NH(C.dbd.O)N(R.sup.1).sub.2;. 2
[0040]
--CH.sub.2C.sub.nF.sub.2n+1,--CH.sub.2CH.sub.2C.sub.nF.sub.2n+1,
--CH(CF.sub.3).sub.2, --CH.sub.2C.sub.nF.sub.2nH,
--CH.sub.2CH.sub.2C.sub- .nF.sub.2nH;
[0041] --P(.dbd.O)(OR.sup.1).sub.3;
[0042] --S(.dbd.O).sub.2(OR.sup.1);
[0043] --S(.dbd.O).sub.2R.sup.1;
[0044] A.sup.3, A.sup.4=independently selected from --H, --F, --Cl,
--Br, R.sup.1;
[0045] E.sup.1, E.sup.2=independently selected from --H, 3
[0046] G.sup.1, G.sup.2=independently selected from --H,
--CH.sub.3, --(CH.sub.2).sub.mCO.sub.2R.sup.1, --F, --Cl, --Br,
--I;
[0047] M.sup.1, M.sup.2=independently selected from --H,
--C.ident.N, --(C.dbd.O)OR.sup.1, --F, --Cl, --Br, --I;
[0048] Q=C.sub.1-C.sub.8 straight-chain or branched alkyl,
--OR.sup.3, residue from radical decomposition of azo initiators
(azonitrile, azoamidine, cyclic azoamidine, azoamide, azoalkyl
classes) such as --C(R.sup.4).sub.2C.ident.N;
[0049] R=C.sub.1-C.sub.50 straight-chain or branched alkyl,
C.sub.2-C.sub.50 straight-chain or branched alkenyl containing 1-5
double bonds;
[0050] C.sub.5-C.sub.8 cycloalkyl, C.sub.5-C.sub.8
cycloalkenyl;
[0051] phenyl, (CH.sub.2).sub.m-phenyl, 1- or 2-naphthyl,
-4-benzoylphenyl (where any phenyl group may be substituted with up
to 2 R.sup.2), anthracenyl, anthracenylmethyl;
[0052] --(CH.sub.2).sub.mO(C.dbd.O)R.sup.1,
--(CH.sub.2).sub.m(C.dbd.O)OR- .sup.1;
[0053] --(CH.sub.2).sub.m(C.dbd.O)R.sup.1;
[0054] (CH.sub.2).sub.m(C.dbd.O)NH.sub.2,
--(CH.sub.2).sub.m(C.dbd.O)NHR.- sup.1,
[0055] --(CH.sub.2).sub.m(C.dbd.O)NH(R.sup.1).sub.2;
--(CH.sub.2).sub.m N(R.sup.1).sub.2,
--(CH.sub.2).sub.mNH.sub.3.sup.(+)X.sup.(-);
[0056] --(CH.sub.2).sub.mOR.sup.1,
--(CH.sub.2CH.sub.2O).sub.mR.sup.1,
--(CH.sub.2CH(CH.sub.3)O).sub.mR.sup.1, -2-tetrahydrofuranyl;
[0057] --(CH.sub.2).sub.mN.dbd.C.dbd.O;
[0058] --CH.sub.2C.sub.nF.sub.2n+1,
--CH.sub.2CH.sub.2C.sub.nF.sub.2n+1, --CH(CF.sub.3).sub.2,
--CH.sub.2C .sub.nF.sub.2nH,
--CH.sub.2CH.sub.2C.sub.nF.sub.2nH;
[0059] --(CH.sub.2)m 4
[0060] linear alkanes containing 1-5 epoxy groups derived from
(poly)unsaturated vegetable oils;
[0061] --(CH.sub.2).sub.pOH, --(CH.sub.2CH.sub.2O).sub.mH,
--[CH.sub.2CH(CH.sub.3)O].sub.mH;
[0062] --(CH.sub.2).sub.mSi(OR.sup.1).sub.3,
--(CH.sub.2).sub.mSi(R.sup.1- )(OR.sup.1).sub.2,
--(CH.sub.2).sub.mSi(R.sup.1).sub.2OR.sup.1,
--(CH.sub.2).sub.mSi(R.sup.1).sub.3; 5
[0063] --(CH.sub.2).sub.mO(C.dbd.O)CH.sub.2(C.dbd.O)R.sup.1;
[0064] R.sup.1=independently selected from C.sub.1-C.sub.8 straight
chain or branched alkyl where (R.sup.1).sub.2 may constitute a
C.sub.5-C.sub.8 cycloalkyl group; phenyl, --CH.sub.2phenyl;
[0065] R.sup.2=C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, --CHO,
--(C.dbd.O)OR.sup.1, --N(R.sup.1).sub.2, --NO.sub.2,
--(C.dbd.O)N(R.sup.1).sub.2, --CF.sub.3, --(C.dbd.O)R.sup.1;
[0066] --F, --Cl, --Br, --I;
[0067] R.sup.3=--H, C.sub.1-C.sub.8 straight chain or branched
alkyl, --R.sup.1(C.dbd.O), --R.sup.1(C.dbd.O)O;
[0068] R.sup.4=C.sub.1-C.sub.8 straight-chain alkyl,
C.sub.5-C.sub.8 cycloalkyl wherein the two adjacent R.sup.4groups
may together form a 5-8 membered ring, C.sub.1-C.sub.4
alkoxy-substituted straight-chain or branched C.sub.1-C.sub.8 alkyl
groups;
[0069] X.sup.(31)=--F.sup.(--), --Cl.sup.(-), --Br.sup.(-),
--I.sup.(-), --HSO.sub.4.sup.(-), --H.sub.2PO.sub.3.sup.(-);
[0070] Y=--OH, --F, --Cl, --Br, --I, --NH.sub.2,
--N(R.sup.1).sub.2;
[0071] m=1-8
[0072] n=1-18
[0073] p=2-8
[0074] x=0-49
[0075] y=0-49
[0076] z=0-49
[0077] x+y+z.ltoreq.49.
