U.S. patent application number 11/199392 was filed with the patent office on 2006-03-09 for process for producing branched polymer and polymer.
This patent application is currently assigned to Kaneka Corporation. Invention is credited to Masayuki Fujita, Kenichi Kitano, Yoshiki Nakagawa, Shigeki Ono.
Application Number | 20060052563 11/199392 |
Document ID | / |
Family ID | 26495112 |
Filed Date | 2006-03-09 |
United States Patent
Application |
20060052563 |
Kind Code |
A1 |
Nakagawa; Yoshiki ; et
al. |
March 9, 2006 |
Process for producing branched polymer and polymer
Abstract
This invention is related to a production method of a branched
polymer which comprises polymerizing a macromonomer [I], said
macromonomer [I] being a vinyl polymer obtainable by radical
polymerization and terminally having one polymerizable
carbon-carbon double bond-containing group per molecule.
Furthermore, by producing the macromonomer by living radical
polymerization, in particular atom transfer radical polymerization,
it becomes possible to produce the above polymers or gels having a
well controlled side chain molecular weights.
Inventors: |
Nakagawa; Yoshiki;
(Kobe-shi, JP) ; Ono; Shigeki; (Kobe-shi, JP)
; Fujita; Masayuki; (Kobe-shi, JP) ; Kitano;
Kenichi; (Kobe-shi, JP) |
Correspondence
Address: |
CONNOLLY BOVE LODGE & HUTZ LLP
SUITE 800
1990 M STREET NW
WASHINGTON
DC
20036-3425
US
|
Assignee: |
Kaneka Corporation
Osaka-shi
JP
|
Family ID: |
26495112 |
Appl. No.: |
11/199392 |
Filed: |
August 9, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09719580 |
Mar 9, 2001 |
6979716 |
|
|
PCT/JP99/03275 |
Jun 18, 1999 |
|
|
|
11199392 |
Aug 9, 2005 |
|
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|
Current U.S.
Class: |
526/318.44 ;
525/135; 525/145; 525/147; 525/172; 526/268; 526/269; 526/312;
526/317.1 |
Current CPC
Class: |
C08F 290/04 20130101;
C08F 299/00 20130101; C08F 2438/01 20130101; C08F 290/046 20130101;
C08F 290/06 20130101; C08F 291/00 20130101 |
Class at
Publication: |
526/318.44 ;
526/268; 526/269; 526/312; 526/317.1; 525/135; 525/145; 525/147;
525/172 |
International
Class: |
C08F 20/10 20060101
C08F020/10 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 19, 1998 |
JP |
10/172960 |
Jun 19, 1998 |
JP |
10/172961 |
Claims
1-32. (canceled)
33. A branched polymer obtainable by the production method
comprising performing living radical polymerization to obtain a
macromonomer [I], said macromonomer [I] being a vinyl polymer
terminally having one polymerizable carbon-carbon double
bond-containing group per molecule, and polymerizing said
macromonomer [I] wherein the macromonomer [I] has a weight average
molecular weight (Mw)-to-number average molecular weight (Mn) ratio
(Mw/Mn) of less than 1.8 as determined by gel permeation
chromatography, wherein the polymerizable carbon-carbon double
bond-containing group is represented by the general formula (1):
OC(O)C(R).dbd.CH.sub.2 (1) wherein R represents a hydrogen atom or
a monovalent organic group containing 1 to 20 carbon atoms:
34. A thermoplastic elastomer comprising the polymer according to
claim 33.
35. A shock resistance improver comprising the polymer according to
claim 33.
36. A pressure sensitive adhesive comprising the polymer according
to claim 33.
37. The branched polymer according to claim 32 wherein R is H or a
methyl group.
38. The branched polymer according to claim 32 wherein the living
radical polymerization is atom transfer radical polymerization.
39. The branched polymer according to claim 38 wherein the atom
transfer radical polymerization is carried out using, as a
catalyst, a transition metal complex whose central metal is an
element of the group 7, 8, 9, 10 or 11 of the periodic table.
40. The branched polymer according to claim 39 wherein the metal
complex to serve as a catalyst is a complex of a metal selected
from the group consisting of copper, nickel, ruthenium and
iron.
41. The branched polymer according to claim 32 wherein the polymer
main chain of the macromonomer (I) is an acrylic (meth)polymer.
42. The branched polymer according to claim 41 wherein the polymer
main chain of the macromonomer (I) is an acrylic ester polymer.
43. The branched polymer according to claim 32 wherein the main
chain of the macromonomer (I) is a styrene type polymer.
44. The branched polymer according to claim 32 wherein the
macromonomer (I) is obtained by substituting a compound having a
radical-polymerizable carbon-carbon double bond for a terminal
halogen group of a vinyl polymer.
45. The branched polymer according to claim 44 wherein the
macromonomer (I) is obtained by reacting a vinyl polymer having a
terminal halogen group represented by the general formula (2):
--CR.sup.1R.sup.2X (2) wherein R.sup.1 and R.sup.2 each represents
a group attached to an ethylenically unsaturated group of a vinyl
monomer and X represents a chlorine, bromine or iodine atom, with a
compound represented by the general formula (3):
M.sup.+-OC(O)C(R).dbd.CH.sub.2 (3) wherein R represents a hydrogen
atom or a monovalent organic group containing 1 to 20 carbon atoms
and M.sup.+ represents an alkali metal or a quaternary ammonium
ion, for substitution for the terminal halogen group.
46. The branched polymer according to claim 32 wherein the
macromonomer (I) is obtained by reacting a hydroxy-terminated vinyl
polymer with a compound represented by the general formula (4):
XC(O)C(R).dbd.CH.sub.2 (4) wherein R represents a hydrogen atom or
a monovalent organic group containing 1 to 20 carbon atoms and X
represents a chlorine, bromine atom or a hydroxyl group.
47. The branched polymer according to claim 32 wherein the
macromonomer (I) is obtained by reacting a hydroxy-terminated vinyl
polymer with a diisocyanate compound and reacting the remaining
isocyanato group with a compound represented by the general formula
(5): HO--R'--OC(O)C(R).dbd.CH.sub.2 (5): wherein R represents a
hydrogen atom or a monovalent organic group containing 1 to 20
carbon atoms and R' represents a divalent organic group containing
2 to 20 carbon atoms.
48. The branched polymer according to claim 32 wherein the
macromonomer (I) has a number average molecular weight of not less
than 3,000.
49. A branched polymer obtainable by the production method
comprising performing radical living polymerization to obtain a
macromonomer (I), said macromonomer (I) being a vinyl polymer
terminally having one polymerizable carbon-carbon double
bond-containing group per molecule, and polymerizing said
macromonomer (I) in the manner of living radical polymerization,
wherein the polymerizable carbon-carbon double bond-containing
group is represented by the general formula (1):
--OC(O)C(R).dbd.CH.sub.2 (1) wherein R represents a hydrogen atom
or a monovalent organic group containing 1 to 20 carbon atoms.
50. The branched polymer according to claim 32 wherein
homopolymerization of the macromonomer (I) gives a stellar
polymer.
51. The branched polymer according to claim 32 wherein the
copolymerization of the macromonomer (I) with a copolymerizable
monomer (II) other than said macromonomer (I) gives a graft
copolymer.
52. The branched polymer according to claim 51, wherein the weight
ratio between the macromonomer (I) and the monomer (II) is 95:5 to
5:95.
Description
[0001] This application is a Divisional of application Ser. No.
09/719,580, filed Mar. 9, 2001, which is a National Stage of
PCT/JP99/03275 in turn claims priority from Japanese Applications
10/172960, filed Jun. 19, 1998, and 10/172,961, filed Jun. 19,
1998.
TECHNICAL FIELD
[0002] The present invention relates to a production method of a
branched polymer by polymerizing a vinyl polymer-based macromonomer
having a terminal polymerizable carbon-carbon double bond.
BACKGROUND ART
[0003] Side by side with block copolymers, graft copolymers having
a comb-like structure have attracted considerable attention in the
field of macromolecular materials for the reason that these
polymers have characteristics of constituent segments, as can be
seen with thermoplastic elastomers and shock resistant plastics,
and at the same time can express unique functions based on their
microscopic phase separation structure.
[0004] Graft polymers have long been used in modifying polymers. It
is, however, only recently that polymers with a well controlled
structure were successfully synthesized. The concept of
"macromolecular monomers" was developed by Milkovich and his
colleagues and, by copolymerizing such monomers, it is now possible
to synthesize polymers having a well-defined comb-like
structure.
[0005] On the other hand, stellar polymers have linear polymer arms
radially extending from the core thereof are known to have various
properties distinct from those of linear polymers.
[0006] Roughly classified, two methods are available for the
synthesis of stellar polymers. One method comprises causing arm
polymers to grow from a compound or polymer, which serves as a
core, while the other comprises first preparing polymer arms and
then joining them together to form a stellar structure. For joining
arms together, there may be mentioned the technique comprising
reacting a compound having a plurality of functional groups capable
of reacting with the terminal functional groups of the
arm-polymers, the technique comprising adding a compound having a
plurality of polymerizable groups after preparation of arms by
polymerization, and the technique comprising polymerizing a polymer
having a terminal polymerizable group (hereinafter referred to as
"macromonomer"), among others.
[0007] Such stellar polymers are constituted of homopolymers and
copolymers of various kinds, such as polystyrenes,
poly(meth)acrylates, polydienes, polyethers, polyesters and
polysiloxanes. For obtaining a controlled stellar structure, it is
necessary, irrespective of method of production, for the
polymerization to be controlled. Therefore, the anionic
polymerization, living cationic polymerization or polycondensation
technique is employed in most instances.
[0008] Contrary to those polymers obtainable by ionic
polymerization or polycondensation, such as specifically mentioned
above, those vinyl polymers which are obtainable by radical
polymerization and have a stellar structure have scarcely been put
to practical use. In particular, any method has not yet been
successfully developed for causing chain extension or constructing
a stellar structure through binding of macromonomer molecules.
Generally, vinyl polymers have those characteristics which the
above-mentioned polyether polymers, hydrocarbon polymers or
polyester polymers cannot have, for example high weathering
resistance and transparency and, therefore, those having an alkenyl
group or a crosslinkable silyl group on a side chain thereof are
utilized in high weathering resistance coating compositions, for
instance.
[0009] While graft polymers and stellar polymers can be obtained by
using macromonomers, it is not yet easy to synthesize the
macromonomers. In particular, it is difficult to control the
polymerization in preparing vinyl polymer macromonomers to be
generally subjected to radical polymerization, hence few such
macromonomers have been synthesized. It is not easy, because of
side reactions, to control the polymerization of acrylic polymers,
among others, and, therefore, it is difficult to produce
macromonomers having a terminal polymerizable group.
[0010] Accordingly, it is an object of the invention to provide a
production method of a branched polymer using vinyl polymer
macromonomers prepared by radical polymerization.
SUMMARY OF THE INVENTION
[0011] The invention thus provides a production method of a
branched polymer by polymerizing a macromonomer (I),
[0012] said macromonomer (I) being a vinyl polymer obtainable by
radical polymerization and having one polymerizable carbon-carbon
double bond-containing group at one molecular terminus thereof per
molecule.
[0013] The polymerizable carbon-carbon double bond-containing group
is preferably represented by the general formula (1):
--OC(O)C(R).dbd.CH.sub.2 (1) wherein R represents a hydrogen atom
or a monovalent organic group containing 1 to 20 carbon atoms and,
more preferably, is a hydrogen atom or a methyl group.
[0014] The main chain of the macromonomer (I) is not particularly
restricted but preferably is produced by living radical
polymerization, more preferably by atom transfer radical
polymerization. The atom transfer radical polymerization is
preferably carried out using, as a catalyst, a transition metal
complex whose central metal is an element of the group 7, 8, 9, 10
or 11 of the periodic table of the elements, more preferably a
metal complex the metal of which is selected from the group
consisting of copper, nickel, ruthenium and iron, in particular a
copper complex.
[0015] The main chain of the macromonomer (I) is not restricted but
preferably includes (meth) acrylic polymers and styrene type
polymers, more preferably acrylic ester polymers.
[0016] The macromonomer (I) is not restricted but preferably those
obtainable by substituting a compound having a
radical-polymerizable carbon-carbon double bond for a terminal
halogen group of a vinyl polymer, more preferably those obtainable
by reacting a vinyl polymer having a terminal halogen group
represented by the general formula (2): --CR.sup.1R.sup.2X (2)
wherein R.sup.1 and R.sup.2 each represents a group attached to an
ethylenically unsaturated group of a vinyl monomer and X represents
a chlorine,.bromine or iodine atom, with a compound represented by
the general formula (3): M.sup.+-OC(O)C(R).dbd.CH.sub.2 (3) wherein
R represents a hydrogen atom or a monovalent organic group
containing 1 to 20 carbon atoms and M.sup.+ represents an alkali
metal or a quaternary ammonium ion, for substitution for said
compound.
