CA2023546A1 - Catalysts - Google Patents

Abstract

ABSTRACT

CATALYSTS

A polymerisation process which comprises contacting at least one polar acrylic type or maleimide monomer under polymerisation conditions with a catalyst comprising (i) and (ii):
(i) a tetracoordinate organosilicon, organotin or organogermanium initiator having at least one initiating site in which a silicon, tin or germanium atom is bound by a nitrogen or phosphorus atom to a nitrogen- or phosphorus-containing group which is devoid of any reactive hydrogen atom, and (ii) a co-catalyst which is a complex of a) a source of fluoride, bifluoride, cyanide, cyanate, aliphatic or aromatic mono-sulphonate or azide ions or a Lewis acid, which ion source or Lewis acid is available in the polymerisation medium, with b) a complexing agent, and the catalyst and the co-catalyst.

Description

QM 35402 2023~i46 CATALYSTS
This invention relates to a polymerisation process and more particularly to a process for polymeriæing polar olefinic monomers.
The group transfer polymerisation of acrylic type and maleimide monomers using certain organosilicon, organotin or organogermanlum lnitiators and co-catalysts which are Lewis acids or sources of fluoride, bifluoride, cyanide or azide ions has been described in United States Pa~ents No 4414372 and 4417034. The products are said to be ~living~ polymers by which is meant polymers which contain at least one active terminal group and are capable of polymerising further in the presenc~ of monomer(s) and co-catalyst.
Whilst solvents are said to be not essential, it is acknowledged in the above mentioned patents that they are beneficial in controlli~g temperature during the exothermic polymerisations. In fact, in the absence of solvents the rate of polymerisation is extremely high and hitherto this polymerisation technique has been of no practical value in bulk polymerisation processes.
It has now been found that the rate of polymerisation in polymerisation processes (especially in the bulk) can be moderated by using the co-catalyst in the form of a complex. By contrast, the rate of polymerisation cannot be satisfactorily controlled by merely reducing the concentration of the initiator or the co-catalyst.
It is also desirable to be able to produce high molecular weight polymers in catalysed addition polymerisation, in particular of polar olefinic (including acrylic type) monomers, with a narrow molecular weight distribution, in particular in the bulk polymerisation of such monomers.

: ~- , : . - : .

2023~46 -- 2 -- .

~owever, hi~herto this has been difficult to achieve.
We have now found that certain types of catalysts may be used advantageously to produce high molecular weight polymers with a narrow molecular weight distribution, and especially in some cases in the controlled bulk polymerisation of polar olefinics, in particular of acrylics.
Accordingly, the invention provides a polymerisation process which comprises contacting at least one polar acrylic type or maleimide monomer under polymerisation conditions with a catalyst comprising (i) and (ii):
(i) a tetracoordinate organosilicon, organotin or organogermanium initiator having at least one initiating site in which a silicon, tin or germanium atom is bound - :~
by a nitrogen or phosphorus atom to a nitrog~n- or phosphorus-containing group which is devoid of any -:~
reactive hydrogen atom, and (ii) a co-catalyst which is a complex of a) a source of fluoride, bifluoride, cyanide, cyanate, aliphatic or aromatic mono-sulphonate or C
azide ions or a Lewis acid, which ion source or : - .
Lewis acid is available in the polymerisation medium, with b) a complexing agent. ~
Monomers which may be polymerised by the process : :
of the invention include monomers of the formula:
- ::
CH= CH
I . ' . -.
CH2=C(Y)X, or O=C C=O :
N ~ :

R

202~4~

wherein:
X iS CN, -CH=CHC(0)X' or -C(O)X';
Y iS -H, -CH3,-CN or -C02R, provided, however, when X' is -CH=CHC(0)X', Y iS -H or -CH3;
S X' iS -OSi(Rl)3, -R, -OR or -NR'R"; each Rl independently is H or a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, provided that at least one Rl group is not H; 0 R is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic aromatic radical containing up to 20 carbon atoms, or a polymeric radical containing at least 20 carbon atoms, any of said radicals optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally containing one or more functional substituents that are unreactive under polymerizing conditions, and optionally containing one or more reactive substituents of the formula:
-Z'(O)C-C(Yl)=CH~ wherein yl is H or CH3 and Z' is O or NR';
and each of R' and R" is independently selected from C~-4 alkyl.
As indicated above in the definition of R in the formulas for the monomer, substituents having oxygen-nitrogen- or silicon-containing groups which are devoid of reactive hydrogen atoms under polymerizing conditions may be used. Groups such as OSi(Rl), and CONH~ are -nonreactive under such conditions and therefore can be tolerated. On the other hand, groups such as CO~H and OH are reactive under polymerizing conditions. Such groups must be chemically protected, i.e. deactivated.

-- 2023~4~

Monomers containing such deactivated group~ are useful in the preparation of polymers which upon treatment to remove the protective group, have functional sites along the polymer chain. Monomers which contain sufficiently sterically hindered amine and alcohol groups that remain inert under reactive conditions may be used directly without deactivation.
Typical examples of vinylic monomers with such functional groups, which may be polymerised in the process of the present invention include:
methacrylic acid esters such as methyl methacrylate, ethyl methacryl~te, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tricyclo[5,2,1,0l' 6 ] dec-3-en-8-yl -~
methacrylate and p-tolyl methacrylate.
substituted methacrylic acid esters such as 2-(dimethylamino)ethyl methacrylate, 2-acetoxyethyl methacrylate; 3-methoxypropyl methacrylate and 2-(trimethylslloxy)ethyl methacrylate, polyfunctional methacrylic acid esters such as sorbyl methacrylate, glycidyl methacrylate, 2-~(1-propenyl)oxy]ethyl methacrylate, allyl acrylate, methacryloxyethyl acrylate and linoleate and triethyleneglycol dimethacrylate.
acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, phenyl acrylate and cyclohexyl acrylate;
substituted acrylic acid esters such as 2-(dimethylamino)ethyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, ethyl 2-cyanoacrylate, 4-fluorophenyl acrylate, and ethyl 2-chloroacrylate;
polyfunctional acrylic acid esters such as sorbyl acrylate, 3-methacryloxypropyl acrylate, ;

3~ 2-[~1-propenyl)-oxy]ethyl acrylate and allyl acrylate;

. , ~ . . ~ ...... . ...... ..

2023~
.

unsaturated nitriles such as methacrylonitrile, methylene malononitrile and acrylonitrile;
N,N-dialkyl unsaturated amides such as N,N-dimethylacrylamide; and vinyl compounds, in particular aromatic vinyl compounds, such as propyl vinyl ketone, styrene, o-, m-or p-methylstyrene, o-, m- or p-methoxystyrene a-methylstyrene, o-, m- or p-dimethylaminostYrene or m-or p-chlorostyrene.
Preferred amongst these monomers are:
methyl methacrylate, lauryl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and tricyclo[5,2,1,0~' 6 ] dec-3-en-8-yl methacrylate;
2-(trimethylsiloxy)ethyl methacrylate, 2-methacryloxyethyl acrylate, 2-acetoxyethyl methacrylate and 2-(dimethylamino)ethyl methacrylate;
glycidyl methacrylate and sorbyl methacrylate;
butyl acrylate, methyl acrylate and butyl acrylate; -sorbyl acrylate;
acrylonitrile and methacrylonitrile;
styrene, a-methylstyrene and p-chlorostyrene;
Methyl methacrylate is especially preferred.
Mixtures of two or more monomers may be used if desired.
The catalyst consisting of the componemts (i) and (ii) and the complex co-catalyst component (ii) itself used ln the process of the f~rst aspect of present invention form respectively a second and third aspect of the invention.
Tetracoordinate organosillcon, organotin or organogermanium initiators which may be used in the process of the invention include any having at least one initiating site in which .. . ~ , .... . .. .