[0078] The invention is also directed to a mixture that
contains:
[0079] (1) about 50 to 90% by weight, based on the weight of the
mixture, of a first oligomer having terminal unsaturation of
Formula (I), where at least one of E.sup.1 and E.sup.2 is an
endgroup of the formula: 6
[0080] (II)
[0081] and when only one of E.sup.1 and E.sup.2 is an endgroup of
Formula (II) then the other endgroup is selected independently from
H, 7
[0082] (2) about 10 to 50% by weight, based on the weight of the
mixture, of a second oligomer having no terminal unsaturation of
Formula (I), wherein E.sup.1 and E.sup.2 are independently selected
from 8
DETAILED DESCRIPTION OF THE INVENTION
[0083] As used herein, the term "(meth)acrylate" refers to
methacrylate and acrylate, the term "(meth)acrylic" refers to
methacrylic and acrylic and the term "(meth)acrylamide" refers to
methacrylamide and acrylamide. As used herein, the term
"substantially free" means less than 0.5% by weight. As used
herein, the term "ambient conditions" means at a temperature of
20.degree. C.-40.degree. C. and at a pressure of 1 bar. As used
herein, the term "homooligomer" means an oligomer containing the
same monomer units and the term "co-oligomer" means an oligomer
containing at least two different monomer units. As used herein,
the term "neat" means a composition that contains only the oligomer
and is substantially free of solvent and other additives. As used
herein, the phrase "carboxylic-acid containing monomers and their
salts" means monoethylenically unsaturated monocarboxylic acids,
and the alkali metal, alkaline earth metal, and ammonium salts
thereof, and monoethylenically unsaturated dicarboxylic acids, and
the alkali metal, alkaline earth metal, and ammonium salts thereof,
and the anhydrides of the cis-dicarboxylic acids.
[0084] The first step of the process of the invention is forming a
reaction mixture, substantially free of carboxylic acid-containing
monomers and their salts, containing:
[0085] (a) from 0.5 to 99.95% by weight of the reaction mixture of
at least one ethylenically unsaturated monomer; and
[0086] (b) from 0.05 to 25% by weight, based on the weight of the
ethylenically unsaturated monomer, of at least one free-radical
initiator.
[0087] Preferably, the reaction mixture contains 10% to 99.9% by
weight, and most preferably, 50% to 98% by weight, based on the
weight of the reaction mixture, of at least one ethylenically
unsaturated monomer. Preferably, the reaction mixture contains 0.1%
to 5% by weight, and most preferably, 1% to 2% by weight, based on
the weight of the ethylenically unsaturated monomer, of at least
one free-radical initiator.
[0088] The process of the invention is suitable for polymerizing
any ethylenically unsaturated monomer, except carboxylic
acid-containing monomers and their salts. Suitable monomers
include, but are not limited to,
[0089] n-alkyl(meth)acrylates, such as methyl acrylate, butyl
methacrylate, octadecyl acrylate;
[0090] branched alkyl(meth)acrylates, such as isopropyl
methacrylate, 2-ethyl hexyl acrylate, isobornyl methacrylate;
[0091] cycloalkyl(meth)acrylates, such as cyclopentyl methyl
acrylate, cyclohexyl methacrylate;
[0092] straight chain or branched haloalkyl(meth)acrylates, such as
2,2,2-trifluoroethyl acrylate, hexafluoroisopropyl methacrylate,
2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl acrylate;
[0093] aromatic alkyl(meth)acrylates, such as benzyl acrylate,
4-chlorophenethyl methacrylate;
[0094] aromatic (meth)acrylates, such as phenyl acrylate, 4-benzoyl
phenyl acrylate;
[0095] hydroxyalkyl(meth)acrylates, such as 2-hydroxyethyl
acrylate, 4-hydroxybutyl methacrylate;
[0096] heterocyclyl(meth)acrylates, such as 3-oxazolidinyl ethyl
methacrylate, N-ethyl-ethylene ureido methacrylate;
[0097] aminoalkyl(meth)acrylates, such as N,N-dimethyl aminoethyl
acrylate and acid salts of 2-aminoethyl acrylate, N,N-diethyl
aminopropyl methacrylate;
[0098] ether-containing (meth)acrylates, such as ethoxyethoxyethyl
acrylate, 2-tetrahydrofuranyl acrylate, ethyl ether of a
polyalkoxylated ester of methacrylic acid;
[0099] silicon-containing (meth)acrylates, such as
trimethoxysilylpropyl acrylate, diethoxymethylsilylpropyl
methacrylate, isopropoxydimethylsilyl- propyl acrylate;
[0100] (meth)acrylamides, such as N-methyl acrylamide,
N,N-dimethylaminopropyl methacrylamide;
[0101] epoxide-containing (meth)acrylates, such as glycidyl
(meth)acrylate, (meth)acrylates derived from partially or
completely epoxidized (poly)unsaturated vegetable oils;
[0102] unsaturated alkyl(meth)acrylates, such as vinyl acrylate,
allyl methacrylate, 2,4 hexadienyl methacrylate;
[0103] (meth)acrylate esters derived from (poly)unsaturated
vegetable oils; terminal alkenes, such as ethylene, 1-hexene,
3-vinyl cyclohexene; aralkenes, such as styrene, 4-methyl styrene,
.alpha.c-methyl styrene, 4-methoxy styrene, 4-benzoyl styrene,
4-N,N-dimethylaminostyrene;
[0104] heterocyclyl alkenes, such as 2,-3,or 4-vinyl pyridines and
N-vinyl imidazole;
[0105] dienes, such as butadiene, isoprene, vinylidene chloride,
vinyl fluoride;
[0106] vinyl halides, such as vinyl chloride,
tetrafluoroethylene;
[0107] vinyl esters, such as vinyl acetate, vinyl benzoate;
[0108] vinyl ketones, such as methyl vinyl ketone;
[0109] aldehyde containing vinyl functionality, such as
(meth)acrolein and their acetal derivatives;
[0110] epoxyalkenes, such as 3,4-epoxybut-1-ene;
[0111] vinyl monomers, such as (meth)acrylonitrile, N-vinyl
formamide, N-vinyl acetamide, fumaronitrile;
[0112] vinylsilanes and alkoxyvinylsilanes, such as
vinyltrimethylsilane, vinyltrimethoxy silane,
vinyldiethoxymethylsilane;
[0113] unsaturated diesters, such as dimethylmaleate,
dibutylfumarate, diethyl itaconate;
[0114] functional (meth)acrylates, such as isocyanatoethyl
methacrylate, acryloylchloride, aceto acetoxylethyl
methacrylate
[0115] Preferred ethylenically unsaturated monomers include those
monomers whose neat homooligomer of a degree of polymerization of
about 5 to about 10 is a liquid under ambient conditions.