[0017] Further, the macromonomer (I) is preferably obtainable by
reacting a hydroxy-terminated vinyl polymer with a compound
represented by the general formula (4): XC(O)C(R).dbd.CH.sub.2 (4)
wherein R represents a hydrogen atom or a monovalent organic group
containing 1 to 20 carbon atoms and X represents a chlorine or
bromine atom or a hydroxy group, or by reacting a
hydroxy-terminated vinyl polymer with a diisocyanate compound and
then reacting the residual isocyanato group with a compound
represented by the general formula (5):.
HO--R'--OC(O)(R).dbd.CH.sub.2 (5) wherein R represents a hydrogen
atom or a monovalent organic group containing 1 to 20 carbon atoms
and R' represents a divalent organic group containing 2 to 20
carbon atoms. Among them, the one obtainable by the terminal
halogen substitution method mentioned above is preferred.
[0018] The number average molecular weight of the polymeric
macromonomer (I) is not restricted but preferably is not less than
3,000, and the weight average molecular weight (Mw)-to-number
average molecular weight (Mn) ratio (Mw/Mn) of the macromonomer (I)
as determined by gel permeation chromatography is preferably less
than 1.8.
[0019] The method of polymerizing the macromonomer (I) in
accordance with the present invention is not restricted but
preferably is radical polymerization, more preferably living
radical polymerization, still more preferably atom transfer radical
polymerization. The atom transfer radical. polymerization is
carried out using, as a catalyst, a transition metal complex the
central metal of which is an element of the group 7, 8, 9, 10 or 11
of the periodic table of the elements, more preferably a metal
complex the metal of which is selected from the group consisting of
copper, nickel, ruthenium and iron, in particular a copper
complex.
[0020] As the method of polymerizing the macromonomer (I) are
preferably initiated by active radiation and the application of
heat.
[0021] The polymerization of the macromonomer (I) may also be
conducted in the manner of anionic polymerization.
[0022] Homopolymerization of the macromonomer (I) according to the
present invention gives a stellar polymer, while copolymerization
of the macromonomer (I) with a copolymerizable monomer (II) other
than the macromonomer gives a graft copolymer. Further,
copolymerization of the macromonomer (I) with a polyfunctional
compound having two or more polymerizable carbon-carbon double
bonds per molecule, preferably a polymer (III) having such double
bonds at the molecular termini thereof, gives a crosslinked polymer
(gel).
[0023] The present invention also covers a branched polymer
obtainable by the method of the invention.
[0024] The polymers of the invention are not restricted in their
applications but, for example, they are used as thermoplastic
elastomers, impact resistance modifiers and adhesives.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The present invention is directed to a production method of
a branched polymer which comprises polymerizing a macromonomer (I),
said macromonomer (I) being a vinyl polymer obtainable by radical
polymerization and having one polymerizable carbon-carbon double
bond-containing group at one molecular terminus thereof per
molecule.
[0026] The polymerizable carbon-carbon double bond-containing group
is preferably represented by the above general formula (1).
[0027] Referring to the general formula (1), a specific example of
R is not particularly restricted as far as it is a monovalent
organic group containing 1 to 20 carbon atoms, but includes
substituted or unsubstituted hydrocarbon groups containing 1 to 20
carbon atoms, ether groups, acyl groups, carbon- and
nitrogen-containing groups, carbon- and sulfur-containing groups,
carbon- and oxygen-containing groups, more specifically, --H,
--CH.sub.3, --CH.sub.2CH.sub.3, --(CH.sub.2).sub.nCH.sub.3 (n being
an integer of 2 to 19), --C.sub.6H.sub.5, --CH.sub.2OH, --CN and so
forth. Preferred are --H and --CH.sub.3, however.
<Main Chain of the Macromonomer (I)>
Monomer
[0028] The monomer constituting the main chain of the macromonomer
(I) according to the invention is not particularly restricted but
includes various species. As examples, there may be mentioned
(meth)acrylic acid, methyl(meth)acrylate, ethyl(meth)acrylate,
n-propyl(meth)acrylate, isopropyl(meth)acrylate,
n-butyl(meth)acrylate, isobutyl(meth)acrylate,
tert-butyl(meth)acrylate, n-pentyl(meth)acrylate,
n-hexyl(meth)acrylate, cyclohexyl(meth)acrylate,
n-heptyl(meth)acrylate, n-octyl(meth)acrylate,
2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate,
decyl(meth)acrylate, dodecyl(meth)acrylate, phenyl(meth)acrylate,
tolyl(meth)acrylate, benzyl(meth)acrylate,
2-methoxyethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate,
2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,
stearyl(meth)acrylate, glycidyl(meth)acrylate,
2-aminoethyl(meth)acrylate,
.gamma.-(methacryloyloxypropyl)trimethoxysilane, adducts of
(meth)acrylic acid with ethylene oxide,
trifluoromethylmethyl(meth)acrylate,
2-trifluoromethylethyl(meth)acrylate,
2-perfluoroethylethyl(meth)acrylate,
2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate,
2-perfluoroethyl(meth)-acrylate, perfluoromethyl(meth)acrylate,
diperfluoromethylmethyl(meth)acrylate,
2-perfluoromethyl-2-perfluoroethylmethyl(meth)acrylate,
2-perfluorohexylethyl(meth)acrylate,
2-perfluorodecylethyl(meth)acrylate,
2-perfluorohexadecylethyl(meth)acrylate and like (meth)acrylic
monomers; styrene, vinyltoluene, .alpha.-methylstyrene,
chlorostyrene, styrenesulfonic acid and salts thereof and like
styrene type monomers; perfluoroethylene, perfluoropropylene,
vinylidene fluoride and like fluorine-containing vinyl monomers;
vinyltrimethoxysilane, vinyltriethoxysilane and like
silicon-containing vinyl monomers; maleic anhydride, maleic acid,
maleic acid monoalkyl esters and dialkyl esters; fumaric acid,
fumaric acid monoalkyl esters and dialkyl esters; maleimide,
methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,
hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide,
phenylmaleimide, cyclohexylmaleimide and like maleimide monomers;
acrylonitrile, methacrylonitrile and like nitrile group-containing
vinyl monomers; acrylamide, methacrylamide and like amide
group-containing vinyl monomers; vinyl acetate, vinyl propionate,
vinyl pivalate, vinyl benzoate, vinyl cinnamate and like vinyl
esters; ethylene, propylene and like alkenes; butadiene, isoprene
and like conjugated dienes; vinyl chloride, vinylidene chloride,
allyl chloride and allyl alcohol, among others. These may be used
singly or a plurality of such monomers maybe copolymerized. Among
them, styrene type monomers and (meth)acrylic monomers are
preferred from the standpoint of physical properties of products,
among others. Acrylic ester monomers and methacrylic ester monomers
are more preferred and butyl acrylate is still more preferred. In
the practice of the invention, these preferred monomers may be
copolymerized with some other monomer(s) and, in that case, the
proportion of the preferred monomers is preferably 40% by
weight.
[0029] The macromonomer (I) according to the invention has a
molecular weight distribution, namely the ratio of weight average
molecular weight to number average molecular weight as determined
by gel permeation chromatography, of less than 1.8, preferably not
more than 1.7, more preferably not more than 1.6, still more
preferably not more than 1.5, in particular not more than 1.4 and
most preferably not more than 1.3. In the practice of the
invention, the GPC determination is generally carried out on a
polystyrene column, among others, using chloroform or
tetrahydrofuran, among others, as the mobile phase, and the
molecular weight values are determined in terms of polystyrene
equivalents, for instance. When the molecular weight distribution
is narrower, the macromonomer has a lower viscosity and the
branched polymer produced by the method of the invention has a
better controlled structure.
[0030] The macromonomer (I) of the invention preferably has a
number average molecular weight within the range of 500 to 100,000,
more preferably 3,000 to 40,000. When the molecular weight is not
more than 500, the characteristics intrinsic to the vinyl polymers
are hardly expressed. When it is in excess of 100,000, polymer
handling becomes difficult.
<Polymerization of the Main Chain of Macromonomer (I)>
[0031] The vinyl polymer constituting the main chain of the
macromonomer (I) of the invention is produced by radical
polymerization. The radical polymerization includes "ordinary
radical polymerization" by which a monomer having a specific
functional group and a vinyl monomer are simply copolymerized using
an azo compound or a peroxide, for instance, as a polymerization
initiator, and "controlled radical polymerization" by which a
specific functional group can be introduced at such a controlled
site as a terminus.
[0032] The "ordinary radical polymerization" is a simple and easy
method but a monomer having a specific functional group can be
introduced into a polymer only randomly by this method and, for
obtaining a highly functionalized polymer, it is necessary to use
this monomer having a specific functional group in a fairly large
amount. If it, is used only in a small, amount, there arises a
problem, namely the proportion of polymer molecules having no such
specific functional group introduced therein increases. Another
problem is that since free radical polymerization is involved
there, only those polymers are obtained which have a broad
molecular weight distribution and a high viscosity.
[0033] The "controlled radical polymerization" can be further
classified into "chain transfer agent process" which is carried out
using a chain transfer agent having a specific functional group to
thereby give a vinyl polymer having the specific functional group
terminally, and "living radical polymerization" which can give a
polymer having a molecular weight approximately as designed since
the growing polymer terminus can grow without undergoing a
termination reaction and/or the like.
[0034] The "chain transfer agent process" can give highly
functionalized polymers but requires a chain transfer agent having
a specific functional group in considerably large amounts as
compared with the initiator, hence raises economic problems,
inclusive of treatment problems. Since it involves free radical
polymerization, like the above-mentioned "ordinary radical
polymerization", it has problems; for example, the molecular weight
distribution is broad and high-viscosity polymers only can be
obtained.
[0035] Unlike these polymerization methods, the "living radical
polymerization" proceeds at a high rate of polymerization and, on
the other hand, hardly undergoes termination reactions and gives a
polymer with a narrow molecular weight distribution (an Mw/Mn value
of about 1.1 to 1.5) in spite of its being a mode of that radical
polymerization which is regarded as difficult to control because of
the tendency toward occurrence of termination reactions due to
radical-to-radical coupling and the like. It is also possible, in
living radical polymerization, to arbitrarily control the molecular
weight by adjusting the monomer/initiator charge ratio.
[0036] The "living radical polymerization" method thus can give a
low viscosity polymer with a narrow molecular weight distribution
and, in addition, makes it possible to introduce a specific
functional group-containing monomer into the polymer mostly at the
desired sites and, therefore, is more preferred as the method of
producing the above specific functional group-containing vinyl
polymer.
[0037] While the term "living polymerization", in its narrower
sense, means polymerization in which molecular chains grow while
the termini thereof always retain their activity, said term
generally includes, within the meaning thereof, quasi-living
polymerization in which terminally inactivated molecules and
terminally active molecules grow in a state of equilibrium. The
latter definition is applied to the practice of the invention.
[0038] Such "living radical polymerization" has recently been
studied actively by various groups of researchers. As examples,
there may be mentioned, among others, the use of a cobalt-porphyrin
complex as described in the J. Am. Chem. Soc., 1994, vol. 116,
pages 7943 ff, the use of a radical capping agent such as a
nitroxide compound as described in Macromolecules, 1994, vol. 27,
pages 7228 ff., and the technique of "atom transfer radical
polymerization (ATRP)" which uses an organic halide or the like as
the initiator and a transition metal complex as the catalyst.
[0039] Among the "living radical polymerization" techniques, the
above-mentioned "atom transfer radical polymerization" technique,
which uses an organic halide or halogenated sulfonyl compound or
the like as the initiator and a transition metal complex as the
catalyst for polymerizing vinyl monomers, has, in addition to the
above-mentioned advantageous features of "living radical
polymerization", the advantages in that it gives a polymer having a
halogen or the like, which is relatively advantageous to functional
group conversion, at main chain termini and that the degree of
freedom is great in initiator and catalyst designing and,
therefore, it is more preferred as the method of producing vinyl
polymers having a specific functional group. This atom transfer
radical polymerization is described, for example, by Matyjaszewski
et al. in the J. Am. Chem. Soc., 1995, vol. 117, pages 5614 ff.;
Macromolecules, 1995, vol. 28, pages 7901 ff.; Science, 1996, vol.