- 20235~

a) a silicon, tin or germanium atom is bound to a nitrogen or phosphorus-containing group and b) the group is devoid of any reactive hydrogen atom : :
by the nitrogen or phosphorus atom, including any of those disclosed in European Patent publication ~ :
the disclosure of which is incorporated herein by reference.
Examples of specific initiators which are useful in the process and catalyst system of the invention -~
include an (initiator) first component of formula (I)~

M(Xm)(Yn)ZP (I) wherein M is Si, Ge or Sn m and p are each an integer and n is 0 or an integer such that (m ~ n + p) =4;
X is QR~R22 : .
where Q is N, P, As or P(=T)G.D where T ls O or S
and G and D are each independently a bond, O or S and R1 and R2 are each independently optionally substituted hydrocarbyl or together are optionally ~ :
substituted hydrocarbadiyl which are inert in the process conditions o~ the present invention, or, when Q
is P(=T)G.D as hereinbefore defined, Rl and R2 are each independently M(Yn)Zp as hereinbefore defined.
Y is independently any group as defined for X, or any group selected from a group OA where A is optionally substituted hydrocarbyl inert in the process conditions of the present invention, or trialkylsilylalkyl;
Z is independently any group as defined for Y, or an organic polymer radical comprising further M(Yn)Zp : -moieties; or .
p is 2 and ., ' '~' ', : - .::

2023~46 Z~ is a group Z1 2 of th~ formula OSiR5R~OSiR7R~O-where Rs, R6, R7 and R~ are each independently selected ~rom any of the values defined for Rl or R2, or Zl 2 iS a moiety -EBE- where E is a bond or O
and B is a polymer diradical, or E is O and B is an inorganic solid on whose surface the two -O- groups are located, which comprises further -OMXmYnO-moieties.
In the (initiator) first component (i) of the catalyst system of formula (I):
Favoured M is Si.
The term 'optionally substituted' herein in relation to X, Y and Z groups includes substitution by pendent mono-or di-valent groups, and, in relation to X
only, substitution by hetero-atoms.
It will be appreciated that, although bonds between M and at least one of X, Y or Z break in the catalytic process of the present invention, the groups themselves should be inert in the process conditions.
For this reason such groups, even when described as optionally substltuted, are often unsubstituted by pendent monovalent substituents.
Within X (ie QRlR2 as hereinbefore defined), Q is often N, P, P=O or O-P(=O)-O, in particular N and P.
Suitable Rl and R~ optionally substituted hydrocarbyl include optionally substituted alkyl, cycloalkyl (including polycycloalkyl), alkenyl, cycloalkenyl, aryl aralkyl and aralkenyl.
Suitable ~1 and R2 optionally sub~tituted alkyl and such alkyl as a component within Rl or R~ include optionally substituted Cl_. alkyl, in particular methyl. Such alkyl groups are often unsubstituted.
When X is N or P, such R~ and R2 groups include optionally substituted oxo-substituted alkyl, i.e. such Cl_~ alkanoyl, in particular acetyl.

. ~ ~ . . .

Suitable R1 and R2 optionally substituted cycloalkyl include such Cs_a cycloalkyl, for example cyclohexYl, and polycycloalkyl. Such cycloalkyl groups are often unsubstituted.
Suitable optionally subsituted alkenyl as or within Rl and R2 include optionally substituted C-_-alkenyl, in particular methylprop-1-enyl.
Suitable R1 and R2 op~ionally substituted cycloalkenyl include such C5-~ cycloakenyl, for example cyclohex-l-enyl, especially when Q is N. Such cycloalkenyl groups are often unsubstituted.
Suitable R1 and R2 optionally substituted aryl include phenyl optionally substituted by substituents inert in the desired polymerisation conditions, which include alkyl and aryl. Such aryl groups are however often unsubstituted.
Suitable R1 and R2 optionally substituted aralkyl groups include the abovP suitable alkyl groups substituted by the above suitable aryl groups, and thus include benzyl optionally substituted in the phenyl ring, but more often unsubstituted benzyl.
Suitable R1 and R2 optionally subsituted aralkenyl include the above suitable alkenyl groups substituted by the above suitable aryl groups, and thus include 2-methyl-1-phenylprop-1-enyl ~phenylmethallyl) optionally substituted in the phenyl ring, but more `
often unsubstitued 2-methyl-1-phenylprop-1-enyl.
When Q is N, R1 and R2 are favourably together optionally substituted hydrocarbadiyl.
In one preferred group, such (R1 ~ R2) are unsubstituted by hetero-atoms.
In a second preferred group, such (R1 + R3) are substituted by hetero-atoms other than nitrogen.
In a third preferred group, such (Rl + R2) are unsubstituted by pendent monovalent substituents.

2023~46 g In a fourth preferred group, such (R1 + Rl) have and/or w saturated carbon atoms substituted by oxo groups.
Por all values of Q :
S Suitable (R1 ~ R2) optionally substituted hydrocarbadiyl exclude 1,2-diyl, but include optionally substituted alkadiyl, (poly)cycloalkadiyl, alkenediyl, alkapolyenediyl, cycloalkenediyl and arylene, and diradical combinations of such diradicals such as arylenealkyl, arylenealkenyl and arylenecycloalkYl.
Suitable (R1 + R2) optionally substituted alkadiyl include ,w-C 3 _ 6 alkadiyl optionally substituted by at least one hetero-atom or -group such as O, S or NR3 where R~ is independently any of the values of R1, or independently another group M(Y n)Zp as hereinbefore de f ined.
Corresponding QR1R2 groups thus include 4 to 7-member heterocyclyl groups, such as pyrrolidino, piperidino and morpholino, and N'-C1_~ alkylpiperazino, and phosphs-analogues thereof, in particular morpholino.
Such groups are often not further substituted.
When X is N, such (R1 + R2) groups include æimilarly op~ionally substituted, a-oxo- or ,w-dioxo-substituted alkadiyl.
Corresponding QR'R2 may be a 4 to 7-member lactamido or cycloimido group such as N-piperidonyl or succinimido. Such groups are often not further substituted.
Suitable (R~+R2) optionally substituted alkenediyl and alkapolyenediyl include ~,w- C~_~ alkenediyl, , W-C ~ _ 6 alkadienediyl and ,w- hexatrienediyl optio~ally substituted by at least one hetero-atom or group, such as O or S, or NR3 where R' is independently any of the values of R1.