[0116] Suitable initiators for carrying out the processes of the
present invention are any conventional free-radical initiators
including, but are not limited to, hydrogen peroxide, certain alkyl
hydroperoxides, dialkyl peroxides, peresters, percarbonates,
persulfates, peracids, oxygen, ketone peroxides, azo initiators and
combinations thereof. Specific examples of some suitable initiators
include hydrogen peroxide, oxygen, t-butyl hydroperoxide,
di-tertiary butyl peroxide, tertiary-amyl hydroperoxide,
methylethyl ketone peroxide and combinations thereof.
[0117] The monomers may be polymerized as dilute solutions,
although the process does not require solvent, nor is the use of
solvents preferred. The reaction mixture may contain one or more
solvents at a level of from 0% to 99.5% by weight of the reaction
mixture, preferably from 30% to 97% by weight of the reaction
mixture, and most preferably from 50% to 95% by weight of the
reaction mixture. As the relative amount of one or more solvents in
the reaction mixture decreases, particularly below 60%, the
molecular weight and the polydispersity of the resulting oligomer
mixture increases. Suitable solvents for the process of the present
invention are capable of dissolving the one or more monomers,
especially under the supercritical fluid conditions of the process,
and the oligomers formed therefrom. Suitable solvents for the
present invention include, for example, ethers such as
tetrahydrofuran, ketones such as acetone; esters such as ethyl
acetate; alcohols such as methyl alcohol and butyl alcohol; alkanes
such as hexane and heptane; aromatic hydrocarbons such as benzene,
toluene and xylene; supercritical fluids such as carbon dioxide;
water; and mixtures thereof. Supercritical fluids such as carbon
dioxide are particularly useful because the solvent readily is
stripped from the product and may be recycled.
[0118] In the second step of the process of the present invention,
the reaction mixture is continuously passed through a heated zone,
wherein the reaction mixture is maintained at a temperature of at
least 150.degree. C. under elevated pressure. Once the reaction
mixture is formed, it is preferable to have the passing reaction
mixture reach the polymerization temperature as rapidly as
possible. Preferably, the reaction mixture reaches the
polymerization temperature within 2 minutes, more preferably within
1 minute, most preferably within 30 seconds. Prior to reaching the
reaction temperature, the reaction mixture may be at any suitable
temperature, preferably at a temperature of from room temperature
to 450.degree. C., most preferably from a temperature of from room
temperature to 60.degree. C. to 400.degree. C. The oligomerization
is conducted at a temperature of at least 150.degree. C., and is
preferably conducted at a temperature in the range of from
200.degree. C. to 500.degree. C., and most preferably at a
temperature in the range of from 275.degree. C. to 450.degree. C.
At temperatures below 150.degree. C., the molecular weight of the
oligomer increases and the relative amount of by-products, a
particularly non-terminally unsaturated compounds, increases.
[0119] The oligomerization at the elevated temperatures of the
process of the invention is rapid. Thus, the reaction mixture can
be maintained at the polymerization temperature for as little as
0.1 seconds up to 4 minutes, preferably from 0.5 seconds to 2
minutes, most preferably from 1 second to 1 minute. Under extended
periods of time at which the reaction mixture is exposed to the
polymerization temperature, the yield of terminally unsaturated
oligomer decreases. However, extended periods at the polymerization
temperature have been found to have little effect on both the
conversion of monomer and the molecular weight of the products
formed.
[0120] The elevated temperatures of the polymerization require that
the polymerization reactor be equipped to operate at elevated
pressure of at least 30 bars to maintain the contents of the
reactor as a fluid at the reaction temperature. In general, it is
preferred to conduct the polymerization at from 70 bars to 350
bars, and more preferably at from 200 bars to 300 bars.
[0121] In the process of the present invention, the ethylenically
unsaturated monomers, initiator and, optionally, solvent are
combined to form a reaction mixture. The order of combining the
components of the reaction mixture is not critical to the process
of the present invention. In one embodiment of the present
invention, it may be desirable to use one or more solvents, heat
the one or more solvents to an elevated temperature, and add the
one or more monomers and the at least one initiator to the heated
solvent to form the reaction mixture. It is preferred to add the
initiator last. The reaction mixture can be formed at a temperature
below, at or above the oligomerization temperature. In one
embodiment of the invention, it may be desirable to add an
additional amount of solvent to the oligomer product while the
oligomer product is at an elevated temperature to maintain
desirable fluidity and viscosity properties of the oligomer
product.
[0122] Reactors suitable for use in the process of invention
include tubular reactors having no moving parts and of any
cross-sectional shape that permit continuous, steady state flow and
that may operate under elevated temperatures and pressures. Such
reactors are typically made from inert materials, such as stainless
steel or titanium. The reactor may be of any length and
cross-sectional dimension that permits effective temperature and
pressure control.
[0123] Depending upon the final application of the oligomeric
products of the invention, the reaction mixture may optionally
contain metal ions, such as copper, nickel or iron ions or
combinations thereof. However, their presence is not preferred.
[0124] The process of the present invention generally results in a
relative conversion of the monomers into oligomer product of from
10% to greater than 95% relative to the initial amount of the one
or more monomers present in the reaction mixture. If residual
monomer levels in the oligomer mixture are unacceptably high for a
particular application, their levels can be reduced by any of
several techniques known to those skilled in the art, including
rotary evaporation, distillation, and vacuum distillation.
Preferably, any residual monomers which may be present in the
oligomer mixture are distilled or "stripped" and recycled for later
use.