272, pages 866 ff.; WO 96/30421, WO 97/18247, WO 98/01480 and WO
98/40415 and by Sawamoto et al. in Macromolecules, 1995, vol. 28,
pages 1721 ff; Japanese Kokai Publication Hei-09-208616 and
Japanese Kokai Publication Hei-08-41117, among others.
[0040] In the practice of the invention, any of the above methods
may be employed without any particular restriction. Basically,
however, controlled radial polymerization is preferred and, from
the ease of control viewpoint, living radical polymerization is
more preferred and atom transfer radical polymerization is
particularly preferred.
[0041] First, one of the controlled radical polymerization
techniques, namely the technique of polymerization using a chain
transfer agent is described. As regards the radical polymerization
using a chain transfer agent (telomer), as the process for
obtaining a vinyl polymer having a terminal structure suited for
the practice of the invention, it is not particularly restricted
but includes the following two processes.
[0042] Thus, there are available the process for producing
halogen-terminated polymers using a halogenated hydrocarbon as the
chain transfer agent, as disclosed in Japanese Kokai Publication
Hei-04-132706, and the process for producing hydroxy-terminated
polymers using a hydroxy-containing mercaptan or hydroxy-containing
polysulfide as the chain transfer agent, as disclosed in Japanese
Kokai Publication Sho-61-271306, Japanese Patent 2,594,402 and
Japanese. Kokai Publication Sho-54-47782.
[0043] The living radical polymerization is now described.
[0044] Among the techniques of such polymerization, the one which
uses a radical capping agent such as a nitroxide compound is first
described. In this polymerization technique, a stable nitroxy free
radical (.dbd.N--O.) is generally used as a radical capping agent.
Such compound is not restricted but is preferably a
2,2,6,6-tetrasubstituted-1-piperidinyloxy radical, a
2,2,5,5-tetrasubstituted-1-pyrrolidinyloxy radical or a cyclic
hydroxyamine-derived nitroxy free radical. Preferred as the
substituents are alkyl groups containing not more than four carbon
atoms, such as methyl or ethyl. As specific nitroxy free radical
compounds, they are not restricted but include
2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO),
2,2,6,6-tetraethyl-1-piperidinyloxy radical,
2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical,
2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical,
1,1,3,3-tetramethyl-2-isoindolinyloxy radical and
N,N-di-tert-butylamine-oxy radical, among others. Such a stable
free radical as galvinoxyl free radical may be used in lieu of the
nitroxy free radical.
[0045] The above radical capping agent is used in combination with
a radical generator. It is supposed that the reaction product from
the radical capping agent and radical generator serve as a
polymerization initiator to thereby cause the polymerization of an
addition-polymerizable monomer(s) to proceed. The quantity ratio
between both is not particularly restricted but the radical
initiator is judiciously used in an amount of 0.1 to 10 moles per
mole of the radical capping agent.
[0046] While various compounds can be used as the radical
generator, a peroxide capable of generating a radical under
polymerization temperature conditions is preferred. Such peroxide
is not restricted but includes, among others, diacyl peroxides such
as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as
dicumyl peroxides and di-tert-butyl peroxide; peroxycarbonates such
as diisopropyl peroxydicarbonate and bis(4-tert-butylcyclohexyl)
peroxydicarboante; and alkyl peresters such as tert-butyl
peroxyoctanoate and tert-butyl peroxybenzoate. In particular,
benzoyl peroxide is preferred. Further, such a radical generator as
a radical generating azo compound, for example
azobisisobutyronitrile, may also be used in lieu of the
peroxide.
[0047] As reported in Macromolecules, 1995, vol. 28, pages 2993
ff., alkoxyamine compounds such as illustrated below may be used in
lieu of the combined use of a radical capping agent and a radical
generator: ##STR1##
[0048] When an alkoxyamine compound is used as the initiator and
when the alkoxyamine compound is a hydroxy- or like functional
group-containing one such as illustrated above, polymers terminally
having a hydroxy or like functional group are obtained. When this
is applied to the present invention, functional group-terminated
polymers are obtained.
[0049] The polymerization conditions, such as the monomer, solvent,
polymerization temperature, etc., to be used in carrying out the
polymerization using the above nitroxide compound or like radical
capping agent are not restricted but may be the same as those to be
used in the atom transfer radical polymerization to be described
below.
[0050] The technique of atom transfer radical polymerization, which
is preferred as the method of living radical polymerization of the
invention, is described in the following.
[0051] In this atom transfer radical polymerization, an organic
halide, in particular an organic halide having a highly reactive
carbon-halogen bond (e.g. a carbonyl compound having a halogen in
the .alpha.-position or a compound having a halogen at the benzyl
site), or a halogenated sulfonyl compound is used as the
initiator.
[0052] Specific examples are, among others: [0053]
C.sub.6H.sub.5--CH.sub.2X, C.sub.6H.sub.5--C(H)(X)CH.sub.3,
C.sub.6H.sub.5--C(X)(CH.sub.3).sub.2 [0054] (in the above chemical
formulas, C.sub.6H.sub.5 is a phenyl group and X is chlorine,
bromine or iodine); [0055] R.sup.3--C(H)(X)--CO.sub.2R.sup.4,
R.sup.3--C(CH.sub.3)(X)--CO.sub.2R.sup.4,
R.sup.3--C(H)(X)--C(O)R.sup.4,
R.sup.3--C(CH.sub.3)(X)--C(O)R.sup.4, [0056] (in which R.sup.3 and
R.sup.4 each is a hydrogen atom or an alkyl group containing 1 to
20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or
an aralkyl group containing 7 to 20 carbon atoms and X is chlorine,
bromine or iodine); and [0057] R.sup.3--C.sub.6H.sub.4--SO.sub.2X
[0058] (in which R.sup.3 is a hydrogen atom or an alkyl group
containing 1 to 20 carbon atoms, an aryl group containing 6 to 20
carbon atoms or an aralkyl group containing 7 to 20 carbon atoms
and X is chlorine, bromine or iodine).
[0059] It is also possible to use, as the initiator in atom
transfer radical polymerization, an organic halide or halogenated
sulfonyl compound having a functional group other than the
functional group for initiating the polymerization. In such a case,
vinyl polymers having the functional group at one main chain
terminus and a structure represented by the above general formula
(2) at the other main chain terminus are produced. As such
functional group, there may be mentioned alkenyl, crosslinking
silyl, hydroxy, epoxy, amino and amide groups, among others.
[0060] The alkenyl-containing organic halide is not restricted but
may be one having the structure shown by the general formula (6),
for instance:
R.sup.6R.sup.7C(X)--R.sup.8--R.sup.9--C(R.sup.5).dbd.CH.sub.2 (6)
wherein R.sup.5 is a hydrogen atom or a methyl group, R.sup.6 and
R.sup.7 each is a hydrogen atom or an alkyl group containing 1 to
20 carbon atoms, an aryl group containing 6to 20 carbon atoms or an
aralkyl group containing 7 to 20 carbon atoms and R.sup.6 and
R.sup.7 may be bound to each other at respective other termini,
R.sup.8 is --C(O)O-- (ester group), --C(O)-- (keto group) or an o-,
m- or p-phenylene group, R.sup.9 is a direct bond or a divalent
organic group containing 1 to 20 carbon atoms, which may optionally
contain one or more ether bonds, and X is chlorine, bromine or
iodine.
[0061] As specific examples of the substituents R.sup.6 and
R.sup.7, which are not particularly restricted, there may be
mentioned hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl,
pentyl, hexyl, etc. R.sup.6 and R.sup.7 may be bound to each other
at respective other termini to form a cyclic skeleton.
[0062] As specific examples of the alkenyl-containing organic
halide represented by the general formula (6), there may be
mentioned the following: [0063]
XCH.sub.2C(O)O(CH.sub.2)CH.dbd.CH.sub.2,
H.sub.3CC(H)(X)C(O)O(CH.sub.2).sub.nCH.dbd.CH.sub.2,
(H.sub.3C).sub.2C(X)C(O)O(CH.sub.2).sub.nCH.dbd.CH.sub.2,
CH.sub.3CH.sub.2C(H)(X)C(O)O(CH.sub.2).sub.nCH.dbd.CH.sub.2,
##STR2## [0064] (in the above formulas, X is chlorine, bromine or
iodine and n is an integer of 0 to 20); [0065]
XCH.sub.2C(O)O(CH.sub.2)O(CH.sub.2).sub.mCH.dbd.CH.sub.2,
H.sub.3CC(H)(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mCH.dbd.CH.sub.2,
(H.sub.3C).sub.2C(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mCH.dbd.CH.sub.2-
,
CH.sub.3CH.sub.2C(H)(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mCH.dbd.CH.s-
ub.2, ##STR3## [0066] (in the above formulas, X is chlorine,
bromine or iodine, n is an integer of 1 to 20 and m is an integer
of 0 to 20); [0067] o, m,
p-XCH.sub.2--C.sub.6H.sub.4--(CH.sub.2).sub.n--CH.dbd.CH.sub.2,
[0068] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.n--CH.dbd.CH.sub.-
2, [0069] o, m,
p-CH.sub.3CH.sub.2C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.n--CH.dbd.CH.su-
b.2, [0070] (in the above formulas, X is chlorine, bromine or
iodine and n is an integer of 1 to 20); [0071] o, m,
p-XCH.sub.2--C.sub.6H.sub.4--(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--CH.db-
d.CH.sub.2, [0072] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--
-CH.dbd.CH.sub.2, [0073] o, m,
p-CH.sub.3CH.sub.2C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.n--O--(CH.sub.2-
).sub.m--CH.dbd.CH.sub.2, [0074] (in the above formulas, X is
chlorine, bromine or iodine, n is an integer of 1 to 20 and m is an
integer of 0 to 20); [0075] o, m,
p-XCH.sub.2--C.sub.6H.sub.4--O--(CH.sub.2).sub.n--CH.dbd.CH.sub.2,
[0076] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--O--(CH.sub.2).sub.n--CH.dbd.CH.sub.2,
[0077] o, m, p-CH.sub.3CH.sub.2C(H)
(X)--C.sub.6H.sub.4--O--(CH.sub.2).sub.n--CH.dbd.CH.sub.2, [0078]
(in the above formulas, X is chlorine, bromine or iodine and n is
an integer of 1 to 20); [0079] o, m,
p-XCH.sub.2--C.sub.6H.sub.4--O--(CH.sub.2).sub.n--O--(CH.sub.2).sub.m--CH-
.sub.2, [0080] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--O--(CH.sub.2).sub.n--O--(CH.sub.2).sub-
.m--CH.dbd.CH.sub.2, [0081] o, m,
p-CH.sub.3CH.sub.2C(H)(X)--C.sub.6H.sub.4--O--(CH.sub.2).sub.n--O--(CH.su-
b.2).sub.m--CH.dbd.CH.sub.2, [0082] (in the above formulas, X is
chlorine, bromine or iodine, n is an integer of 1 to 20 and m is an
integer of 0 to 20).
[0083] As the alkenyl-containing organic halide, there may further
be mentioned compounds represented by the general formula (7):
H.sub.2C.dbd.C(R.sup.5)--R.sup.9--C(R.sup.6)(X)--R.sup.10--R.sup.7
(7) [0084] wherein R.sup.5, R.sup.6, R.sup.7, R.sup.9 and X are as
defined above and R.sup.10 is a direct bond, --C(O)O-- (ester
group), --C(O)-- (keto group) or an o-, m- or p-phenylene
group.
[0085] R.sup.8 is a direct bond or a divalent organic group
containing 1 to 20 carbon atoms (which may optionally contain one
or more ether bonds) and, when it is a direct bond, the vinyl group
is bound to the carbon to which the halogen is bound, to form an
allyl halide. In this case, the carbon-halogen bond is activated by
the neighboring vinyl group, so that it is not always necessary for
R.sup.10 to be a C(O)O group or a phenylene group, for instance,
but it may be a direct bond. When R.sup.9 is not a direct bond,
R.sup.10 is preferably a C(O)O group, C(O) group or phenylene group
so that the carbon-halogen bond may be activated.