. . ~ :: :. : , ~ , 2~2354~

Corresponding QR~R2 groups thus include 5- to 7-member unsaturated heterocyclyl groups such as 1-pyrryl, pyrrolinyl, imidazolyl and imidazolinyl, in particular imldazolyl, which are are often not further substituted.
When X is ~, such (R1 + Rl) ~roups include similarly optionally subsititued ~-oxo- or a,w-dioxo-disubstituted alkenediyl, ie QR1R2 may be a heterocyclyl group such as oxazolid-2-on-3-yl.
R' and R 2 may each be alkylene - or arylene-1~ carbonyl in a polyamlde chain bearing other M(Yn)Zp groups.
Suitable (R~ + R2) optionally substituted arylene groups include biphenyl-2,2'-diyl optionally substituted as for R' and R~ aryl.
Corresponding QR1R2 groups thus include optionally substituted 9-carbazolyl and its phospha analogue. Such groups may be substituted in the aryl moiety by alkyl but are often unsubstituted.
Suitable (R~ t R~) optionally substituted arylene-alkyl groups include groups composed of a 1,2-arylene moiety and an a,~-C 2 _ ~ alkadiyl, which latter may be -oxo-substituted.
Corresponding QR1R2 groups thus include benzo-fused 5- to 7-member saturated heterocyclyl groups such as N-indanyl and N-indan-2-onyl and their phospha analogues. Such ~roups may be substitued in the aryl moiety by alkyl but are often unsubstituted.
Suitable (R1 + RZ) optionally substituted arylenealkenyl groups include groups composed of a 1,2-arylene moiety and an a,w C a _ - alkenediyl.
Corresponding QR~R~ groups thus include benzo-fused 5- to 7-member unsaturated heterocyclyl groups ~uch as N-indolyl and its phospha analogue. Such groups may be substituted in the aryl moiety by alkyl but are often unsubstituted.

. . . -2023~

Suitable (Rl + R2) optionally substituted arylene-cycloalkyl groups include groups composed of a 1,~-arylene moiety and 1',2'-Cs_ 7 cycloalkadiyl moiety.
Corresponding QR~R2 groups thus include 1,2,3,4-tetrahydro-9-carbazolyl and its phospha analogue. Such groups may be substituted in the aryl moiety by alkyl bu~ are often unsubstituted.
Suitable A groups within Y and Z include optionally substituted alkyl, cycloalkyl (including polycycloalkyl), alkenyl, cycloalkenyl, aryl, aralkyl, alkyl disubstituted by arylene and alkenyl disubstituted by arylene.
Suitable Y, Z and A alkyl groups include C1_ 2 0 alkyl groups, such as C1_~ alkyl groups. Suitable C~_O
alkyl groups include favoured straight-chain C~_~ alkvl ~ ;
groups, eg methyl and ethyl, and also include branched -C._~ alkyl groups, in particular those with a high degree of branching, eg optionally substituted (but often unsubstituted) neopentyl. ~ ;
Within Y, Z and A groups comprising component alkyl groups, favoured alkyl groups include C~_~ alkyl, in particular methyl.
Suitable Y and Z alkoxy groups include C~_~
alkoxy, in particular methoxy and ethoxy.
Suitable Y, Z and A cycloalkyl ~roups include polycycloalkyl, in particular adamantyl.
Suitable Y and Z optionally substituted cycloalkoxy ~roups include C--7 cycloalkoxy, thus including cyclohexyloxy, any of which may be a-oxo or a,w-dioxo substituted.
Within Y, Z and A aralkyl groups, favoured ~ ~-optionally substituted aryl groups include optionally substituted phenyl and 1-naphthyl. Suitable substituents for such aryl groups include substituents inert in the desired polymerisation conditions.

, ~ . ; . . . ~

- ~ , 2023~4~

Preferably, the conjugate protic acid of such aryl groups has a PKa in DMS0<18. Such groups will be readily apparent, but include alkyl and aryl groups.
Such aryl groups are often unsubstituted.
Suitable Y and Z optionally substituted aryloxy groups include optionally substituted phenoxy, such as phenoxy. Other suitable substituents include those listed above for Y and z aryl groups.
Favoured ~ and Z aralkoxy groups include phenyl 0 C~_4 alkoxy, in particular benzyloxy, optionally substituted in the phenyl ring. Suitable substituents include those listed above for Y and Z aryl groups.
When A in Y or Z is optionally substituted alkyl disubstituted by arylene, the latter may be optionally substituted biphenyl-2,2'-diyl or 1,2-phenylene, so that corresponding suitable Y and Z optionally substltuted alkoxy disubstituted by arylene include methoxy disubst.ttuted by optionally substituted biphenyl-2,2'-diyl, ie fluorenyl-9-oxy, and propoxy 1,3-disubstituted by 1,2-phenylene, ie indanyloxy.
Such groups are often unsubstituted. However if any arylene moiety in A is substituted, suitable substituents include those listed above for substituents -of aryl groups within Y, Z and A.
When A in Y or Z is optionally substituted alkenyl disubstituted by arylene the latter may be 1,2-phenylene so that corresponding suitable Y and Z optionally substituted alkenyloxy disubstituted by arylene include allyloxy 1,3-disubstituted by optionally substituted -~
1',2'-phenylene, ie optionally substituted 1-indenyloxy.
Such groups are often unsubstituted.
Catalysts of the present invention in which the lnitiator co~ponent (i) has at least one group Y, Z or A
which is a) optionally substituted aralkyl .-- ~ . . ~ ,... -., -:

20235~

b) optionally substituted cycloalkyl (especlallY
polycycloalkyl) or c) optionally substituted branched alkyl may be used advantageously in vinylic bulk polymerisation systems. This is specially so where any such group is bulkily substituted aralkyl, or adamantyl or neopentyl, and other such suitable Y and Z groups also include fluorenyl-9-oxy and indenyl-1-oxy.
The same advantages attach to initiator components where X is a suitable 1-aza analogue of the foregoing Y, Z or A groups.
When p is 2, favoured Zl groups include -OSiR2R6OSiR7R~0- where R5 to R~ are the same and are optionally substituted benzyl (in particular benzyl), lS C~-6 alkyl or optionally substituted phenyl. R~ to R~
are often unsubstituted.
Where Z is an organic polymer radical, or Z2 iS or ~ -comprises a polymer diradical, the polymer is preferably a particulate one insoluble in any desired polymerisation system (for example a highly-cross-linked polymer with the MXmYn moieties on its surface).
Preferably the polymer is a solid granulate of relatively high surface area, for example in the range 200 to 600 m~/gm, favourably with a concentration of MXm~nZ moieties of 1 per 3 to 30 s~uare Angstrom.
M in each MXmYnZ moiety may be linked to the polymer via a carbon atom on e.g. a pendent alkyl containing chain of the type described for Y and Z
straight chain alkyl above.
Depending on the polymerisatlon medium, highly cross-linked alkylene, arylene, acrylic or styrene homo-or co-polymers may be appropriate for B polymer diradicals.

- , . ~

2023~46 Favoured Z 2 groups also lnclude -OBO- where B
is an inorganic solid with a plurality of surface hydroxyl functions, such as silica or a metal hydroxide or hydrated oxide, e.g. alumina. B may be inter alia a flat body of low specific surface area or (preferably) particulate with a relatively hlgh specific surface area, for example in the range 200 to 600 m~/gm.
Favourably, the -OMXmYnO-moieties are present on the surface at a concentration of 1 per 3 to 30 square Angstrom.
This may be achieved by involving at least 20%, preferably at least 60X, of the available surface hydroxyl functions in -OBO-bonding to MmYn moieties.