[0125] The process of the present invention results in oligomers
having low molecular weights and narrow polydispersities.
Furthermore, embodiments of the process result in products that do
not require the removal of organic solvents (if none were used in
the process) and are not contaminated with high levels of salt. The
process of the present invention may be used to produce oligomers
having number average molecular weights below 5,000, preferably
below 3,000, and most preferably from 200 to 1,000.
[0126] The process of the invention may contain an optional third
step wherein the terminal unsaturation of the terminally
unsaturated oligomers is removed by hydrogenation under conditions
known to those skilled in the art, with or without solvent.
Preferably, the hydrogenation may be carried out utilizing a wide
variety of hydrogenation catalysts on an alkaline metal salt
support. Preferred metal catalysts include those comprising metals
selected from groups 3, 4, 5, 6 , 7, 8, 9, 10, 11 or 12 of the
Periodic Table of Elements as published in Chemical and Engineering
News 63(5), 27, 1985, is preferably present in the reaction at a
ratio of 0.01 to 5.0, and preferably 0.02 to 2.0 grams of catalyst
per gram of unsaturated oligomer. The degree of hydrogenation is
determined from proton NMR measurements at 25.degree. C. using
oligomer solutions in CDCl.sub.3 with TMS as the internal
reference. Upon hydrogenation the resonances associated with
olefinic protons are converted to aliphatic protons. Thus the
saturation efficiency can be measured by analyzing the remaining
olefinic proton resonances.
[0127] The process of the invention is useful for preparing
oligomers of the formula: 9
[0128] (I)
[0129] where
[0130] A, A.sup.1 and A.sup.2=independently selected from --H;
[0131] C.sub.1-C.sub.50 straight-chain or branched alkyl,
optionally substituted with a Y group;
[0132] C.sub.2-C.sub.50 straight-chain or branched alkenyl
containing 1-5 double bonds, optionally substituted with 1-2 Y
groups;
[0133] C.sub.5-C.sub.8 cycloalkyl, C.sub.5-C.sub.8
cycloalkenyl;
[0134] phenyl, (CH.sub.2).sub.m-phenyl, 1- or 2-naphthyl;
[0135] --(C.dbd.O)H;
[0136] --C(OR.sup.1).sub.2H;
[0137] --(C.dbd.O)R.sup.1, --(C.dbd.O)CF.sub.3;
[0138] --C(OR.sup.1).sub.2R.sup.1;
[0139] --(C.dbd.O)OR, --O(C.dbd.O)R.sup.1;
[0140] --(C.dbd.O)Cl;
[0141] --O(C.dbd.O)OR.sup.1;
[0142] --OR;
[0143] --(C.dbd.O)NH.sub.2, --(C.dbd.O)NHR.sup.1,
--(C.dbd.O)N(R.sup.1).su- b.2, --NH(C.dbd.O)R.sup.1,
--NH(C.dbd.O)H, --(C.dbd.O)NH(CH.sub.2).sub.m(N-
H.sub.3).sup.(+)(X).sup.(-),
--(C.dbd.O)NH(CH.sub.2).sub.m(NR.sup.1).sub.2- ;
[0144] --Si(OR.sup.1).sub.3, --Si(OR.sup.1).sub.2R.sup.1,
--Si(OR.sup.1)(R.sup.1).sub.2, --Si(R.sup.1).sub.3;
[0145] --F, --Cl, --Br, --I;
[0146] --C.ident.N; oxiranyl;
[0147] --NH(C.dbd.O)NH.sub.2, --NH(C.dbd.O)NHR.sup.1,
--NH(C.dbd.O)N(R.sup.1).sub.2; 10
[0148] --CH.sub.2C.sub.nF.sub.2n+1,
--CH.sub.2CH.sub.2C.sub.nF.sub.2n+1, --CH(CF,).sub.2,
--CH.sub.2C.sub.nF.sub.2nH, --CH.sub.2
CH.sub.2C.sub.nF.sub.2nH;
[0149] --P(.dbd.O)(OR.sup.1).sub.3; --S(.dbd.O).sub.2(OR.sup.1);
--S(.dbd.O).sub.2R.sup.1;
[0150] A.sup.3, A.sup.4=independently selected from --H, --F, --Cl,
--Br, R.sup.1;
[0151] E.sup.1, E.sup.2=independently selected from --H, 11
[0152] G.sup.1, G.sup.2=independently selected from --H,
--CH.sub.3, --(CH.sub.2).sub.mCO.sub.2R.sup.1, --F, --Cl, --Br,
--I;
[0153] M.sup.1, M.sup.2=independently selected from --H, --C.dbd.N,
--(C.dbd.O)OR.sup.1, --F, --Cl, --Br, --I;
[0154] Q=C.sub.1-C.sub.8 straight-chain or branched alkyl,
--OR.sup.3, residue from radical decomposition of azo initiators
(azonitrile, azoamidine, cyclic azoamidine, azoamide, azoalkyl
classes) such as --C(R.sup.4).sub.2C.ident.N;
[0155] R=C.sub.1-C.sub.50 straight-chain or branched alkyl,
C.sub.2-C.sub.50 straight-chain or branched alkenyl containing 1-5
double bonds;
[0156] C.sub.5-C.sub.8 cycloalkyl, C.sub.5-C.sub.8
cycloalkenyl;
[0157] phenyl, (CH.sub.2).sub.m-phenyl, 1- or 2-naphthyl,
-4-benzoylphenyl (where any phenyl group may be substituted with up
to 2 R.sup.2), anthracenyl, anthracenylmethyl;
[0158] --(CH.sub.2).sub.mO(C.dbd.O)R.sup.1,
--(CH.sub.2).sub.m(C.dbd.O)OR- .sup.1;
[0159] --(CH.sub.2).sub.m(C.dbd.O)R.sup.1;
[0160] --(CH.sub.2).sub.m(C.dbd.O)NH.sub.2,
--(CH.sub.2).sub.m(C.dbd.O)NH- R.sup.1,
--(CH.sub.2).sub.m(C.dbd.O)NH(R.sup.1).sub.2;
[0161] --(CH.sub.2).sub.mN(R.sup.1).sub.2,
--(CH.sub.2).sub.mNH.sub.3.sup- .(+)X.sup.(-);
[0162] --(CH.sub.2).sub.mOR.sup.1,
--(CH.sub.2CH.sub.2O).sub.mR.sup.1,
--(CH.sub.2CH(CH.sub.3)O).sub.mR.sup.1, -2-tetrahydrofuranyl;
[0163] --(CH.sub.2).sub.mN.dbd.C.dbd.O;