[0086] Specific examples of the compound of the general formula (7)
are, among others, the following: [0087] CH.sub.2.dbd.CHCH.sub.2X,
CH.sub.2.dbd.C(CH.sub.3)CH.sub.2X, CH.sub.2.dbd.CHC(H)(X)CH.sub.3,
CH.sub.2.dbd.C(CH.sub.3)C(H)(X)CH.sub.3,
CH.sub.2.dbd.CHC(X)(CH.sub.3).sub.2,
CH.sub.2.dbd.CHC(H)(X)C.sub.2H.sub.5,
CH.sub.2.dbd.CHC(H)(X)CH(CH.sub.3).sub.2,
CH.sub.2.dbd.CHC(H)(X)C.sub.6H.sub.5,
CH.sub.2.dbd.CHC(H)(X)CH.sub.2C.sub.6H.sub.5,
CH.sub.2.dbd.CHCH.sub.2C(H)(X)--CO.sub.2R,
CH.sub.2.dbd.CH(CH.sub.2).sub.2C(H)(X)--CO.sub.2R,
CH.sub.2.dbd.CH(CH.sub.2).sub.3C(H)(X)--CO.sub.2R,
CH.sub.2.dbd.CH(CH.sub.2)C(H)(X)--CO.sub.2R,
CH.sub.2.dbd.CHCH.sub.2C(H)(X)--C.sub.6H.sub.5,
CH.sub.2.dbd.CH(CH.sub.2).sub.2C(H)(X)--C.sub.6H.sub.5,
CH.sub.2.dbd.CH(CH.sub.2).sub.3C(H)(X)--C.sub.6H.sub.5, [0088] (in
the above formulas, X is chlorine, bromine or iodine and R is an
alkyl group containing 1-to 20 carbon atoms, aryl group or aralkyl
group).
[0089] Specific examples of the alkenyl-containing halogenated
sulfonyl compound are as follows: [0090] o, m,
p-CH.sub.2.dbd.CH--(CH.sub.2).sub.n--C.sub.6H.sub.4--SO.sub.2X and
[0091] o, m,
p-CH.sub.2.dbd.CH--(CH.sub.2).sub.n--O--C.sub.6H.sub.4--SO.sub.2X,
[0092] wherein, in each formula, X is chlorine, bromine or iodine
and n is an integer of 0 to 20.
[0093] The above-mentioned crosslinking silyl-containing organic
halide is not particularly restricted but includes, among others,
those having a structure shown by the general formula (8):
R.sup.6R.sup.7C(X)--R.sup.8--R.sup.9--C(H)(R.sup.5)CH.sub.2--[Si(R.sup.11-
).sub.2-b(Y).sub.bO--Si(R.sup.12).sub.3-a(Y).sub.a (8) [0094]
wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and X are as
defined above, R.sup.11 and R.sup.12 each represents an alkyl group
containing 1 to 20 carbon atoms, an aryl-group containing 6 to 20
carbon atoms or an aralkyl group containing 7 to 20 carbon atoms or
a triorganosiloxy group of the formula (R').sub.3SiO-- (in which R'
is a monovalent hydrocarbon group containing 1 to 20 carbon atoms,
and the three R' groups may be the same or different) and, when
there are two or more R.sup.11 or R.sup.12 groups, they may be the
same or different, Y represents a hydroxy group or a hydrolyzable
group and, when there are two or more Y groups, they may be the
same or different, a represents 0, 1, 2 or 3, b represents 0, 1 or
2 and m is an integer of 0 to 19, provided that the relation
a+mb.gtoreq.1 should be satisfied. Specific examples of the
compound of the general formula (8) are as follows: [0095]
XCH.sub.2C(O)O(CH.sub.2).sub.nSi(OCH.sub.3).sub.3,
CH.sub.3C(H)(X)C(O)O(CH.sub.2).sub.nSi(OCH.sub.3).sub.3,
(CH.sub.3).sub.2C(X)C(O)O(CH.sub.2).sub.nSi(OCH.sub.3).sub.3,
XCH.sub.2C(O)O(CH.sub.2).sub.nSi(CH.sub.3)(OCH.sub.3).sub.2,
CH.sub.3C(H)(X)C(O)O(CH.sub.2).sub.nSi(CH.sub.3)(OCH.sub.3).sub.2,
(CH.sub.3).sub.2C(X)C(O)O(CH.sub.2).sub.n--Si(CH.sub.3)(OCH.sub.3).sub.2,
[0096] (in the above formulas, X is chlorine, bromine or iodine and
n is an integer of 0 to 20); [0097]
XCH.sub.2C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mSi(OCH.sub.3).sub.3,
H.sub.3CC(H)(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mSi(OCH.sub.3).sub.3,
(H.sub.3C).sub.2C(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mSi(OCH.sub.3).s-
ub.3,
CH.sub.3CH.sub.2C(H)(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mSi(OCH.-
sub.3).sub.3,
XCH.sub.2C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mSi(CH.sub.3)(OCH.sub.3).su-
b.2,
H.sub.3CC(H)(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mSi(CH.sub.3)(OCH-
.sub.3).sub.2,
(H.sub.3C).sub.2C(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mSi(CH.sub.3)(OC-
H.sub.3).sub.2,
CH.sub.3CH.sub.2C(H)(X)C(O)O(CH.sub.2).sub.nO(CH.sub.2).sub.mSi(CH.sub.3)-
(OCH.sub.3).sub.2, [0098] (in the above formulas, X is chlorine,
bromine or iodine, n is an integer of 1 to 20 and m is an integer
of 0 to 20); [0099] o, m,
p-XCH.sub.2--C.sub.6H.sub.4--(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0100] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.2Si(OCH.sub.3).s-
ub.3, [0101] o, m,
p-CH.sub.3CH.sub.2C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.2Si(OCH.sub.3).-
sub.3, [0102] o, m,
p-XCH.sub.2--C.sub.6H.sub.4--(CH.sub.2).sub.3Si(OCH.sub.3).sub.3,
[0103] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.3Si(OCH.sub.3).s-
ub.3, [0104] o, m,
p-CH.sub.3CH.sub.2C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.3Si(OCH.sub.3).-
sub.3, [0105] o, m,
-p-XCH.sub.2--C.sub.6H.sub.4--(CH.sub.2).sub.2--O--(CH.sub.2).sub.3Si(OCH-
.sub.3).sub.3, [0106] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.2--O--(CH.sub.2).sub.3S-
i(OCH.sub.3).sub.3, [0107] o, m,
p-CH.sub.3CH.sub.2C(H)(X)--C.sub.6H.sub.4--(CH.sub.2).sub.2--O--(CH.sub.2-
).sub.3Si(OCH.sub.3).sub.3, [0108] o, m,
p-XCH.sub.2--C.sub.6H.sub.4--O--(CH.sub.2).sub.3Si(OCH.sub.3).sub.3,
[0109] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--O--(CH.sub.2).sub.3Si(OCH.sub.3).sub.3-
, [0110] o, m,
p-CH.sub.3CH.sub.2C(H)(X)--C.sub.6H.sub.4--O--(CH.sub.2).sub.3Si(OCH.sub.-
3).sub.3, [0111] o, m,
p-XCH.sub.2--C.sub.6H.sub.4--O--(CH.sub.2).sub.2--O--(CH.sub.2).sub.3Si(C-
H.sub.3).sub.3, [0112] o, m,
p-CH.sub.3C(H)(X)--C.sub.6H.sub.4--O--(CH.sub.2).sub.2--O--(CH.sub.2).sub-
.3Si(OCH.sub.3).sub.3, [0113] o, m,
p-CH.sub.3CH.sub.2C(H)(X)--C.sub.6H.sub.4--O--(CH.sub.2).sub.2--O--(CH.su-
b.2).sub.3Si(OCH.sub.3).sub.3, [0114] (in the above formulas, X is
chlorine, bromine or iodine), and the like.
[0115] As further examples of the crosslinking silyl-containing
organic halide, there may be mentioned those having a structure
represented by the general formula (9):
(R.sup.12).sub.3-a(Y).sub.aSi--[OSi(R.sup.11).sub.2-b(Y).sub.b].sub.m--CH-
.sub.2--C(H)(R.sup.5)--R.sup.9--C(R.sup.6)(X)--R.sup.10--R.sup.7
(9) [0116] wherein R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10,
R.sup.11, R.sup.12, a, b, m, X and Y are as defined above.
[0117] Specific examples of such compounds are as follows: [0118]
(CH.sub.3O).sub.3SiCH.sub.2CH.sub.2C(H)(X)C.sub.6H.sub.5,
(CH.sub.3O).sub.2(CH.sub.3)SiCH.sub.2CH.sub.2C
(H)(X)C.sub.6H.sub.5,
(CH.sub.3O).sub.3Si(CH.sub.2).sub.2C(H)(X)--CO.sub.2R,
(CH.sub.3O).sub.2(CH.sub.3)Si(CH.sub.2).sub.2C(H)(X)--CO.sub.2R,
(CH.sub.3O).sub.3Si(CH.sub.2).sub.3C(H)(X)--CO.sub.2R,
(CH.sub.3O).sub.2(CH.sub.3)Si(CH.sub.2).sub.3C(H)(X)--CO.sub.2R,
(CH.sub.3O).sub.3Si(CH.sub.2).sub.4C(H)(X)--CO.sub.2R,
(CH.sub.3O).sub.2(CH.sub.3)Si(CH.sub.2).sub.4C(H)(X)--CO.sub.2R,
(CH.sub.3O).sub.3Si(CH.sub.2).sub.9C(H)(X)--CO.sub.2R,
(CH.sub.3O).sub.2(CH.sub.3)Si(CH.sub.2).sub.9C(H)(X)--CO.sub.2R,
(CH.sub.3O).sub.3Si(CH.sub.2).sub.3C(H)(X)--C.sub.6H.sub.5,
(CH.sub.3O).sub.2(CH.sub.3)Si(CH.sub.2).sub.3C(H)(X)--C.sub.6H.sub.5,
(CH.sub.3O).sub.3Si(CH.sub.2).sub.4C(H)(X)--C.sub.6H.sub.5,
(CH.sub.3O).sub.2(CH.sub.3)Si(CH.sub.2).sub.4C(H)(X)--C.sub.6H.sub.5,
[0119] (in the above formulas, X is chlorine, bromine or iodine and
R is an alkyl group containing 1 to 20 carbon atoms, an aryl group
containing 6 to 20 carbon atoms or an aralkyl group containing 7 to
20 carbon atoms), and the like.
[0120] The above-mentioned hydroxy-containing organic halide or
halogenated sulfonyl compound is not particularly restricted but
includes, among others, compounds of the formula: [0121]
HO--(CH.sub.2).sub.n--OC(O)C(H)(R)(X) [0122] wherein X is chlorine,
bromine or iodine, R is a hydrogen atom or an alkyl group
containing 1 to 20 carbon atoms, an aryl group containing 6 to 20
carbon atoms or an aralkyl group containing 7 to 20 carbon atoms
and n is an integer of 1 to 20.
[0123] The above-mentioned amino-containing organic halide or
halogenated sulfonyl compound is not particularly restricted but
includes, among others, compounds of the formula: [0124]
H.sub.2N--(CH.sub.2).sub.n--OC(O)C(H)(R)(X) [0125] wherein X is
chlorine, bromine or iodine, R is a hydrogen atom or an alkyl group
containing 1 to 20 carbon atoms, an aryl group containing 6 to 20
carbon atoms or an aralkyl group containing 7 to 20 carbon atoms
and n is an integer of 1 to 20.
[0126] The above-mentioned epoxy-containing organic halide or
halogenated sulfonyl compound is not particularly restricted but
includes, among others, compounds of the formula: ##STR4## [0127]
wherein X is chlorine, bromine or iodine, R is a hydrogen atom or
an alkyl group containing 1 to 20 carbon atoms, an aryl group
containing 6 to 20 carbon atoms or an aralkyl group containing 7 to
20 carbon atoms and n is an integer of 1 to 20.
[0128] Since the macromonomer of the invention terminally has one
polymerizable carbon-carbon bond, it is generally preferred to use
an initiator having one terminal initiation site, such as mentioned
above. In some instances, however, an organic halide or halogenated
sulfonyl compound having two or more initiation sites is used as
the initiator in atom transfer radical polymerization. Such an
initiator is suitable in producing a polymer having two or more
terminal polymerizable carbon-carbon double bonds which can give a
crosslinked polymer (gel) by polymerizing with the macromonomer of
the invention. Specific examples are as follows: ##STR5##
##STR6##
[0129] In the above formulas X represents a halogen atom.
[0130] The vinyl monomer to be used in this polymerization is not
particularly restricted but any of those already mentioned
specifically hereinabove can favorably be used.