Further examples of specific initiators which are useful in the process and catalyst system of the invention include an (initiator) first component of formula (II)~
MXl(Yn)Zp (II) wherein M is Si, Ge or Sn;
n is 0 or an integer, and p ls an lnteger such that (n + p) = 3;
R~

xl is a radical - Q - C(Q2) -Q1 - R13 R' where Q and Q1 are each independently N, P or As;
Q2 is O, S, NR or PR where R is C1-4 alkyl;

' . .. ~

: 202~4~

R1, R2 and R13 are each independently optionally substituted hydrocarbyl; or R~ and R13 together are optionally substituted aliphatic hydrocarbadiyl and R1 is optionally substituted hydrocarbyl;
all such R~, R2 and R13 being inert in the conditions of the process of the present invention; ~ -Y and Z are as defined in formula (I).
In the (initiator) first component (i) of formula (II):
Favoured M is Si. ~ ;
The term 'optionally substituted' is as defined in formula (I).
Within xl as hereinbefore defined each of Q and Q' independently is often N or P; preferably both are N
or P, and in particular both are N.
Q2 is often -Sultable, favoured and preferred Rl, R2 and R3 optionally substituted hydrocarbyl are as so described in formula (I) with respect to R1 and R2.
Suitable Rl, R2 and R3 optionally substituted alkyl and such alkyl as a component within the same include optionally substituted Cl_~ alkyl, optionally substituted by hetero-atoms.
A group of preferred Rl, R2 and R13 includes methyl, ethyl and methoxy, especially methyl and methoxy.
In a second preferred group, when Q and/or Q' is N or P, in particular when both are N, such R~ include sila-substituted alkyl, eg trialkylsilyl, especially trimethylsilyl.
When Ql is N, R2 and R13 may together be optionally substituted hydrocarbadiyl.
In one group, such (R2 I R13) are unsubstituted by hetero-atoms.
.~ .

:, . . .
.,. ~; ~, .. ~ - ' :

-` 2023~4~

In a second group, such (R~ + R13) are substituted by hetero-atoms other than nitrogen.
In a third group, such (R~ + . R13) are unsubstituted by pendent monovalent substituents.
For all values of Q1 Suitable, favoured and preferred (R2 + R13) are as æo described in formula (I) with respect to (Rl I R2) Additionally, Rl may be alkylene or arylene and either R2 or R13 may be alkylene or arylene in a ~ -polyurea chain bearing other M(Yn)pZ groups.
Suitable corresponding X will consist of a ;~
repeat moiety of formula:

- R10 - N - ~O - N - R11 -- ~ ~
R2 /13 : ~ .:

where R10 and R11 are each independently alkylene or arylene.
Suitable, favoured and preferred Y, Z and A
~roups are as so described in formula (I).
Part~cular components within a preferred sub-group within formula (II) are those in which q=0 and r=3.
~et further examples of specific initiators which are useful in the process and catalyst system of the lnvention include an (lnitiator) first component comprising a plurality of atoms M as hereinbefore -~
deflned each independently in a moiety of formula ~ ;
(III):

MX2(Y~)ZP (III) wherein ~.. , .. ... . . ~, -: ~ . . ; , ~
:, :' .
~: . . ~ . : :

: : ~ :: ~-. ~

202354~
~
. .
.

M is Si, Ge or Sn n is O or an integer, and p is an integer such that (n + p) = 3;
x2 is a diradical - Q - Rl bound via Q to M ~ ~-R12 :.~
where Q is N, P, As or P(=T)G.D where T is O or S and G and D are each independently a bond, O or S, -~
Rl is optionally substituted hydrocarbyl, or, when Q is P, M(Yn)Zp as herein defined, R12 is optionally substituted hydrocarbadiyl, or R1 and R12 together are optionally substituted hydrocarbatrlyl, all such R1 and R12 being inert in the conditions of the process of the present invention; ~
Y and Z are as defined in formula (I). -In the (initiator) first component (i) of formula (III):
R12 may be linked directly or indirectly to any group as defined for X2, or an organic radical comprising further moieties of formula (I) (which may be a polymer as hereinafter defined in relation to formula (III) only, or one or more M(Yn)Zp moieties as herein defined.
The term "polymer" herein in relation to the initlator components of formula (III) includes a reference to oli~omers. The term ln partlcular includes polymers of vinylic monomers.
Favoured M is Si.
The term 'optionally substituted' is as defined ln formula (I). ~-~
Suitable, favoured and preferred R' optionally substituted hydrocarbyl are as so described in formula (I) with respect to R1 and R2.

2023~4~ ~

In a further preferred group within suitable R~
optionally substituted alkyl when Q is N or P, such R
include optionally further substituted ~-oxo-subst$tuted alkyl, i.e. optionally substituted C~_~
alkanoyl, in particular substituted 2-methylpropionyl, acetyl and formyl.
Formyl may be substituted by alkoxy, such as iso-propoxy and ter.-butoxy. The corresponding groups R' will be isopropoxycarbonyl and tert.-butoxycarbonYl.
Such R1 groups may also favourably be aza-substituted ~ to the Q nitrogen atom, so that X
comprises a ureido group. For example 2-methyl-propionyl may be substituted by N. Such R' groups may also favourably be substituted by substituted amino such as amino substituted by aliphatic substituents, such as alkyl or cycloalkyl, again so that X comprises a ureido group. For example formyl may be substituted by substituted amino such as amino substituted as above.
In both cases the corresponding group R1 will comprise a carbamoyl moiety, eg dimethylcarbamoyl.

Suitable R12 optionally substituted hydro-carbadlyl lnclude optionally substltuted alkanediyl and cycloalkanediyl (lncludlng polycycloalkanediyl).
Suitable R12 optionally substituted hydrocarbadiyl also lnclude alkenediyl and cycloalkenediyl.
Suitable R12 optionally substituted hydrocarbadiyl further include arylene.
Suitable R12 optionally substituted hydrocarbadiyl also include diradical combinations of the foregoing diradicals, such as arylenealkyl, aralkanediyl, arylenealkenyl and aralkenediyl.

:. . . . ~ . . ..................................... .
; . : ~ -. -;. . . ~ . . .

2023~4~

-- 19 -- ~

Suitable R12 optionally substituted alkanediYl include optionally substituted C~_~ alkanediyl, in ~ -particular methylene, ethylene and propylene. Two corresponding MX(Yn)Zp moieties may be joined by their R2 (eg propylene) groups to glve a present catalYst system component (i) in which the two M atoms are bridged by an alkylene (eg 1,6-hexylene) moiety.
When Q is N or P, such Ra groups include alkanediyl which is oxo-substituted to Q and ,w-dioxo-substituted alkanediyl, all optionally inertly substituted.
Such R2 groups may also favourably be aza-substituted ~ to the ~ nitrogen atom, so that X
comprises a ureido group. For example, R2 propane-1,2-diyl may be so substituted to comprise an N-methylcarbamoyl group, with a free valency to the N
atom.
Two corresponding MX(Yn)Zp moieties may be ~-joined by their R2 groups by C2_g straight chain alkylene, in particular 1,6-hexylene, to give a present catalyst system component (i) in which the two M atoms are bridged by a hexylene-1,6-bis(N-methylcarbamoyl) moiety.
Suitable R12 optionally substituted cycloalkanediyl include such C5_~ cycloalkanediyl, eg ~ ~-cyclohexane-1,4-diyl, and polycycloalkanedlyl.
Such cycloalkanediyl groups are often unsubstituted.
Optionally substituted alkenediyl as R12 and as a component within R12 includes optionally substituted C~-alkenediyl, in particular 2-methylprop-1-ene-1,3-diyl.
Suitable R12 optionally substituted cycloalkenediyl include such Cs_s cycloalkenediyl, eg cyclohex-1-ene-1-4-diyl, especially when Q is N.