[0164] --CH.sub.2C.sub.nF.sub.2n+1,
--CH.sub.2CH.sub.2C.sub.F.sub.2n+1, --CH(CF.sub.3).sub.2,
--CH.sub.2C.sub.nF.sub.2nH, --CH.sub.2CH.sub.2C.sub-
.nF.sub.2nH;
[0165] --(C.sub.2).sub.m 12
[0166] linear alkanes containing 1-5 epoxy groups derived from
(poly)unsaturated vegetable oils;
[0167] --(CH.sub.2).sub.pOH, --(CH.sub.2CH.sub.2O).sub.mH,
--[CH.sub.2CH(CH.sub.3)O].sub.mH;
[0168] --(CH.sub.2).sub.mSi(OR.sup.1).sub.3,
--(CH.sub.2).sub.mSi(R.sup.1- )(OR.sup.1).sub.2,
--(CH.sub.2).sub.mSi(R.sup.1).sub.2R.sup.1,
--(CH.sub.2).sub.mSi(R.sup.1),.sup.3; 13
[0169] --(CH.sub.2).sub.mO(C.dbd.O)CH.sub.2(C.dbd.O)R.sup.1;
[0170] R.sup.1=independently selected from C.sub.1-C.sub.8 straight
chain or branched alkyl where (R.sup.1).sub.2 may constitute a
C.sub.5-C.sub.8 cycloalkyl group; phenyl, --CH.sub.2phenyl;
[0171] R.sup.2=C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, --CHO,
--(C.dbd.O)OR1, --N(R.sup.1).sub.2, --NO.sub.2,
--(C.dbd.O)N(R.sup.1).sub.2, --CF.sub.3, --(C.dbd.O)R.sup.1;
[0172] --F, --Cl, --Br, --I;
[0173] R.sup.3=--H, C.sub.1-C.sub.8 straight chain or branched
alkyl, --R.sup.1(C.dbd.O), --R.sup.1(C.dbd.O)O;
[0174] R.sup.4=C.sub.1-C.sub.18 straight-chain alkyl,
C.sub.5-C.sub.8 cycloalkyl wherein the two adjacent R.sup.4 groups
may together form a 5-8 membered ring, C.sub.1-C.sub.4
alkoxy-substituted straight-chain or branched C.sub.1-C.sub.8 alkyl
groups;
[0175] X.sup.(-)=--F.sup.(--), --Cl.sup.(-), --Br.sup.(-),
--I.sup.(-), --HSO.sub.4.sup.(-), --H.sub.2PO.sub.3.sup.(-);
[0176] Y=--OH, --F, --Cl, --Br, --I, --NH.sub.2,
--N(R.sup.1).sub.2;
[0177] m=1-8
[0178] n=1-18
[0179] p=2-8
[0180] x=0-49
[0181] y=0-49
[0182] z=0-49
[0183] x+y+z.ltoreq.49.
[0184] It is understood that the residues of the monomers, Z.sub.1,
Z.sub.2 and Z.sub.3, in the oligomers of Formula (I) above may be
randomly arranged to form alternating, random or block polymer
structures. It is also understood that, not only are homooligomers
and co-oligomers contemplated, but oligomers formed from more than
two different types of monomers, such as low molecular weight
terpolymers or "ter-oligomers", are also contemplated. In the
broadest sense, it is understood that in the oligomer where there
are up to 49 possible residues of monomers (whether of Z.sub.1,
Z.sub.2 or Z.sub.3 structure) the monomers are each independently
selected such that it would be possible to form an oligomer from 49
different monomers.
[0185] The process of the present invention is useful for producing
a mixture of oligomers containing:
[0186] (1) about 50 to 90% by weight, based on the weight of the
mixture, of a first oligomer having terminal unsaturation of
Formula (I), where at least one of E.sup.1 and E.sup.2 is an
endgroup of the formula: 14
[0187] (II) and when only one of E.sup.1 and E.sup.2 is an endgroup
of Formula (II) then the other endgroup is selected independently
from H, 15
[0188] (2) about 10 to 50% by weight, based on the weight of the
mixture, of a second oligomer having no terminal unsaturation of
Formula (I), wherein E.sup.1 and E.sup.2 are independently selected
from 16
[0189] The mixture may optionally contain an oligomer formed by a
chain-chain termination reaction.
[0190] Terminal unsaturation may be detected and measured by
conventional techniques, including .sup.1H NMR spectroscopy,
.sup.13C NMR spectroscopy, and bromine titration. The endgroups may
be identified by conventional techniques, including MALDI-MS.
[0191] The terminally-unsaturated oligomers, fully saturated
oligomers and mixtures of the invention may be supplied neat and
flow under ambient conditions. The consistency of the products
ranges from a thin, water-like fluid to a viscous, taffy-like
fluid. Furthermore, they do not require the use of water or other
solvents in the preparation or use and are substantially free of
contaminants, including, salts, surfactants, metals and the
like.
[0192] The oligomers of the invention may be used neat, provided in
solvent or provided emulsified in water with at least one
surfactant. The emulsified oligomer in water is preferred if the
neat form of the oligomer is too viscous for use in an application.
Suitable surfactants include conventional anionic, cationic,
nonionic, amphoteric surfactants and mixtures thereof. The
surfactant may be added at a level of at least 0.1% solids based on
the weight of the oligomer. The emulsified composition may be
prepared by mixing at least one surfactant, at least one oligomer,
water and mixing vigorously. Other minor components, such as
wetting agent, may be added to the emulsified composition.