[0131] The transition metal catalyst to be used as the
polymerization catalyst is not particularly restricted but metal
complexes having, as the central metal, an element of the group 7,
8, 9, 10 or 11 of the periodic table are preferred. More preferred
are complexes of copper of valence 0 (zero), monovalent copper,
divalent ruthenium, divalent iron or divalent nickel. In
particular, copper complexes are preferred. Specific monovalent
copper compounds are cuprous chloride, cuprous bromide, cuprous
iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the
like. When a copper compound is used, a ligand, such as
2,2'-bipyridyl or a derivative thereof, 1,10-phenanthroline or a
derivative thereof, tetramethylethylenediamine,
pentamethyldiethylenetriamine, hexamethyltris(2-aminoethyl)amine or
a like polyamine, is added for increasing the catalytic activity. A
tristriphenylphosphine-ruthenium (II) chloride complex
(RuCl.sub.2(PPh.sub.3).sub.3) is also suited for use as the
catalyst. When a ruthenium compound is used as the catalyst, an
aluminum alkoxide is added as an activator. Further, a
bistriphenylphosphine complex of divalent iron
(FeCl.sub.2(PPh.sub.3).sub.2), a bistriphenylphosphine complex of
divalent nickel (NiCl.sub.2(PPh.sub.3).sub.2) and a
bistributylphosphine complex of divalent nickel
(NiBr.sub.2(PBu.sub.3).sub.2) are also suited as the catalysts.
[0132] The polymerization can be carried without using any solvent
or in various solvents. The solvents include hydrocarbon solvents
such as benzene and toluene, ether solvents such as diethyl ether
and tetrahydrofuran, halogenated hydrocarbon solvents such as
methylenechloride and chloroform, ketone solvents such as acetone,
methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents
such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol
and tert-butyl alcohol, nitrile solvents such as acetonitrile,
propionitrile and benzonitrile, ester solvents such as ethyl
acetate and-butyl acetate, and carbonate solvents such as ethylene
carbonate and propylene carbonate, among others. These may be used
singly or two or more of them may be used in admixture. The
polymerization can be carried out in a temperature range of room
temperature to 200.degree. C., preferably 50 to 150.degree. C.
<Method of Functional Group Introduction>
[0133] In the following, the introduction of a terminal functional
group into a polymer to give a macromonomer (I) in the practice of
the invention is described.
[0134] For introducing a group represented by the general formula
(1) terminally into a polymer in the practice of the invention, the
following methods, among others, may be mentioned.
[0135] {circle around (1)} The production method which comprises
substituting a compound having a radical-polymerizable
carbon-carbon double bond for the terminal halogen group of a vinyl
polymer. In a specific example, a vinyl polymer having a terminal
structure represented by the above general formula (2) is reacted
with a compound represented by the above general formula 43).
[0136] {circle around (2)} The method which comprises reacting a
hydroxy-terminated vinyl polymer with a compound represented by the
above general formula (4).
[0137] {circle around (3)} The method which comprises reacting a
hydroxy-terminated vinyl polymer with a diisocyanate compound and
then reacting the residual isocyanato group with a compound
represented by the above general formula (5).
[0138] In the following, these methods are described in detail.
<Functional Group Introduction Method {circle around
(1)}>
[0139] This method {circle around (3)} is now described.
[0140] The vinyl polymer having a terminal structure represented by
the general formula (2) is produced by the method comprising
polymerizing a vinyl monomer using the above-mentioned organic
halide or halogenated sulfonyl compound as the initiator and a
transition metal complex as the catalyst, or by the method
comprising polymerizing a vinyl monomer using a halogen compound as
the chain transfer agent. The former method is preferred,
however.
[0141] The compound represented by the general formula (3) is not
particularly restricted. Thus, R is not particularly restricted as
far as it is a monovalent organic group containing 1 to 20 carbon
atoms but includes, for example, substituted or unsubstituted
hydrocarbon groups containing 1 to 20 carbon atoms, ether groups,
acyl groups, carbon- and nitrogen-containing groups, carbon- and
sulfur-containing groups, carbon- and oxygen-containing groups, and
the like, more specifically, --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--(CH.sub.2).sub.nCH.sub.3 (n being an integer of 2 to 19),
--C.sub.6H.sub.5, --CH.sub.3OH, --CN and so forth. Preferred are
--H and --CH.sub.3, however. M.sup.+ is a counter cation to the oxy
anion and, as species of M.sup.+, there may be mentioned alkali
metal ions, specifically the lithium ion, sodium ion and potassium
ion, and quaternary ammonium ions. As the quaternary ammonium ions,
there may be mentioned the tetramethylammonium ion,
tetraethylammonium ion, tetrabenzylammonium ion,
trimethyldodecylammonium ion, tetrabutylammonium ion,
dimethylpiperidinium ion and the like. Among these, the sodium ion
and potassium ion are preferred. The oxy anion of the general
formula (3) is used preferably in an amount of 1 to 5 equivalents,
more preferably 1.0 to 1.2 equivalents, relative to the
halogen-containing terminal group of the general formula (2).
[0142] The solvent to be used in carrying out this reaction is not
particularly restricted but, since the reaction is a nucleophilic
substitution reaction, a polar solvent is preferred. Thus, for
example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl
sulfoxide, dimethylformamide, dimethylacetamide,
hexamethylphosphoric triamide, acetonitrile and the like are used.
The reaction temperature is not restricted but generally it is
carried out at 0 to 150.degree. C., preferably at room temperature
to 100.degree. C. so that the polymerizable terminal group may be
retained.
<Functional Group Introduction Method {circle around
(2)}>
[0143] This method {circle around (2)} is now described.
[0144] The compound represented by the above general formula (4) is
not particularly restricted. Thus, R is not particularly restricted
as far as it is a monovalent organic group containing 1 to 20
carbon atoms but includes, for example, substituted or
unsubstituted hydrocarbon groups containing 1 to 20 carbon atoms,
ether groups, acyl groups, carbon- and nitrogen-containing groups,
carbon- and sulfur-containing groups, carbon- and oxygen-containing
groups, and the like, more specifically, --H, --CH.sub.3,
--CH.sub.2CH.sub.3, --(CH.sub.2).sub.nCH.sub.3 (n being an integer.
of 2 to 19), --C.sub.6H.sub.5, --CH.sub.2OH, --CN and so forth.
Preferred are --H and --CH.sub.3, however.
[0145] The hydroxy-terminated vinyl polymer is produced by the
method comprising polymerizing a vinyl monomer using the
above-mentioned organic halide or halogenated sulfonyl compound as
the initiator and a transition metal complex as the catalyst, or by
the method comprising polymerizing a vinyl monomer using a
hydroxy-containing compound as the chain transfer agent. The former
method is preferred, however. These methods of producing
hydroxy-terminated vinyl polymers are not restricted but include,
for example, the following techniques.
[0146] (a) The technique comprising reacting a compound having both
a polymerizable alkenyl group and a hydroxy group in each molecule,
such as a compound represented by the general formula (10) given
below, as a second monomer, in synthesizing a vinyl polymer by
living radical polymerization.
H.sub.2C.dbd.C(R.sup.13)--R.sup.14--R.sup.15--OH (10) wherein
R.sup.13 is a monovalent organic group containing 1 to 20 carbon
atoms, preferably a hydrogen atom or a methyl group, R.sup.14
represents --C(O)O-- (ester group) or an o-, m- or p-phenylene
group and R.sup.15 represents a direct bond or a divalent organic
group containing 1to 20 carbon atoms, which may optionally have one
or more ether bonds. When R.sup.14 is an ester group, the compound
is a (meth) acrylate compound and, when R.sup.4 is a phenylene
group, the compound is a styrene type compound.
[0147] The timing of subjecting to reaction the compound having
both a polymerizable alkenyl group and a hydroxy group in each
molecule is not restricted. When, however, rubber-like properties
are particularly expected, it is preferred to effect the reaction
of the monomer as a second one at the final stage of the
polymerization reaction or after completion of the reaction of a
predetermined monomer.
[0148] (b) The technique comprising reacting a compound having both
a low-polymerizability alkenyl group and a hydroxy group in each
molecule as a second monomer at the final stage of the
polymerization reaction or after completion of the reaction of a
predetermined monomer in synthesizing a vinyl polymer by living
radical polymerization.
[0149] Such a compound is not particularly restricted, but includes
compounds represented by the general formula (11):
H.sub.2C.dbd.C(R.sup.13)--R.sup.16--OH (11) wherein R.sup.13 is as
defined above and R.sup.16 represents a divalent organic group
containing 1 to 20 carbon atoms, which may optionally contain one
or more ether bonds.
[0150] The compound represented by the above general formula (11)
is not particularly restricted but, from the ready availability
viewpoint, alkenyl alcohols such as 10-undecenol, 5-hexenol and
allyl alcohol are preferred.
[0151] (c) The technique disclosed in Japanese Kokai Publication
Hei-04-13270.6, namely the technique comprising effecting terminal
hydroxy group introduction by hydrolyzing the halogen atom of a
vinyl polymer having at least one carbon-halogen bond represented
by the above general formula (2) as obtained by atom transfer
radical polymerization or reacting that halogen atom with a
hydroxy-containing compound.
[0152] (d) The technique comprising reacting a vinyl polymer having
at least one carbon-halogen bond represented by the above general
formula (2) as obtained by atom transfer radical polymerization
with a hydroxy-containing stabilized carbanion represented by the
general formula (12) for effecting halogen substitution.
M.sup.+C.sup.-(R.sup.17)(R.sup.18)--R.sup.16--OH (12) wherein
R.sup.16 is as defined above, R.sup.17 and R.sup.18 each represents
an electron-attracting group capable of stabilizing the carbanion
C-- or one of them represents such an electron-attracting group and
the other represents a hydrogen atom, an alkyl group containing 1
to 10 carbon atoms or a phenyl group. As the electron-attracting
group represented by R.sup.17 and R.sup.18, there may be mentioned,
for example, --CO.sub.2R (ester group), --C(O)R (keto group),
--CON(R.sub.2)(amide group), --COSR (thioester group), --CN
(nitrile group) and --NO.sub.2 (nitro group). The substituent R is
an alkyl group containing 1 to 20 carbon atoms, an aryl group
containing 6 to 20 carbon atoms or an aralkyl group containing 7 to
20 carbon atoms, preferably an alkyl group containing 1 to 10
carbon atoms or a phenyl group. Particularly preferred as R.sup.17
and R.sup.18 are --CO.sub.2R, --C(O)R and --CN.
[0153] (e) The technique comprising reacting a vinyl polymer having
at least one carbon-halogen bond represented by the above general
formula (2) as obtained by atom transfer radical polymerization
with a simple substance metal, such as zinc, or an organometallic
compound and then reacting the thus-prepared enolate anion with an
aldehyde or ketone.
[0154] (f) The technique comprising reacting a vinyl polymer having
at least one terminal halogen, preferably in the form represented
by the above general formula (2), with a hydroxy-containing oxy
anion represented by the general formula (13) given below or a
hydroxy-containing carboxylate anion represented by the general
formula (14) given below or the like to effect substitution of a
hydroxy-containing substituent for the above halogen.
HO--R.sup.16--O.sup.-M.sup.+ (13) (R.sup.16 and M.sup.+ being as
defined above); HO--R.sup.16--C(O)O.sup.-M.sup.+ (14) (R.sup.16 and
M.sup.+ being as defined above).
[0155] In cases that no halogen is directly involved in hydroxy
group introduction, as in (a) and (b), the technique (b) is more
preferred in the practice of the invention because of easier
controllability.
[0156] In cases that hydroxy group introduction is effected by
converting the halogen atom of a vinyl polymer having at least one
carbon-halogen bond, as in (c) to (f), the technique (f) is more
preferred because of easier controllability.
<Terminal Functional Group Introduction {circle around
(3)}>
[0157] This method {circle around (3)} is now described.
[0158] The compound represented by the above general formula (5) is
not particularly restricted. Thus, R is not particularly restricted
as far as it is a monovalent organic group containing 1 to 20
carbon atoms but includes substituted or unsubstituted hydrocarbon
groups containing 1 to 20 carbon atoms, ether groups, acyl groups,
carbon- and nitrogen-containing groups, carbon- and
sulfur-containing groups, carbon- and oxygen-containing groups, and
the like, more specifically, --H, --CH.sub.3, --CH.sub.2CH.sub.3,
--(CH.sub.2).sub.nCH.sub.3 (n being an integer of 2 to 19),
--C.sub.6H.sub.5, --CH.sub.2OH, --CN and so forth. Preferred are
--H and --CH.sub.3, however. As a specific compound, there maybe
mentioned 2-hydroxypropyl methacrylate.
[0159] The hydroxy-terminated vinyl polymer to be used may be the
same as mentioned hereinabove.