', ;,'.:"

~ 2023~4~

Suitable R12 optionally substituted cycloalkenediyl also include polycycloalkenediyl.
Such cycloalkenediyl groups are often unsubstituted.
Suitable R12 optionally substituted arylene include phenylene optionally substituted by substituents inert in the conditions of the process of the present invention.
Suitable R12 optionally substituted arylenealkyl and such arylenealkyl as a component within R12 include optionally phenylene-C1_4 alkyl. -~
Suitable R12 optionally substituted aralkenediyl include the above suitable alkenediyl groups substituted by aryl groups corresponding to the above suitable arylene groups. They are more often unsubstituted.
When Q is N, Rl and R12 may be together optionally substltuted hydrocarbatriyl.
In one group, such (Rl + R12) are unsubstituted by hetero-atoms.
In a second group, such (R1 + R12) are substituted by hetero-atoms other than nltrogen.
In a third group, such (R~ + R12) are unsubstituted by pendent monovalent substituents.
In a fourth group, such (Rl + R12) have one or two saturated carbon atoms a to Q~ and in particular also ~ to vinylic unsaturation, substituted by oxo groups.
For all values of Q:
Suitable, favoured and preferred (R1 + R12) are ~enerally as so described for corresponding R12 hereinbefore.
Suitable (Rl + R12) include optionally substituted alkanetriyl and cycloalkanetriyl (including polycycloalkenetriyl).

.

.: . . . .
- . . :........................... .
. ~ , ~ , . .

202354~

Suitable (R' + R12) also include optionally substituted alkenetriyl, alkapolyenetriyl and cycloalkenetriyl, Suitable (R~ + R12) further include optionally substituted arenetriyl, arenetriylalkyl, arylene-alkanediyl, arenetriylalkenyl, arylenealkenediyl, arenetrlylcycloalkyl, and arylenecycloalkanediYl.
Suitable (Rl ~ R12) optionally substituted alkanetriyl include alkanetriyl optionally substituted by at least one hetero-atom or -group such as O, S or NR23 where R23 is independently a bond, any of the values of R', or independently another group M(Yn)Zp as hereinbefore defined.
Corresponding QRlR12 groups thus include 4 to 7-member heterocyclic groups, such as pyrrolidine-1,3-diyl, piperidine-1,4-diyl and piperazine-1,4-diyl, and phospha-analogues thereof. Such groups are often not further substituted.
When Q is N, such (R1 + R12) groups include similarly optionally substltuted, -oxo- or -w-dioxo-substituted alkanetriyl, i.e. QRlR~ may comprise a 4 to 7-member lactamido or cycloimido group, and include imidazolidine-2,4-dione-1,3-diyl, ~
pyrrolid-2-one-1,4-diyl, piperazine-2,5-dione-1,4~diyl ;
and piperid-2-one-1,4-diyl. Such groups are often not further substituted.
Suitable (R' + R12) optionally substituted alkenetriyl and alkapolyenetriyl include C~ _ 6 ~ -alkenetriyl, ,w-C~_ 6 alkadienetriyl and hexatrienetriyl optionally substltuted by at least one hetero-atom or group, such as O or S, or NR3 where R3 is ~ndependently a bond, any of the values of Rl. ~-Corresponding QR'R12 groups thus include 5- to 7- member unsaturated heterocyclodiyl ~roups such as pyrrole-1,3-diyl and pyrroline-1,3-diyl. ~ -', ~-:::, r ~ ~ : : . ' . , 2023~

Such QR'R12 groups thus also include imidazole-1,3-diyl and imidazollne-1,3-diyl, in particular imidazole-1,3-diyl.
Such groups are often not further substituted.
Optionally substituted a-oxo- or a-w-dioxo-substituted alkenetriyl, i.e. QR1R12 may be a hetero-cyclodiyl group, which is eg O-substituted, such as oxazolid-2-one-3,5-diyl. ~- -Suitable (R~ + R12) optionally substituted arenetriyl groups include biphenyl-2,k,2'-triyl, where k is an integer between 3 and 6, optionally substituted as for R~ aryl.
Corresponding QRlR12 groups thus include optionally substituted, u-9-carbazolediyl, where u is 1 or 2, and its phospha analogue. If any arene moiety therein is substituted, suitable substituents include alkyl, and such alkyl as a substituent within (R~ +
R12) include optionally substituted Cl-~ alkyl, ln particular methyl. Such groups are often unsubstituted.
Suitable (R1 + R12) optionally substituted arenetriylakyl and arylenealkanediyl groups lnclude groups composed of a 1,2,k-arenetriyl moiety, where k is integer between 3 and 6, and an a,w-C~_~ alkanediyl, or o~ a 1,2-arylene moiety and a C~_. alkanetriyl moiety, where the aliphatic moieties may be a-oxo-substituted.
Corresponding QRlR12 groups thus include benzo-fused 5 to 7-member saturated heterocyclic groups, such as N-indanyl and N-indan-2-onyl with a second bond to either ring, and their phospha analogues. Such ~R1 + R12) groups may be substituted in the arene moiety by alkyl, but are often unsubstltuted.

, - . . . .

" ::, ' . ..

- 2023~6 Suitable ~Rl + R12) optionally substituted arenetriylalkenyl and arylenealkenediyl groups include groups composed of a 1,2,k-arenetriyl moiety, where k is an integer between 3 and 6, and an a,w-C 2 _ alkenediyl, or of a 1,2-arylene moiety and a C 2 _ ~
alkenetriyl moiety, where the aliphatic moieties may be a-oxo-substituted.
Corresponding QR~R~ groups thus include benzo-fused 5 to 7-member unsaturated heterocyclic ~roups, such as N-indolyl with a second bond to either ring, and its phospha analogue. Such of the (Rl + R12) groups may be substituted in the arene moiety by alkyl, but are often unsubstituted.
Suitable (R~ + R12) optionally substituted arenetriylcycloalkyl and arylenecycloalkanediyl groups include groups composed of a 1,2-k-arenetriyl moiety, -where k is an integer between 3 and 6, and an 1,~-C2_~ ;
cycloalkanediyl, or of a 1,2-arylene moiety and a C2--cycloalkanetriyl moiety, where the aliphatic moieties ~0 may be a-oxo-substituted.
Corresponding QR~R12 groups thus lnclude benzo-fused heteropolycyclics, such as 1,2,3,4-tetrahydro-u,9-carbazolediyl, where u is 1 or 2, and its phospha analogue. Such groups may be substituted in the arene moiety by alkyl but are often unsubstituted.
Suitable, favoured and preferred Y, Z and A
groups are as so described in formula (I).
Favourably R12 in each moiety of the formula (I) may be linked to the rest of the initiator (whether another moiety of the formula (I) or a polymer -including oligomer - backbone) via an alkylene~
containing chain, or via an O or C atom of an alkyleneoxy-containing group.

~. ~ . . . . . . .