Alternatively, the emulsified composition may be prepared by adding
the surfactant to the reaction mixture containing the ethylenically
unsaturated monomer and initiator prior to oligomerization.
[0193] The oligomers of the invention are useful in many
applications, including, for example, in binders and additives
(surfactants, emulsifiers, rheology modifiers) for architectural
coatings (paints, primers, lacquers, varnishes, stains, EIFS); in
industrial coatings (including automotive finishes, metal finishes,
printing inks and resins); in building products (wood coatings and
binders, caulks, sealants, concrete modifiers and coatings,
impregnants, polishes) in coatings and additives for paper,
textiles, and nonwovens; in adhesives; in leather chemicals; in
formulation chemicals (including detergents, dispersants, water
treatment, scale inhibitors, suspension aids); in plastics and
plastic additives (plasticizers, processing aids); in rubber and
rubber additives (plasticizers, processing aids); in biocides and
adjuvants; in agricultural chemicals and adjuvants; in electronic
chemicals; in ion exchange resins (adsorbents and adsorbents); in
oil additives; in solvents; in lubricants and hydraulic fluids; and
the like.
EXAMPLES
The Equipment and General Procedures
[0194] A 10 foot long section of stainless steel tubing having an
inner diameter of {fraction (1/16)}th inch and a wall thickness of
0.050 inch was connected at one end to a high pressure pump
(Hewlett Packard Model HP 1050 TI) and at another end to a
back-pressure control device. Between the two ends, the section of
tubing was coiled about a torus-shaped metal mandrel. The mandrel
was situated above a primary coil of a transformer so that the
coils of tubing and the mandrel functioned as secondary coils of
the transformer. The coils of tubing were further equipped with one
end of a temperature probe. The other end of the temperature probe
was connected to a temperature controlling device. The temperature
controlling device regulated the current supplied to the primary
coil of the transformer which had the effect of regulating the heat
of inductance imparted to the coiled steel tubing.
[0195] A reaction mixture was prepared by mixing solvent (if
present), monomers, comonomers (if present) and initiator. Nitrogen
was bubbled through the mixture while stirring. Under solvent-free
conditions, the initiator and monomers/comonomers were separately
fed into the reactor.
[0196] Solvent was pumped through the tubing via the high pressure
pump at a rate of from 0.05 to 10 milliliters per minute
("ml/min"). The pressure was maintained at a level of from 200 bars
to 350 bars. Current was supplied to the primary coil of the
transformer to increase the temperature within the tubing to the
desired polymerization temperature. After about 15 minutes, the
solvent being pumped through the tubing was replaced by the
reaction mixture which was continuously pumped through the tubing
at the same rate, temperature and pressure. After allowing a
suitable amount of time for the solvent to be cleared from the
tubing, product was collected as the effluent from the
back-pressure control device. When the reaction mixture was nearly
gone, solvent was pumped through the tubing at the same rate,
pressure and temperature as the reaction mixture. Solvent and
residual monomer were removed on a rotary evaporator.
[0197] Terminal unsaturation was detected and measured by both
.sup.1H NMR spectroscopy and .sup.13C NMR spectroscopy; endgroups
were identified by MALDI-MS.
[0198] Examples 1-103 are oligomerizations conducted according to
the general procedure outlined above. The reaction conditions and
final properties of the oligomers are shown in Table 1.
1TABLE 1 Viscosity Ethylenically Reactor of neat Unsaturated
Initiator Solvent Temperature oligomer T.sub.g.sup.7 Example
Monomer (BOM).sup.1 (w/w).sup.2 (.degree. C.) % Conversion.sup.3
M.sub.w/M.sub.n.sup.4 dp.sup.5 (cps).sup.6 (.degree. C.) 1 EA 1%
dTBP 50% in acetone 375 99 --/-- <7 -- -- 2 EA 1% dTBP 50% in
acetone 325 97 1670/640 7.3 -- 54 3 EA 1% dTBP 50% in acetone 250
97 2900/1080 10.9 -- -- 4 BA 2% dTBP none 300 82 2800/1000 -- --
-72 5 BA 1% dTBP 50% in 350 93-98 -- -- -- -80 .fwdarw. -75 heptane
6 BA 1% dTBP 50% in ethyl 350 93-98 -- -- -- -80 .fwdarw. -75
acetate 7 BA 1% dTBP 50% in acetone 350 93-98 -- -- -- -80 .fwdarw.
-75 8 BA 1% dTBP 50% in 300 93-98 -- 11.5 -- -80 .fwdarw. -75
heptane 9 BA 1% dTBP 50% in ethyl 300 93-98 -- 9.4 -- -80 .fwdarw.
-75 acetate 10 BA 1% dTBP 50% in acetone 300 93-98 -- 7.9 -- -80
.fwdarw. -75 11 BA 1% dTBP 50% in 250 93-98 -- 13.8 -- -80 .fwdarw.