[0160] The diisocyanate compound is not particularly restricted but
includes those known in the art. Thus, for example, mention may be
made of isocyanate compounds such as tolylene diisocyanate,
4,4'-diphenylmethanediisocyanate, hexamethylene diisocyanate,
xylylene diisocyanate, metaxylylene diisocyanate,
1,5-naphthalenediisocyanate, hydrogenated
diphenylmethanediisocyanate, hydrogenated toluylene dilsocyanate,
hydrogenated xylylene diisocyanate and isophoronediisocyanate.
These may be used singly or two or more of them may be used
combinedly. Blocked isocyanates may also be used.
[0161] For putting better weathering resistance to use, the use of
aromatic ring-free diisocyanate compounds, such as hexamethylene
diisocyanate and hydrogenated diphenylmethanediisocyanate, is
preferred.
<Method of Polymerizing the Polymer of the Invention>
[0162] The method of polymerizing the macromonomer (I) according to
the invention is not restricted but preferably is radical
polymerization, more preferably living radical polymerization,
still more preferably atom transfer radical polymerization. The
atom transfer radical polymerization is carried out preferably
using a transition metal complex having, as the central metal, an
element of the group 7, 8, 9, 10 or 11 of the periodic table, more
preferably a metal complex the metal of which is selected from the
group consisting of copper, nickel, ruthenium-and iron,
particularly preferably a copper complex.
[0163] The polymerization of the macromonomer (I) is also
preferably effected by using active radiation for initiating the
polymerization or by initiating the polymerization by heating.
[0164] The polymerization of the macromonomer (I) may also effected
by anionic polymerization.
[0165] Homopolymerization of the macromonomer (I) of the invention
gives a stellar polymer, copolymerization of the macromonomer (I)
with a copolymerizable monomer other than the macromonomer gives a
graft copolymer, and copolymerization of the macromonomer (I) with
a polyfunctional compound having two or more polymerizable
carbon-carbon double bonds per molecule, preferably a polymer (III)
terminally having such double bonds, gives a gel.
[0166] In the following, the method of polymerizing the
macromonomer (I) is described in detail.
(Anionic Polymerization)
[0167] The initiator to be used in the anionic polymerization is
not particularly restricted but includes, among others,
monofunctional initiators such as sec-butyllithium and
tert-butyllithium, 1,4-dilithiobutane, dilithiobutadiene and
dilithionaphthalene. These may be used in combination with
diphenylethylene, .alpha.-methylstyrene or the like to form
initiation systems.
[0168] As the coplymerizable monomer (II) other than the
macromonomer, there may be mentioned anionically polymerizable
monomers, for example, aromatic monomers such as styrene,
.alpha.-methylstyrene, p-methylstyrene, o-methylstyrene,
p-butylstyrene, methoxystyrene, 1-vinylnaphthalene,
3-ethyl-1-biphenylnaphthalene and p-N,N-diemthylaminostyrene;
(meth)acrylic monomers such as (meth)acrylic acid, methyl
(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,
isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl
(meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate,
n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl
(meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl
(meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate,
benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate,
3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl
(meth)acrylate, 2-aminoethyl (meth)acrylate,
.gamma.-(methacryloyloxypropyl)trimethoxysilane,
trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl
(meth)acrylate, 2-perfluoroethylethyl (meth)acrylate,
2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate,
2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate,
diperfluoromethylmethyl (meth)acrylate,
2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate,
2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)
acrylate, 2-perfluorohexadecylethyl (meth) acrylate and the like;
conjugated dienes such as 1,3-butadiene, 1,3-pentadiene,
2,3-dimethyl-1,3-butadiene, 2,4-hexadiene, 2-phenyl-1,3-butadiene
and isoprene; and nitriles such as acrylonitrile. These maybe used
singly or a plurality thereof may be copolymerized. Among them,
styrene type monomers and (meth).acrylic monomers are preferred
from the viewpoint of physical properties of products, among
others. Acrylic ester monomers and methacrylic ester monomers are
more preferred and butyl acrylate is still more preferred. In the
practice of the invention, these preferred monomers may be
copolymerized with some other monomer(s) and, in that case, the
proportion of these preferred monomers is preferably 40% by
weight.
[0169] While the anionic polymerization can also be carried in the
absence of a solvent, it is possible to carry out the
polymerization in the presence of an appropriate organic solvent.
As the organic solvent, there may be mentioned, for example,
aromatic hydrocarbon solvents such as benzene, toluene and xylene;
aliphatic hydrocarbon solvents such as n-hexane, n-octane and
isooctane; alicyclic hydrocarbon solvents such as
methylcyclopentane, cyclohexane and cyclooctane; and ether solvents
such as tetrahydrofuran, dioxane and diethyl ether.
[0170] As for the polymerization conditions, those conditions
employed in ordinary anionic polymerization can be used. For
preventing the living sites of the polymerization initiator and at
the polymer terminus from being inactivated, however, it is
preferred to carry out the polymerization under conditions such
that oxygen, carbon dioxide or water, for instance, cannot enter
the polymerization system. For example, a polymerization initiator
is added to a solvent deaerated and dehydrated under high vacuum or
in a nitrogen atmosphere almost free of moisture and, then, the
anionically polymerizable monomer mentioned above is added and the
anionic polymerization is allowed to proceed. It is also possible
to carry out the polymerization by adding the polymerization
initiator and monomer gradually, not by adding them all at
once.
[0171] When two or more of the above-mentioned anionically
polymerizable monomers are combinedly subjected to polymerization,
polymers having an arbitrary monomer composition can be obtained.
When another or other monomers are subjected in succession to
polymerization following completion of the polymerization of one
monomer, block copolymers, diblock copolymers, triblock copolymers,
multiblock copolymers and the like respectively having an arbitrary
monomer composition and structure can be obtained. When the
macromonomer (I) is added during such polymerization, graft
copolymers with the macromonomer (I) incorporated at an appropriate
position(s) are obtained.
[0172] The polymerization temperature may vary according to the
polymerization initiator, monomer(s) and solvent employed, among
others, but, generally, it is preferably within the range of
-100.degree. C. to 150.degree. C., more preferably within the range
of -78.degree. C. to 80.degree. C. The polymerization time may vary
according to the polymerization initiator, monomer(s), solvent and
reaction temperature employed, among others, but, generally, it is
preferably within the range of 10 minutes to 10 hours. The
polymerization reaction may be carried out batchwise, semibatchwise
or continuously.
(Radical Polymerization)
[0173] The radical polymerization is not particularly restricted in
mode but may be carried out in the manner of ordinary free radical
polymerization, chain transfer radical polymerization or living
radical polymerization, for instance.
[0174] In the radical polymerization, all the radical-polymerizable
monomers mentioned hereinabove referring to the production of the
main chain of the macromonomer (I) can be used as the monomer (II)
copolymerizable with the macromonomer (I).
[0175] The radical polymerization may be carried out without using
any solvent or using any of those solvents mentioned above
referring to the production of the main chain of the macromonomer
(I).
[0176] The initiator to be used in free radical polymerization is
not particularly restricted but includes, among others, radical
initiators such as organic peroxides, e.g. benzoyl peroxide and
tert-butyl peroxide, and azo compounds, e.g.
2,2'-azobisisobutyronitrile,
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis(2-cyclopropyl-propionitrile) and 2,2'-azobis
(2-methylbutyronitrile).
[0177] In the chain transfer radical polymerization, a chain
transfer agent is added to the system of the above-mentioned free
radical polymerization. As the initiator, any of those mentioned
above can be used. The chain transfer agent is not particularly
restricted but may be n-dodecylmercaptan, tert-dodecylmercaptan,
n-octylmercaptan, n-octadecylmercaptan,
3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,
3-mercaptopropylmethyldimethoxysilane,
3-mercaptopropylmethyldiethoxysilane,
(H.sub.3CO).sub.3Si--S--S--Si(OCH.sub.3).sub.3,
CH.sub.3(H.sub.3CO).sub.2Si--S--S--SiCH.sub.3(OCH.sub.3).sub.2,
(C.sub.2H.sub.5O).sub.3Si--S--S--Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3(C.sub.2H.sub.5O).sub.2Si--S--S--SiCH.sub.3(OC.sub.2H.sub.5).sub.-
2, (H.sub.3CO).sub.3Si--S.sub.3--Si(OCH.sub.3).sub.3,
(H.sub.3CO).sub.3Si--S.sub.4--Si(OCH.sub.3).sub.3,
(H.sub.3CO).sub.3Si--S.sub.6--Si(OCH.sub.3).sub.3 or the like. In
particular when a chain transfer agent having an alkoxysilyl
group(s) within the molecule, for example
3-mercaptopropyltrimethoxysilane, is used, the alkoxysilyl group(s)
can be introduced terminally into the polymer.
[0178] The living radical polymerization is not restricted but
includes SFRP (stable free radical polymerization) in which the
growing polymerization terminal radical is capped by TEMPO
(tetramethylpiperidine oxide) or a cobalt-porphyrin complex, and
that atom transfer polymerization which has been mentioned
referring to the polymerization of the main chain of the
macromonomer (I) of the invention, and the latter is preferred.
These polymerizations are carried out under those conditions
already mentioned hereinabove. When the macromonomer (I) is
polymerized by living radical polymerization, it is expected that
the molecular weight and molecular weight distribution of the
resulting polymer chain can be controlled. As a result, when it is
copolymerized with another monomer (II), graft copolymers better
controlled with respect to the number of side chains in the polymer
as compared with ordinary free radical polymerization can be
obtained and, when the macromonomer (I) is homopolymerized,
polymers better controlled with respect to the number of arms of a
stellar polymer as compared with ordinary free radical
polymerization can be obtained.
(Polymerization by Means of Active Radiation)
[0179] The macromonomer (I) of the invention can be polymerized by
means of active radiation, such as UV rays and electron beams.
[0180] This method is not restricted but is suited for use in
producing gels by polymerizing the macromonomer (I) with a polymer
(III) having two or more terminal polymerizable carbon-carbon
double bonds.
[0181] In actinic energy polymerization, the system preferably
contains a photopolymerization initiator.
[0182] The photopolymerization initiator to be used in the practice
of the invention is not particularly restricted but preferably
includes photo radical initiators and photo anion initiators. Among
these, photo radical initiators are preferred. As such, there may
be mentioned, for example, acetophenone, propiophenone,
benzophenone, xanthol, fluorescein, benzaldehyde, anthraquinone,
triphenylamine, carbazole, 3-methylacetophenone,
4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone,
3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene,
3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone,
4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone,
3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone,
benzoin, benzoin methyl ether, benzoin butyl ether, bis
(4-dimethylaminophenyl) ketone, benzylmethoxy ketal,
2-chlorothioxanthone and the like. These initiators may be used
singly or in combination with another compound. Specifically, they
may be combined with an amine such as diethanolmethylamine,
dimethylethanolamine and triethanolamine, and in further
combination with an iodonium salt such as diphenyliodonium
chloride, or with a dye, such as methylene blue, and an amine.
[0183] It is also possible to use a near infrared absorbing
cationic dye as a near infrared photopolymerization initiator.
Preferred as the near infrared absorbing cationic dye are those
near infrared absorbing cationic dye-borate anion complexes capable
of being excited by light energy in the region of 650 to 1500 nm
which are disclosed in, for example, Japanese Kokai Publication
Hei-03-111402 and Japane se Kokai Publication Hei-05-194619, and
the like. The combined use of a boron-based sensitizer is more
preferred.
[0184] Since it is necessary to photofunctionalize the system only
slightly, the addition amount of the photopolymerization initiator
is preferably 0.001 to 10 parts by weight per 100 parts by weight
of the polymer of this composition, although the addition amount is
not particularly restricted.
[0185] The technique of effecting polymerization by means of active
radiation is not particularly restricted but includes irradiation
with light and/or electron beams using a high pressure mercury
lamp, low pressure mercury lamp, electron beam irradiating
apparatus, halogen lamp, light emission diode or semiconductor
laser or the like, according to the properties of the
photopolymerization initiator employed.
(Thermal Polymerization)
[0186] The macromonomer (I) of the invention can be polymerized by
means of heat.
[0187] This method is not restricted but is suited for use in
producing gels by polymerizing the macromonomer (I) with a polymer
(III) having two or more terminal polymerizable carbon-carbon
double bonds.
[0188] In thermal polymerization, the system preferably contains a
thermal polymerization initiator.
[0189] The thermal polymerization initiator to be used in the
practice of the invention is not particularly restricted but
includes azo initiators, peroxides, persulfuric acid salts and
redox initiators.