-- 2023~4~

Suitable groups therefor comprise alkylene of the type described above for R2, including C~_~ straight chain alkylene, in particular methylene and ethylene.
Where the moiety of formula (III) iS bonded to a polymer (as hereinbefore defined), the polymer may be a particulate one insoluble in any desired polymerisation system) for example a highly-cross-linked polymer as defined for Y and/or Z in formula (I) or a corresponding oligomer soluble ln the the same system.
Favoured (Rl + R12) groups in the initiators of formula (III) include acyclic QR'R12 as hereinbefore defined such as and cyclic QR1R12 as hereinbefore defined such as u,9-carbazolediyl, where u is 1 or 2, imidazolidine-1,4-dione-1,3-diyl, imidazole-1,3-diyl, and oxazolid-2-one-3,5-diyl.
In one preferred group such (Rl + R12) are unsubstituted by hetero-atoms, and preferred X include u,9-carbazolediyl as hereinbefore defined.
In a second preferred group, such (Rl + R12) are substituted by hetero-atoms other than N.
In a third preferred group, such (R~ + R12) unsubstituted by pendent monovalent substituents.
Corresponding QRlR12 groups thus include correspondingly unsubstituted 4 to 7-member heterocycllc groups.
Specific initiator components (1) of interest ~;
are listed ln the Descriptions hereinafter.
The co-catalysts which form the third aspect of the present inventlon may be obtalned by reacting a c~mplexing agent wl~h a source of the anlons recited herelnbefore. The uncomp~exed co-catalysts used in the lnventlon process are either 2023~46 a) known compounds or b) can be prepared by known methods from or analogously to known compounds.
Where the complex co-catalyst is a complexed Lewis acid, it is generally rendered available in the polymerisation medium by being soluble in a polymerising monomer and/or any vehicle.
Complex co-catalysts which are a source of ions as herelnbefore defined are preferred.
Such a complex co-catalyst will often be a salt in which the anion is complexed, and is generally rendered available in the polymerisation process by containing a cation which renders it soluble in a polymerising monomer and/or any vehicle, even when the anion is complexed. -~ -~
Suitable Lewis acid complex co-catalysts thus include those of zinc iodide, bromide, and chloride, mono- and dialkyl- aluminium halides, bis(dialkyl-aluminium)oxides and boron trifluoride.
Where the complex co-catalyst is a complexed ion source, favoured complexed anions therein include those of azide, cyanide, cyanate, $1uoride, bifluoride, difluorotrlmethylsilicate, difluorophenylstannate, and 21iphatic and aromatic mono-sulphonates, in particular fluoride, bifluoride and methanesulphonate ions.
Favoured cations therein, which render the complex co-catalyst available in the polymerisation medium, are often substituted -on~um ions. These include quaternary ammonium and phosphonium, and -tris(dialkylamino)sulphonium, often substituted by ;
relatively bulky organic-soluble groups eg C3_6 alkyl,such as butyl, or C5-- cycloalkyl.
Alkali and alkal~ earth metal cations are less preferred but may be used if, the catalyst also includes a solublisation aid to complex the cations.

2023~

Examples of such aids include crown ethers.
Favoured complex co-catalysts lnclude those of tris(dimethylamino)sulphonium difluorotrimethyl-æilicate, tris(dimethylamino)sulphonium cyanide, tetraphenylarsonium cyanide, tris(dimethyl-amino)sulphonium azide, tetraethylammonium azide, tris(dlmethylamino)sulphonium difluorphenylstannate, tetraethylammonium cyanide and alkali metal cyanides and azides.
Preferred complex co-catalysts include those of ammonium bifluoride, tetramethylammonium fluoride and bifluoride, tetraethylammonium bifluoride and tetrabutylammonium fluoride and bifluoride.
Preferred complex co-catalysts also include those of tris(dimethylamino)sulphonium bifluorid~, alkali metal fluorides and bifluorides, and tetraphenylphosphonium bifluoride, and the corresponding methanesulphonates.
Particularly preferred complex co-catalysts include are those of fluorides such as tetrabutyl-ammonium fluoride.
Suitable complexing agents for use in the co-catalyst include active hydrogen compounds capable of forming isolable complexes with with the co-catalyst, in -particular those which are capable of complexing the ion source anion of a salt co-catalyst as described hereinbefore, eg by hydrogen bonding.
Such complexes may be formed by mixing the active hydrogen compound with the ionic material in a suitable polar solvent such as acetonitrile or tetrahydrofuran (THF).
Examples of active hydrogen compounds which may be employed as complexing agents include:

- 2023~4~

aromatic nuclei such as benzene and benzo derivatives thereof, substituted by one or more groups with exchangeable protons, such as hydroxyl, amlno, mercapto or phosphino groups, and also preferably ~ubstituted by one or more electron-withdrawing substituents, such as cyanide, cyanate, ester (including sulphonate and carboxylate~ or azide, for example phenols, such as 2,6-di-tert.butyl-4-methylphenol, 4-cyanophenol and methyl p-hydroxy- ~ -benzoate;
heteroaromatic keto-enol tautomers and analogues :
thereof, such as amine heteroaromatic nuclei, eg pyrimidine and pyrazine, and benzo derivatives thereof, : :
substituted in the recited nucleus by one or more groups with exchangeable protons, such as hydroxyl, ~ -amino, mercapto or phosphino groups, and also optionally substituted in the recited nucleus by one or ;~
more electron-withdrawing substituents, such as cyanide, cyanate, ester (including sulphonate and carboxylate) or azide, eg uracil;
saturated aliphatlcs (including cyclo- and polycycloaliphatics), substltuted by one or more groups :
with exchangeable protons, such as hydroxyl, hydroxy-imino, amlno, mercapto or phosphino groups, eg the oximes of camphor and butane-2,3-dione, but which are preferably also subs~ituted by one or more electron-withdrawlng groups, eg one, but preferably two or more, aromatic nuclei such .
as benzene and benzo derivatives thereof, in turn optionally substituted by one or more electron-withdrawing substituents, such as cyanide, cyanate, ester (including sulphonate and carboxylate) or azide, eg alcohols, such as triphenylmethanol (triphenylcarbinol) and oxlmes, such as that of :
acetophenone and 1,2-diphenylethane- 1,2-dioxime; or ,: , . , , . - ~ - . :

:
. ; , , . . - .

20235~

one or more aliphatic electron-withdrawing groups, eg carboxylic acyl such as acetyl, eg 1,2-diacetylethane-1,2-dioxime.
Suitable compounds within the foregoing also include aliphatic keto-enol tautomers, eg aliphatic ketones substituted by electron-withdrawing substituents such as carboxylic acyl, eg hexamethyl-acetylacetone and acetylacetone.
It is often useful to have an additional agent present in the polymerisation mixture to delay the start of polymerisation.
Agents having this effect include any of the above mentioned complexing agents. Any such complexing agent will be in uncomplexed form and present over and above the complexing agent which is in complexed form in the complex co-catalyst. When present, it is often convenient if it is the same species as that in the complex co-catalyst.
Other such agents include water, dimethyl sulphoxide, dimethyl malonate and dimethyl formamide.
(The adverse effect of water on the desirably high molecular weight of the product is noted hereinafter, however.) The complexing agent may usefully be present in a molar ratio of from 0.5 to 100 relative to the uncomplexed co-catalyst precursor.
The co-catalyst is suitably present ln an amount such that the molar ratio of initiator to co-catalyst is in the range 0.1 to 500, preferably 1 to 10. It will be appreciated that, provided that at least sufficient complexing agent is used to completely complex all the uncomplexed co-catalyst precursor, this ratio will correspond to the molar ratio of initiator to uncomplexed co-catalyst precursor used, regardless of the quantity of (excess uncomplex-d) complexant.