-75 heptane 12 BA 1% dTBP 50% in ethyl 250 93-98 -- 12.4 -- -80
.fwdarw. -75 acetate 13 BA 1% dTBP 50% in acetone 250 93-98 -- 10.3
-- -80 .fwdarw. -75 14 BA 1% dTBP 50% in 200 93-98 -- 24.5 -- -80
.fwdarw. -75 heptane 15 BA 1% dTBP 50% in ethyl 200 93-98 -- 14.8
-- -80 .fwdarw. -75 acetate 16 BA 1% dTBP 50% in acetone 200 93-98
-- 14.5 -- -80 .fwdarw. -75 17 MA 1% dTBP 50% in acetone 325 85 --
9.0 -- -39 18 LA 1% dTBP 50% in 350 99 -- 15.8 -- -14 acetone/
(melting hexane point) 19 stearyl acrylate 1% dTBP 50% in 375 98 --
20.8 -- 19 heptane 20 2-EHA 2% dTBP 35% in acetone 285 95 2727/1487
-- cooking oil- -81 like 21 i-bornyl 1% dTBP 50% in acetone 325 96
-- -- 7 acrylate 22 styrene 2% dTBP 30% in ethyl 350 46 1350/674
7.8 -- -24 acetate 23 styrene 2% dTBP 30% in ethyl 300 43 1880/920
17 -- -7 acetate 24 styrene 2% dTBP 50% in toluene 350 73 2530/1360
14.7 -- 1 25 styrene 2% dTBP 50% in toluene 300 64 3630/1950 21.1
-- 13 26 styrene 2% dTBP 50% in toluene 250 56 4740/2310 25.1 -- 13
27 styrene 2% dTBP 50% in acetone 325 42 4680/1950 -- -- -- 28
styrene 2% dTBP 50% in acetone 275 44 4730/1850 -- -- -- 29 styrene
2% dTBP 50% in acetone 225 53 6155/2450 -- -- -- 30 VAc 4% dTBP 50%
in acetone 280 62 --/-- 8.7 -- -7 31 VAc 2% dTBP 50% in acetone 225
58 --/-- 10 -- 6 32 VAc.sup.8 1% dTBP 50% in acetone 190 62
5546/1936 16 -- 10 33 VAc 0.2% H.sub.2O.sub.2 none 325 40 7861/2331
-- -- -- 34 VAc 0.2% H.sub.2O.sub.2 none 375 45 4933/1493 -- -- --
35 VAc 0.2% tBHP none 325 53 6217/1488 -- -- -- 36 VAc 0.2% tBHP
none 375 50 4151/1187 -- -- -- 37 VAc 2% dTBP 50% in acetone 250 --
4734/1316 -- taffy-like -- 38 VAc 2% dTBP 50% in acetone 275 --
4310/1229 -- taffy-like -- 39 VAc 2% dTBP 50% in acetone 275 99
4800/1400* -- taffy-like -- 40 methylvinyl 2% H.sub.2O.sub.2 50% in
methyl 250 82 --/-- 13 -- -- ketone alcohol 41 methylvinyl 2%
H.sub.2O.sub.2 10% in methyl 250 21 --/-- 7 -- -- ketone alcohol 42
methylvinyl 0.1% tBHP 10% in methyl 250 44 --/-- 7 -- -- ketone
alcohol 43 methylvinyl 2% H.sub.2O.sub.2 10% in water 375 70 --/--
5 -- -- ketone 44 MMA 2% dTBP 50% in acetone 200 20 --/--
<5.sup.9 -- -37, -9 45 MMA 2% dTBP 50% in acetone 180 24 --/--
<5.sup.9 -- -20, -1 46 MMA 2% dTBP 50% in acetone 160 27 --/--
30-40.sup.9 -- 68 47 MMA 2% dTBP 50% in acetone 140 22 --/--
>60.sup.9 -- 98 Compar- ative 48 VTMO 2% dTBP 50% in acetone 210
51 1150/800 7.4 -- -76 49 allyl alcohol 2% H.sub.2O.sub.2 25% in
water 350 15-20 --/-- -- -- 106 50 allyl alcohol 2% H.sub.2O.sub.2
25% in water 300 15-20 --/-- -- -- -- 51 allyl alcohol 2%
H.sub.2O.sub.2 25% in water 250 15-20 --/-- -- -- -- 52 allyl
alcohol 2% H.sub.2O.sub.2 25% in water 200 15-20 --/-- -- -- 106 53
isoprene 1% dTBP 50% in toluene 300 47 13700/3995 -- -- -- 54
isoprene 1% dTBP 50% in toluene 225 31 22550/5738 -- -- -59 55
acrylamide 1% H.sub.2O.sub.2 20% in water 200 85-95 --/-- -- -- 124
56 EA/MMA.sup.11 2% dTBP 50% in acetone 350 91/47 --/-- 5 -- -- 57
EA/MMA.sup.11 2% dTBP 50% in acetone 300 87/56 --/-- 6 -- -- 58
EA/MMA.sup.11 2% dTBP 50% in acetone 250 67/56 --/-- 12 -- -17 59
EA/MMA.sup.11 2% dTBP 50% in acetone 200 66/66 --/-- -- -- -- 60
100 EA/0 MMA 1% dTBP 50% in acetone 250 99/-- --/-- Mn = 1076 --
-54 61 50 EA/50 MMA 1% dTBP 50% in acetone 250 67/56 --/-- Mn =
1270 -- -17 62 25 EA/75 MMA 1% dTBP 50% in acetone 300 91/41 --/--
Mn = 830 -- -56 63 25 EA/75 MMA 1% dTBP 50% in acetone 250 79/37
--/-- Mn = 900 -- -44 64 25 EA/75 MMA 1% dTBP 50% in acetone 200
54/35 --/-- Mn = 1300 -- -18 65 15 EA/85 MMA 1% dTBP 50% in acetone
300 89/37* --/-- -- -- -61 66 15 EA/85 MMA 1% dTBP 50% in acetone
250 81/29* --/-- -- -- -48 67 15 EA/85 MMA 1% dTBP 50% in acetone
200 50/24* --/-- Mn = 950 -- -24 68 EA/styrene.sup.10 2% dTBP 50%
in acetone 350 93/87 --/-- Mn = 620 -- -- 69 EA/styrene.sup.10 2%
dTBP 50% in acetone 300 85/88 --/-- Mn = 710 -- -- 70
EA/styrene.sup.10 2% dTBP 50% in acetone 250 69/79 --/-- Mn = 1209
-- -- 71 EA/styrene.sup.10 2% dTBP 50% in acetone 200 63/74 --/--
Mn = 1810 -- -- 72 MMA/styrene.sup.10 2% dTBP 50% in acetone 320
50/70 --/-- <5 -- -- 73 MMA/styrene.sup.10 2% dTBP 50% in
acetone 300 49/64 --/-- <5 -- -- 74 MMA/styrene.sup.10 2% dTBP
50% in acetone 280 47/61 --/-- <5 -- -- 75 MMA/styrene.sup.10 2%
dTBP 50% in acetone 260 47/57 --/-- <5 -- -- 76 BA/VAc.sup.10 2%
dTBP 50% in acetone 350 99/78 --/-- Mn = 790 -- -50 77
BA/VAc.sup.10 2% dTBP 50% in acetone 300 99/67 --/-- Mn = 1056 --
-53 78 BA/VAc.sup.10 2% dTBP 50% in acetone 250 99/64 --/-- Mn =