[0190] Suitable azo initiators are not restricted but include
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33),
2,2'-azobis(2-amidinopropane) dihydrochloride (VAZO 50),
2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO 52),
2,2'-azobis(isobutyronitrile) (VAZO 64),
2,2'-azobis-2-methylbutyronitrile (VAZO 67),
1,1'-azobis(1-cyclohexanecarbonitrile) (VAZO 88) (all available
from Du Pont Chemicals), 2,2'-azobis(2-cyclopropylpropionitrile)
and 2,2'-azobis(methyl isobutyrate) (V-601)(available from Wako
Pure Chemical Industries), among others.
[0191] Suitable peroxide initiators are not restricted but include
benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl
peroxide, dicetyl peroxydicarbonate,
di(4-tert-butylcyclohexyl)peroxydicarbonate (Perkadox 16S)
(available from Akzo Nobel), di(2-ethylhexyl) peroxydicarbonate,
tert-butyl peroxypivalate (Lupersol 11)(available from Elf
Atochem), tert-butyl peroxy-2-ethylhexanoate (Trigonox 21-C50)
(available from Akzo Nobel) and dicumyl peroxide, among others.
[0192] Suitable persulfate initiators are not restricted but
include potassium persulfate, sodium persulfate and ammonium
persulfate.
[0193] Suitable redox (oxidation-reduction) initiators are not
restricted but include combinations of such a persulfate initiator
as mentioned above with a reducing agent such as sodium hydrogen
metasulfite or sodium hydrogen sulfite; systems based on an organic
peroxide and a tertiary amine, for example the system based on
benzoyl peroxide and dimethylaniline; and systems based on an
organic hydroperoxide and a transition metal, for example the
system based on cumene hydroperoxide and cobalt naphthenate; among
others.
[0194] Other initiators are not restricted but include pinacols
such as tetraphenyl 1,1,2,2-ethanediol, and the like.
[0195] Preferred thermal polymerization initiators can be selected
from the group consisting of azo initiators and peroxide
initiators. More preferred are 2,2'-azobis(methyl isobutyrate),
tert-butyl peroxypivalate and
di(4-tert-butylcyclohexyl)peroxydicarbonate, and mixtures of
these.
[0196] The thermal initiator to be used in the practice of the
invention is present in a catalytically effective amount and such
amount is not restricted but typically is about 0.01 to 5 parts by
weight, more preferably about 0.025 to 2 parts by weight, per 100
parts by weight of the total amount of the above macromonomer (I)
and another monomer and oligomer mixture added. When an initiator
mixture is used, the total amount of the initiator mixture is equal
to the amount to be employed when only one initiator species is
used.
[0197] In the practice of the invention, the technique of thermal
polymerization is not particularly restricted but the temperature
may vary according to the thermal initiator employed, the
macromonomer (I) and the compound(s) to be added, among others.
Generally, however, the temperature is preferably within the range
of 50.degree. C. to 250.degree. C, more preferably within the range
of 70.degree. C to 200.degree. C. The polymerization time may vary
according to the polymerization initiator, monomer(s), solvent,
reaction temperature and other factors but, generally, within the
range of 1 minute to 10 hours.
(Gel)
[0198] When the macromonomer (I) of the invention and a
polyfunctional compound (monomer/oligomer), preferably a polymer
(II) having two or more terminal polymerizable carbon-carbon double
bonds, are polymerized, gels (crosslinked polymers) can be
obtained.
[0199] The polymer (III) can be produced in the same manner as the
macromonomer (I). Particularly when the technique of atom transfer
radical polymerization is utilized, mention may be made of the
technique comprising carrying out the polymerization using a
polyfunctional initiator, followed by terminal functional group
conversion.
[0200] As the polyfunctional monomer, there may be mentioned
neopentyl glycol polypropoxy diacrylate, trimethylolpropane
polyethoxy triacrylate, bisphenol F polyethoxy diacrylate,
bisphenol A polyethoxy diacerylate, dipentaerythritol
polyhexanolide hexaacrylate, tris (hydroxyethyl)isocyanurate
polyhexanolide triacrylate, tricyclodecanedimethylol diacrylate,
2-(2-acryloyloxy-1,1-dimethyl)-5-ethyl-5-acryloyloxymethyl-1,3-dioxane,
tetrabromobisphenol A diethoxy diacrylate, 4,4-dimercaptodiphenyl
sulfide dimethacrylate, polytetraethylene glycol diacrylate,
1,9-nonanediol diacrylate, ditrimethylolpropane tetraacrylate and
the like.
[0201] As the polyfunctional oligomer, there may be mentioned epoxy
acrylate resins, such as bisphenol A-based epoxy acrylate resins,
phenol novolak-based epoxy acrylate resins and cresol novolak-based
epoxy acrylate resins, COOH-modified epoxy acrylate resins,
urethane acrylate resins obtained by reacting a hydroxy-containing
(meth)acrylate [e.g. hydroxyethyl (meth)acrylate, hydroxypropyl
(meth)acrylate, hydroxybutyl (meth)acrylate, pentaerythritol
triacrylate] with a urethane resin derived from a polyol (e.g.
polytetramethylene glycol, polyester diol derived from ethylene
glycol and adipic acid, .epsilon.-caprolactone-modified polyester
diol, polypropylene glycol, polyethylene glycol, polycarbonate
diol, hydroxy-terminated hydrogenated polyisoprene,
hydroxy-terminated polybutadiene, hydroxy-terminated
polyisobutylene) and an organic isocyanate (e.g. tolylene
diisocyanate, isophoronediisocyanate, diphenylmethanediisocyanate,
hexamethylene diisocyanate, xylylene diisocyanate), resins derived
from the above-mentioned polyols by introducing a (meth)acryl group
via an ester bond, and polyester acrylate resins, among others.
<Utility>
[0202] The branched polymer of the invention can be used in
applications equivalent to those of existing elastomers.
Specifically, it can be used in modifying resins and asphalt, in
compounding with resins and block copolymers (if necessary with
addition of a plasticizer, filler, stabilizer, etc.), as a
shrinkage control agent for thermosetting resins, or as a base
polymer in adhesives, pressure sensitive adhesives and damping
materials. As specific fields of application thereof, there may be
mentioned automobile interior and exterior parts, electric and
electronic fields, films and tubes for food packaging, containers
for drugs and containers for medical use and sealable materials,
among others.
[0203] The branched polymer of the invention can itself serve also
as a molding material, namely as a shock resistant resin and, when
used in admixture with various thermoplastic resins or
thermosetting resins, can serve as a shock resistance improving
agent to provide such resins with high shock resistance. In
addition, it can be used as a processability improving agent,
solubilizing agent, delusterant, heat resistance improving agent or
the like.
[0204] The thermoplastic resins whose shock resistance can be
improved by addition of the branched polymer of the invention are
not restricted but include polymethyl methacrylate resins,
polyvinyl chloride resins, polyethylene resins, polypropylene
resins, cyclic olefin copolymer resins, polycarbonate re sins,
polyester resins, polycarbonate resin-polyester resin mixtures,
homopolymers and copolymers derived from 70 to 100% by weight of at
lest one vinyl monomer selected from the group consisting of
aromatic alkenyl compounds, cyano-containing vinyl compounds and
(meth) acrylic esters and 0 to 30% by weight of another or other
vinyl monomers copolymerizable with the above vinyl monomers, for
example ethylene, propylene and vinyl acetate, and/or conjugated
dienes such as butadiene and isoprene, polystyrene resins,
polyphenylene ether resins, polystyrene resin-polyphenylene ether
resin mixtures and the like. Thus, a wide range of thermoplastic
resins can be used. In particular, polymethyl methacrylate resins,
polyvinyl chloride resins, polypropylene resins, cyclic polyolefin
resins, polycarbonate resins and polyester resins, among others,
are preferred since weathering resistance, shock resistance and
like features can readily be obtained with them.
[0205] As the method of adding the branched polymer of the
invention to various resins, there may be mentioned the method
comprising using a Banbury mixer, roll mill, twin-screw extruder or
like apparatus known in the art, thus effecting mixing mechanically
and shaping into pellets. The extruded and shaped pellets can be
molded in a wide temperature range and, for the molding,
conventional injection molding machines, blow molding machines,
extrusion molding machines and like machines are used.
[0206] In these resin compositions, there may further be
incorporated a shock resistance improver, stabilizer, plasticizer,
lubricant, flame retardant, pigment, filler and so on, as
necessary. Specifically, mention may be made of shock resistance
improvers such as methyl methacrylate-butadiene-styrene copolymers
(MBS resins), acrylic graft copolymers and acryl-silicone composite
rubber-like graft copolymers; stabilizers such as triphenyl
phosphite; lubricants such as polyethylene wax and polypropylene
wax; flame retardants such as triphenyl phosphate, tricresyl
phosphate and like phosphate flame retardants, decabromobiphenyl,
decabromobiphenyl ether and like bromine-containing flame
retardants, and antimony trioxide and like flame retardants;
pigments such as titanium oxide, zinc sulfite and zinc oxide;
fillers such as glass fiber, asbestos, wollastonite, mica, talc and
calcium carbonate; among others.
[0207] The branched polymer, in particular stellar polymer, of the
invention is useful as an additive, desirably a viscosity modifier
(viscosity index improving agent) for lubricant oils and the like,
although the use thereof is not particularly restricted thereto.
The addition amount of the polymer of the invention to lubricant
oils or the like is not particularly restricted but preferably is
about 0.1% by weight to about 30% by weight, more preferably about
1% by weight to about 10% by weight. The target lubricant oils are
not restricted but include oils used in automobiles, airplanes,
ships and railroad vehicles, oils used in spark ignition or
compression ignition, and synthetic oils or mineral oils, for
instance, oils for use in the summer season, oils for use in the
winter season and so forth. Typical lubricant oils preferably have
a boiling point of about 300.degree. C. to about 350.degree. C. For
facilitating the addition of the polymer of the invention to
lubricant oils, it is preferred to use the polymer in the form of a
concentrate containing the same in an amount of about 1 to 50% by
weight, preferably about 0.5 to 20% by weight, in a synthetic oil
or mineral oil.
[0208] The branched polymer of the invention can be used in a
pressure sensitive adhesive composition.
[0209] The pressure sensitive adhesive composition of the invention
preferably comprises a (meth)acrylic polymer as its main component
and therefore it is not always necessary to add a tackifier resin.
If necessary, however, various tackifiers can be used. Specific
examples are phenol resins, modified phenol resins,
cyclopentadiene-phenol resins, xylene resins, coumarone resins,
petroleum resins, terpene resins, terpene-phenol resins and rosin
ester resins.
[0210] In the pressure sensitive adhesive composition of the
invention, various additives, for example an antioxidant,
plasticizer, physical property modifier, solvent and the like may
be incorporated for adjusting the physical properties of the
composition.
[0211] Since the acrylic polymer is intrinsically excellent in
durability, it is not always necessary to add an antioxidant. If
necessary, however, conventional antioxidants and ultraviolet
absorbers can be used each in an appropriate amount.
[0212] For physical property, appearance and/or consistency
modification, the plasticizer includes phthalic esters such as
dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate
and butyl benzyl phthalate; nonaromatic dicarboxylic acid esters
such as dioctyl adipate and dioctyl sebacate; polyalkylene glycol
esters such as diethylene glycol dibenzoate and triethylene glycol
dibenzoate; phosphate esters such as tricresyl phosphate and
tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as
alkyldiphenyls and partially hydrogenated terphenyl; and so forth,
and these may be used singly or two or more of them may be used in
admixture. They are not always necessary, however. These
plasticizers may be incorporated in the step of polymer manufacture
as well.
[0213] As the solvent, there may be mentioned, for example,
aromatic hydrocarbon solvents, such as toluene and xylene, ester
solvents, such as ethyl acetate, butyl acetate, amyl acetate and
cellosolve acetate, and ketone solvents, such as methyl ethyl
ketone, methyl isobutyl ketone and diisobutyl ketone. These
solvents may be used in the step of polymer manufacture.
[0214] Various adhesion improving agents may be added to the
pressure sensitive adhesive composition of the invention to thereby
improve the adhesion to various supports (plastic films, paper,
etc.). Examples are alkylalkoxysilanes such as
methyltrimethoxysilane, dimethyldimethoxysilane,
trimethylmethoxysilane and n-propyltrimethoxysilane; functional
group-containing alkoxysilanes, for example
alkylisopropenoxysilanes such as dimethyldiiso-propenoxysilane,
methyltriisopropenoxysilane and
.gamma.-glycidoxypropylmethyldiisopropenoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-glycidoxy-propyltrimethoxysilane, vinyltrimethoxysilane,
vinyldimethylmethoxysilane, .gamma.-aminopropyltrimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropyltrimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane and
.gamma.-mercaptopropylmethyldimethoxysilane; silicone varnishes;
and polysiloxanes.