` 2023~46 A crown ether may be present, and will of course then be present in an appropriate molar ratio.
In relation to the second component, this may for example be in the range of 0.3:1 to 3:1. ~ -Suitable concentrations of initiator are generally such that the initiator : monomer molar ratio is less than 1, generally less than 1:5, favourably in an amount corresponding to a molar ratio of 1:10 and ;
generally less, and preferably 1:1000 to l:S0 relative -~
to the monomer(s).
However, where the initiator comprises an insoluble polymeric or inorganic solid (ie in formula (I) Z2 is-EBE- where E is a bond or 0 and B is polymer diradical or E is 0 and B is an inorganic solid as hereinbefore defined), the initiator is generally used in an amount corresponding to a molar ratio of 1:100 to 1:5 relative to the monomer(s).
As noted hereinbefore, the ratio of initiator i) to co-catalyst ii) is generally in the molar ratio range of 0.1 to 500, preferably 1 to 10.
It is also useful, in order to moderate the polymerisation further, for the reaction mixture to contain from 0.01 to 2.0 X by weight, based on the weight of monomer, of acetonitrile.
The process may be carried out using a number of different embodiments of the catalysts of the second aspect of the invention.
Thus, for example, the lnitiator component (1) and the ~o-catalyst component (il) may be soluble in a monomer to be polymerised and/or in a reaction vehicle.
In a second embodiment the lnltlator (i) may be ln an lnsoluble form, such as one of those lnitlators whlch comprises an insoluble organlc polymer or -lnorganic moiety. :

. . -: , ~ . : : . :: :

2023~46 Examples where the initiator (i) is in an lnsoluble form, include a) those of formula (I) where p is 2 and Z~ is a group -EBE- as hereinbefore defined; and b) those where the lnitiator is comprised in an lnsoluble composition such as a conventional insoluble catalyst support.
All such insoluble forms are described hereinbefore.
Under the polymerisation process condltions the co-catalyst (ii) must be available to effect polymerisation in the polymerisation medium and this often means it must be soluble in at least one liquid monomer species, in a solvent compatible with the monomer(s) and inert in the present process conditions and/or -in phase which contains at least one monomer species, to such an extent that it can catalyse the reaction adequately.
Thus in bulk polymerisations, if the co-catalyst is not soluble in a monomer, an inert solvent compatible with the monomer(s) may be used, but ~ust in sufficient quantities to dissolve the co-catalyst.
Examples of suitable inert solvents or vehicles (if de~Qired) include ether solvents such as dimethyl ether, diethyl ether, dimethoxyethane, diethoxyethane, diethyleneglycol dimethyl ether or tetrahydrofuran; and aromatic hydrocarbon solvents such as benzene, toluene or xylene. The ether and aromatic hydrocarbon series of solvents are preferred amongst such solvents.
In general such liqulds should not contain labile hydrogen or halogen atoms or activated alkenyl groups.
No particular restrictions are placed on the order -~
in which the polymerization reaction components are added.

: :: :., .. : ... , ~.. : ~,. .. : . . . . . .

202354g Thus, polymerization will proceed in whatever sequence initiator, i) or a composition comprising lt, co-catalyst ii) and monomer are added to the reaction system in the process of this invention.
For example, the catalyst components may be mixed and added to the monomer. However, in terms of being able to control the polymerization reaction easily, especially ln the bulk polymerisation of acrylics, it is desirable 10 a) to add the initiator i) or composition comprising ~t and co-catalyst ii) separately to the monomer, or b) to add one catalyst component to the monomer or vice versa and add the product mixture to the other catalyst component, or vice versa.
Thus, where the initiator and co-catalyst are both soluble in a solvent in which the monomer is also soluble, it is often desirable to add the initiator and co-catalyst ii) separately to the monomer or a solution 2~ thereof, or vice versa.
Initiator i) or co-catalyst ii) added to the reaction mixture will normally be added neat, or in the form of a solution in tetrahydrofuran or the same organic solvent as any used in the polymerization reaction.
Often the initiator is added first to the monomer, or vice versa.
Similarly, where the initiator i) or its c~mposition is insoluble, it is often desired to add ~ -the co-catalyst ii) to the monomer or vice versa, and to contact the product mixture with the lnitiator i) or lts composition.
In all cases further monomer (which may be the same as or different from the initial monomer) may be added in any second mixing step.

. .

2023~

Block copolymers may thus be prepared by a solution process of this lnvention using two or more different monomers. In such a process, after initially polymerizing a first monomer using an initiator and co-catalyst, a second monomer is generallY added to the inltlal product polymer solution ln solution in a suitable organic solvent, which is normally the same as the first reaction solvent.
As noted hereinbefore, an agent (which may be an excess of complexing agent) may be used to delay the start of polymerisation. The latter agent can have the effect of delaying the onset of polymerisation for an induction period of several minutes depending upon the activity and concentration of the added agent.
If desired, however, the agent may be added to a mixture of monomer, initiator and co-catalyst after the onset of polymerisation so as to moderate the polymerisation or to stop it for a time depending upon the activity and concentration of the added agent.
(The adverse effect of water as such an agent on the desira~ly high molecular weight of the product is noted hereinafter, however.) In this case it is also preferable for the reaction mixture to contain from 0.05 to 5.0% by weight, based on the weight of monomer, of acetonitrile in order that the initial polymerisation proceeds at a controllable rate.
When the ~olymerisation has been stopped by --addition of such an agent, the dormant reaction mixture -~
may be reactivated by the addition of more co-catalyst.
The "living" polymer obtained by the method of the invention may be converted to a non-living polymeric product by being contacted with an excess of an active hydrogen compound, for example water or an alcohol. ~

: ' - , . , . : , -,. . , , ~ , -~. . .

` 2023~

The polymerization reactions of this invention may be conducted, for example, at temperatures ranging from -100C to 150C.
For solution polymerlsation, a range of -20 to 60C is favoured, but preferably at or about ambient temperature; 40 to 100C is favoured in the case of bulk polymerization.
The process may be conducted under 0.1 to 50 atomspheres pressure but normally atmospheric pressure is suitable.
It is desirable that processes of this invention should be conducted under anhydrous conditions, and the water content of the monomers, polymerization initiators and co-catalysts and any solvents minimised in order to obtain high molecular weight polymers by this method.
It is desirable to ensure that processes of this invention are conducted in atmospheres that have been dried in order to prevent the penetration of any water.
Such atmospheres include dry air, or atmospheres of dried inert gases such as nitrogen or argon; dried ;
inert gas atmospheres are preferable. ~ -The method of the invention is particularly useful for the bulk polymerisation of acrylics at room temperature, optionally in the presence of ~illers, for the production of sheets, rods etc.
Dispersion type polyacrylates may also be prepared.
The invention is illustrated but not limited by the following Examples.
The preparation of initiators and catalysts used in the process of the preient invention is illustrated by the following Descrlptions~

2023~46 .