1283 -- -51 79 BA/VAc.sup.10 2% dTBP 50% in acetone 200 98/55 --/--
Mn = 1740 -- -42 80 BA/VAc.sup.10 2% dTBP 50% in acetone 150 94/41
--/-- Mn = 5720 -- -32 81 MMA/VAc.sup.10 2% dTBP 50% in acetone 300
73/69 --/-- Mn = 782 -- -9 82 MMA/VAc.sup.10 2% dTBP 50% in acetone
250 38/29 --/-- Mn = 1252 -- 4 83 MMA/VAc.sup.10 2% dTBP 50% in
acetone 200 35/20 --/-- Mn = 1436 -- 7 84 MMA/VAc.sup.10 2% dTBP
50% in acetone 150 24/13 --/-- Mn = 4470 -- 25 85
styrene/VAc.sup.10 2% dTBP 50% in acetone 300 68/21 --/-- Mn = 854
-- -12 86 styrene/VAc.sup.10 2% dTBP 50% in acetone 250 59/14 --/--
Mn = 1113 -- 7 87 styrene/VAc.sup.10 2% dTBP 50% in acetone 200
63/14 --/-- Mn = 1490 -- 34 88 styrene/VAc.sup.10 2% dTBP 50% in
acetone 150 30/10 --/-- Mn = 2830 -- 69 89 1.1 mol 2% dTBP none 300
-- 1700/700 -- 200 -72 EA/VTMO 90 2:1 mol 2% dTBP none 300 --
1100/590 -- 130 -67 EA/VTMO 91 BA/VTMO 2% dTBP none 300 -- 2100/900
-- 190 -75 92 2:1 mol 2% dTBP 50% in acetone 330 -- 3058/946.sup.11
-- syrup -48 EA/HEA 93 2:1 mol 2% dTBP 50% in acetone 330 --
3700/1200.sup.11 -- 5100 at -45 EA/HEA 25.degree. C. 94 4:1 mol 2%
benzoyl 30% in acetone 260 -- 1840/800 .about.8 8300 at -36 EA/GA
peroxide 25.degree. C. 95 40 BA/60 allyl 2% tBHP 50% in butyl 300
99/50 921/638 -- -- -- alcohol alcohol 96 40 BA/60 allyl 2% tBHP
50% in butyl 225 78/41 1580/1030 -- -- -- alcohol alcohol 97 40
BA/60 allyl 2% tBHP 50% in butyl 200 60/36 2208/1391 -- -- --
alcohol alcohol 98 45 VAc/28 BA/ 2% tBHP none 200 23/78/84
6086/1448 -- -- -- 25 Sty 99 45 VAc/28 BA/ 2% tBHP none 250
20/74/80 4386/1015 -- -- -- 25 Sty 100 45 VAc/28 BA/ 2% tBHP none
275 26/83/87 3786/914 -- -- -- 25 Sty 101 45 VAc/28 BA/ 2% tBHP
none 300 34/93/94 3288/810 -- -- -- 25 Sty 102 45 VAc/28 BA/ 2%
tBHP none 325 45/97/97 2865/683 -- -- -- 25 Sty 103 45 VAc/28 BA/
2% tBHP none 350 53/99/98 2435/560 -- -- -- 25 Sty Abbreviations
used in table: EA = ethyl acrylate; BA = butyl acrylate; MA =
methyl acrylate; LA = lauryl acrylate; VAc = vinyl acetate MMA =
methyl methacrylate; VTMO = vinyltrimethoxysilane; HEA =
hydroxyethyl acrylate; GA = glycidyl acrylate; dTBP = di-t-butyl
peroxide; tBHP = tertbutylhydroperoxide; H.sub.2O.sub.2 = hydrogen
peroxide .sup.1Based on weight of monomer .sup.2Percentage of
weight of solvent based on weight of total composition
.sup.3Conversion was measured as a function of product solids, and
was also determined by residual monomer analysis using high
pressure liquid chromatography or gas chromatography .sup.4Measured
by gel permeation chromatography (GPC) using an oligomeric butyl
acrylate or oligomeric ethyl acrylate standard unless specifically
stated otherwise .sup.5Degree of polymerization as measured by
.sup.1H NMR unless specifically stated otherwise. .sup.6Viscosity
measured by a Brookfield viscometer at 25.degree. C. .sup.7Measured
by differential scanning calorimetry at a rate of 20.degree.
C./minute unless specifically stated otherwise .sup.8Neat
oligomeric product was subsequently added to methanol and boiled
with 1% sodium hydroxide until oligomeric vinyl alcohol
precipitated. After solvent removal, the degree of hydrolysis was
determined at > 90% with Mw/Mn = 2850/990 (calculated from
oligomeric vinyl acetate). The T.sub.g was measured at 40.degree.
C. (conventional oligomeric vinyl acetate has Tg of 80.degree. C.).
Oligomeric vinyl acetate readily dissolves to >40% # solids in
water with gentle stirring (conventional oligomeric vinyl acetate
requires prolonged heating to dissolve). .sup.9Estimated from
T.sub.g and a published plot of T.sub.g v. dp. [Haggard et al.,
Prog. Org. Coatings, Volume 12, No. 1, page 19 (1984)] .sup.1050:50
mole ratio .sup.11Determined using pMMA standards and converted to
oBA standards using the following equations (assuming linearity and
accuracy at higher molecular weights) M.sub.w(oBA std) = 432 +
0.447 M.sub.w(pMMA std) M.sub.n(oBA std) = 169 + 0.713 M.sub.n(pMMA
std)
[0199] All of the examples of the invention were liquid, ranging
from low viscosity to high viscosity, when provided neat, whether
or not the reaction mixture contained the optional solvent during
the process of manufacture.
[0200] While only a few embodiments of the invention have been
shown and described herein, it will become apparent to those
skilled in the art that various modifications and changes can be
made in the process and compositions without departing from the
scope of the present invention.
* * * * *