[0215] The pressure sensitive adhesive composition of the invention
can be widely applied to tapes, sheets, labels, foils and the like.
For example, the pressure sensitive adhesive composition, in the
form of a solution, emulsion or hot melt, is applied to films made
of a synthetic resin or modified natural resin, paper, all kinds of
cloths, metal foils, metallized plastic foils, asbestos or glass
fiber and like substrate materials and then cured by means of
actinic energy radiation or heat.
[0216] In addition, the polymer of the invention can be used in
sealing materials, paints, coating compositions, sealants,
adhesives, potting materials, casting materials, molding materials
and so forth.
BEST MODES FOR CARRYING OUT THE INVENTION
[0217] The following specific examples and comparative examples
illustrate the present invention. The examples are, however, by no
means limitative of the scope of the invention.
[0218] In the examples, "part(s)" and "%" indicate "part(s) by
weight" and "% by weight", respectively.
[0219] In the examples, the "number average molecular weight" and
"molecular weight distribution (ratio of weight average molecular
weight to number average molecular weight)" were determined on the
standard polystyrene basis using gel permeation chromatography
(GPC). The GPC column used was a crosslinked polystyrene gel-packed
one and the GPC solvent used was chloroform.
[0220] In the examples, the "mean number of terminal (meth)
acryloyl groups" is the "number of (meth)acryloyl groups introduced
per polymer molecule" as calculated based on the results of .sup.1H
NMR analysis and the number average molecular weight determined by
GPC.
PRODUCTION EXAMPLE 1
Synthesis of Br-Terminated poly(butyl acrylate)--(1)
[0221] A 2-L separable flask equipped with a reflux condenser and
stirrer was charged with CuBr (5.54 g, 38.6 mmol) and the reaction
vessel was purged with nitrogen. Acetonitrile (73.8 mL) was added,
and the contents were stirred on an oil bath at 70.degree. C. for
30 minutes. Thereto were added butyl acrylate (132 g), methyl
2-bromopropionate (14.4 mL, 0.129 mol) and
pentamethyldiethylenetriamine (4.69 mL, 0.022 mol), and the
reaction was started thereby. While heating at 70.degree. C. with
stirring, butyl acrylate (528 g) was added dropwise continuously
over 90 minutes and thereafter heating was continued with stirring
for 80 minutes.
[0222] The reaction mixture was diluted with toluene and passed
through an activated alumina column, and the volatile matter was
distilled off under reduced pressure to give poly(butyl acrylate)
having a Br-containing group at one terminus (hereinafter referred
to as polymer [1]). The polymer [1) had a number average molecular
weight of 5,800 and a molecular weight distribution of 1.14.
PRODUCTION EXAMPLE 2
Synthesis of Potassium Acrylate
[0223] A flask was charged with methanol (500 mL) and the contents
were cooled to 0.degree. C. Thereto was added tert-butoxypotassium
(78 g) in several divided portions. This reaction mixture was
maintained at.0.degree. C. and a methanol solution of acrylic acid
(50 g) was added dropwise thereto. After completion of the
dropping, the temperature of the reaction mixture was returned from
0.degree. C. to room temperature and then the volatile matter was
distilled off from the reaction mixture under reduced pressure to
give potassium acrylate (hereinafter referred to as carboxylic acid
salt [1]) represented by the following formula: [0224]
CH.sub.2.dbd.CHCO.sub.2K.
PRODUCTION EXAMPLE 3
Synthesis of Potassium Methacrylate
[0225] A flask was charged with methanol (800 mL) and the contents
were cooled to 0.degree. C. Thereto was added tert-butoxypotassium
(130 g) in several divided portions. This reaction mixture was
maintained at 0.degree. C. and a methanol solution of methacrylic
acid (100 g) was added dropwise thereto. After completion of the
dropping, the temperature of the reaction mixture was returned from
0.degree. C. to room temperature and then the volatile matter was
distilled off from the reaction mixture under reduced pressure to
give potassium methacrylate (hereinafter referred to as carboxylic
acid salt [2]) represented by the following formula: [0226]
CH.sub.2.dbd.C(CH.sub.3)CO.sub.2K.
EXAMPLE 1
Synthesis of Acryloyl Group-Containing Macromonomer
[0227] A 500-mL flask equipped with a reflux condenser was charged
with the polymer [1] (150 g) obtained in Production Example 1, the
carboxylic acid salt [1] (6.61 g) obtained in Production Example 2
and dimethylacetamide (150 mL) and the mixture was heated at
70.degree. C. for 3 hours with stirring to give poly(butyl
acrylate) having an acryloyl group at one terminus (hereinafter
referred to as macromonomer [1]). The macromonomer (1] was purified
by distilling off the dimethylacetamide from the reaction mixture,
dissolving the residues in toluene, passing the solution through an
activated alumina column and then distilling off the toluene. The
mean number of terminal acryloyl groups of the macromonomer [1] was
1.1 and the number average molecular weight was 6,000 and the
molecular weight distribution was 1.14.
EXAMPLE 2
Synthesis of Methacryloyl Group-Containing Macromonomer
[0228] A 500-mL flask equipped with a reflux condenser was
charged-with the polymer [1] (150 g) obtained in Production Example
1, the carboxylic acid salt (2] (7.45 g) obtained in Production
Example 3 and dimethylacetamide (150 mL) and the mixture was heated
at 70.degree. C. for 3 hours with stirring to give poly(butyl
acrylate) having an methacryloyl group at one terminus (hereinafter
referred to as macromonomer {2]). The macromonomer (2] was purified
by distilling off the dimethylacetamide from the reaction mixture,
dissolving the residues in toluene, passing the solution through an
activated alumina column and then distilling off the toluene. The
mean number of terminal methacryloyl groups of the macromonomer (2]
was 1.0 and the number average molecular weight was 6,000 and the
molecular weight distribution was 1.13.
EXAMPLE 3
Synthesis of a Stellar Polymer--(1)
[0229] The macromonomer [1] (100 parts) was thoroughly blended with
diethoxyacetophenone (0.2 part), which was used as a photo radical
generator, to give a composition. The composition was defoamed
under reduced pressure and poured into a glass mold and covered
with a glass plate to prevent the surface from contacting with the
air. Radical polymerization was effected by irradiating with light
from a high pressure mercury lamp (SHL-100UVQ-2; product of Toshiba
Litech) at an irradiation distance of 20 cm for 5 minutes.
Formation of a macromolecular substance (number average molecular
weight 112,000, molecular weight distribution 1.28) was
confirmed.
EXAMPLE 4
Synthesis of a Stellar Polymer--(2)
[0230] The macromonomer [1] (100 parts) was thoroughly blended with
diethoxyacetophenone (0.2 part), which was used as a photo radical
generator, and laurylmercaptan (1.0 part), which was used as a
chain transfer agent, to give a composition. The composition was
defoamed under reduced pressure and poured into a glass mold and
covered with a glass plate to prevent the surface from contacting
with the air. Radical polymerization was effected by irradiating
with light from a high pressure mercury lamp (SHL-100UVQ-2; product
of. Toshiba Litech) at an irradiation distance of 20 cm for 5
minutes. Formation of a macromolecular substance (number average
molecular weight 17,500, molecular weight distribution 1.38) was
confirmed.
EXAMPLE 5
Synthesis of a Stellar Polymer--(3)
[0231] The procedure of Example 4 was followed in the same manner
except that the macromonomer [2)(100 parts) was used in lieu of the
macromonomer [1] (100 parts). Formation of a macromolecular
substance (number average molecular weight 30,000, molecular weight
distribution 1.17) was confirmed.
EXAMPLE 6
Synthesis of a Graft Copolymer
[0232] A 100-mL three-necked flask equipped with a reflux condenser
was charged with the macromonomer [2] (5.0 g), methyl methacrylate
(7.5 mL, 70 mmol), 2,2'-azobisisobutyronitrile (0.460 g, 2.8 mmol)
and toluene (10 mL), and the dissolved oxygen was removed by
blowing nitrogen gas into the mixture for 15 minutes. Four hours of
heating at 60.degree. C. with stirring gave a graft copolymer. The
graft copolymer was purified by repeated reprecipitation in
methanol. The graft copolymer had a number average molecular weight
of 36,000 and a molecular weight distribution of 1.71.
[0233] The graft copolymer obtained in this experiment is comprised
of poly(methyl methacrylate) as a trunk polymer and poly(butyl
acrylate) as polymer branches.
PRODUCTION EXAMPLE 4
Synthesis of poly(butyl acrylate) having Acryloyl Groups at Both
Termini
[0234] n-Butyl acrylate was polymerized using cuprous bromide as
the catalyst, pentamethyldiethyelenetriamine as the ligand and
diethyl 2,5-dibromoadipate as the initiator, to give
bromine-terminated poly(n-butyl acrylate) with a number average
molecular weight of 10,800 and a molecular weight distribution of
1.15.
[0235] This polymer (300 g) was dissolved in N,N-dimethylacetamide
(300 mL), 7.4 g of the carboxylic acid salt [1] was added, and the
mixture was heated at 70.degree. C. for 3 hours with stirring in a
nitrogen atmosphere to give a mixture of poly(n-butyl acrylate)
having acryloyl groups at both termini (hereinafter referred to as
telechelic oligomer [1]). The telechelic oligomer [1] was purified
by distilling off the N,N-dimethylacetamide from the mixture under
reduced pressure, adding toluene to the residue, filtering off the
insoluble matter and distilling off the toluene from the filtrate
under reduced pressure.
[0236] The mean number of terminal acryloyl groups in the
telechelic oligomer [1] was 2.0.
Example 7 to 9
Preparation of Cured Pressure Sensitive Adhesive Compositions
[0237] The macromonomer [1], the telechelic oligomer (1] and
diethoxyacetophenone were mixed up according to the formulations
shown in Table 1. Each of the resulting compositions was defoamed
under reduced pressure and then filled into a mold, the surface
thereof was covered with a glass plate, to give a test specimen.
The thus-prepared test specimens were irradiated with light using a
high pressure mercury lamp (SHL-100UVQ-2; product of Toshiba
Litech) (irradiation conditions: irradiation time 5 minutes,
irradiation distance 20 cm), whereupon rubber-like cured products
having surface adhesiveness were obtained.
[0238] The cured products obtained were measured for gel fraction.
The gel fraction was calculated in terms of the ratio between the
weight before extracting the uncured portion from the cured product
and the weight after extraction. The extraction of the uncured
portion was-effected by immersing the cured product in toluene. The
thus-obtained results are also shown in Table 1. TABLE-US-00001
TABLE 1 Example 7 Example 8 Example 10 Macromonomer [1] (parts) 70
50 30 Telechelic oligomer (parts) 30 50 70 Diethoxyacetophenone 0.2
0.2 0.2 (parts) Gel fraction (%) 93 93 90
EXAMPLE 10
Preparation and Testing of a Pressure Sensitive Adhesive Sheet
[0239] The macromonomer [1] (70 parts), the telechelic oligomer (1]
(30 parts) and diethoxyacetophenone (2 parts) were mixed up to give
a pressure sensitive adhesive composition. The pressure sensitive
adhesive composition obtained was applied to a corona-treated
50-.mu.m-thick polyethylene terephthalate film (product of Toray)
and irradiated with light in a nitrogen atmosphere using a high
pressure mercury lamp (SHL-100UV4Q-2; product of Toshiba Litech)
for 10 minutes for effecting curing.
[0240] The thus-obtained pressure sensitive adhesive sheet was.
subjected to the inclined ball tack test according to JIS Z 0237.
The maximum ball number was 3. The approach was 100 mm long, the
measuring part-was 100 mm long and the angle of inclination was 20
degrees.
INDUSTRIAL APPLICABILITY
[0241] In accordance with the invention, a vinyl polymer
macromonomer having a polymerizable carbon-carbon double bond, such
as a (meth)acryloyl group, terminally introduced therein with a
high probability is used and, therefore, those graft copolymers,
stellar polymers, gels and the like which have vinyl polymer
branches and have so far been difficult to synthesize can be
synthesized with ease. Furthermore, by producing the macromonomer
by living radical polymerization, in particular atom transfer
radical polymerization, it becomes possible to produce the above
polymers or gels having well controlled side chain molecular
weights.
* * * * *