Descriptions 1 and 2 - Preparation of Initiator Components (i) of General Formula ~I) MXZ3_ Description 1 - Preparation of 9-trimethylsilY1-carbazole (E. 1) To a solution of carbazole tl5g3 in dry THF (200 ml) was added butyllithium (56 ml; 1.6M in hexane).
once the butyllithium addition was completed, the solution was heated to reflux for 1.5 hours and then allowed to cool.
Chlorotrimethylisilane (12 ml) was added dropwise to the cooled mixture and then heated to reflux for 4 hours. Toluene (150 ml) was added to the cool mixture which was then filtered to remove LiC1. -The filtrate was collected and the solvent removed under vacuum leaving a crude gray compound. The crude product was further purified by vacuum distillation (0.03 mm Hg 184-186C) to give a white compound (E.1) in an 84% yield.
It could be further purified by recrystallisation in hexane.
n.m.r. (CDC13) ; 0.7 s 9H SiMe3;
7.08-8.4 broad 8H aromatic-H.

The following compounds were ~repared analogously from the corresponding amine and chlorosilane:
9-trlphenylsilylcarbazole (E.2) N-trimethylsilyl-N-phenyl-2-methyl-1-phenylprop-1-enylamine. ~E.3) N-trimethylsilylmorpholine (E.4) 1-trimethylsilylimidazole (E.5) 3-trimethylsilyloxazolid-2-one (E.6) .

- , . . . . - . ..

.

2023~4~

The following compounds are prepared analogously from the corresponding amine and chlorosilane:
N-trimethylsilyl-N-methylacetamide (E . 7 ) N-trimethylsilyl-N-methyltrifluoroacetamide (E. 8) 5 N-trimethylsilyl-N-cyclohex-1-enylmethylamine (E . 9 ) diphenyl(trimethylsilyl)amine (E.10) dibenzyl(trimethylsilyl)amine (E.11) N-trimethylsllylpyrrole (E.12) 1-N-trimethylsilylpyrrolidine (E.13) N-trimethylsilylpiperidine (E.14) N-triphenylsilylmorpholine (E.15) N-methyl-N'-trimethylsilypiperazine (E.16) N-trimethylsilylindole (E.17) 9-tribenzylsilylcarbazole tE.18) 9-adamantyldimethylsilylcarbazole (E.19) 9-dimethylneopentylsilylcarbazole (E.20) 9-triethoxysilylcarbazole (E.21) 9-triphenoxysilylcarbazole (E.22) 9-tribenzyloxysilylcarbazole (E.23) N-trimethylsilylindan-2-one (E.24) ~:
N-trimethylsilyltrifluoroacetanilide (E.25) N-trimethylsilylpiperidine-2,6-dione (E.26) The ~ollowing compounds were also prepared analogously:
N,N' bis(trimethylsiliyl)piperazine-2,5-dione (E.27) N-trimethylsilylacetanilide (E.28) N-trimethylsilylsuccinimide (E.29) .:
Descri~tion 2 - Preparation of Di~henyl(trimethvl-silYl)~hosDhine (E.30) This was prepared analogously to (E.1) above from diphenylphosphine.
: ~:

: -...................................... .
. .. , -. . ., : . :
- , ~ .. .

2023~46 The following compounds are prepared analogously from the corresponding phosphine and chlorosilane:
9-trimethylsilyl-9-phosphafluorene (E. 31) benzoylphenyltrimethylsilyiphosphine ( E . 32) 1-phospha-1-trimethylsilylcyclopentane (E. 33) diethyltrimethylsilylphosphine (E.34) dibutyl trimethylsilylphosphonate (E.35) dibenzyltrimethylsilylphosphine (E.36) P-trimethylsilyl-P-phenyl-2-methyl-1~ l-phenylpropenylphosphine (E.37) benzylbenzoyltrimethylsilylphosphine ~E.38) 1-phospha-l-trimethylsilylcyclohexane ~E.39) acetylethyltrimethylsilylphosphine (E.40) dicyclohexyl trimethylsilylphosphonate (E.41) ~
1 5 ' ' ~' Descri~tion 3 - Preparation of Initiator comPonents of General Formula (I) MXY(EBE) : .
A suspension of fumed silica (Carbosil-SM) is :
lithiated analogously to Description 1, and the product 20 is treated with an excess of 9-carbazolyldichloro-methylsilane to give the desired product (E.42).
Finely divided alumina may also be used. : :
::
Description 4 - Pre~aration of Initiator comPonents of ~-a) General Formula (I) MXY Z where Z is a PolYmer Radical b) General Formula (I) MXZ~ ~where~ X is a PolYmer Chain 3~ a) Preparation of ~olv(9-carbazolyldimethyl-silvlpropYl methacrYlate -Analogously to Description 1, carbazole is :
N-lithiated, and the product treated with chloro(3-methacryloxypropyl)dimethylsilane to give the above monomer.

.. :

.. . . . .
''' ~ ~ ~ : . .
. , . . -2023~4~
, , ~

The monomer is polymerised conventionally to give the desired product (E.43).

b) Preparation of Poly(N-trimethylsilYl-l-propyl-butYlene carboxamide) An amorphous nylon, poly(1-propylbutylene-carboxamide), is N-lithiated in THF solution at -70C, and the product is treated with chIorotrimethYlsilane to give the desired product (E.44).
" :,, Descriptions 5 and 6 - Pre~aration of Initiator -Components i) of General Formula (II) MXZ3.

pescrition 5 - PreParation of N-trimethvl-silyl-N-hexYl-N',N'-dimethylurea (E.51) To a solution of N-hexyl-N',N'-dimethylurea (15g) in dry THF (200 ml) was added butyllithium (56 ml; 1.6M in hexane). Once the butyllithium addition was completed, the solution was heated to reflux for 1.5 hours and then allowed to cool.
Chlorotrimethylisilane (12 ml) was added dropwise to the cooled mixture and then heated to reflux for 4 hours.
Toluene (150 ml) was added to the cool mixture which was then filtered to remove LiCl.
The filtrate was collected and the solvent removed under vacuum leaving a crude grey compound. The crude product was further purified by vacuum distilla-tion to give a white compound (E.51) in an 84% yield.
It could be further purified by recrystallisation in hexane.
The following compounds were prepared analogously from the corresponding urea and chlorosilane~

.,~ . ~. . . - .
.~. :.: .. , .:

; i :

2023~4~

N-trimethylsilyl-N-methyl-N~,N~-dimethylurea (E.52) N-trimethylsilyl-N',N'-dimethylurea (E.53) ~ :~
N-trimethylsilyl-N-methyl-N'-trimethylsilyl-N'-methyl-urea (E.54) S :'' ~
Description 6 ~;
The following compounds are prepared analogously -from the corresponding urea and chlorosilane~
N-phenyl-N-trimethylsilyl-N~,N'-dimethylurea (E.55) : :
N-benzyl-N-trimethylsilyl-N',N'-dimethylurea (E.56) :
N-(N'-methyl-N'-trimethylsilyl-carbamoyl)pyrrolidine (E.57) N-(N'-methyl-N'-trimethylsilyl-carbamoyl)piperidine (E.58) N-(N''-methyl-N'-trimethylsilyl- -:
carbamoyl)-N'-methylpiperazine (E.59) N-(N'-methyl-N'-trimethylsilyl- :
carbamoyl)imidazolidine (E.60) N-(N'methyl-N'-trimethylsilyl-carbamoyl)oxazolidine (E.61) Description 7 - Preparation of Initiator Components of~ :~
General Formula (II) MXY(EBE) :
A suspension of fumed silica (Carbosil-SM) is lithiated analogously to Description 5, and the product :
is treated with an excess of N-dimethylcarbamoyl-N-hexylaminodichloromethylsilane to give the desired product (E.62).
Finely divided alumina may also be used.

202354~

.
Description 8 - Preparation of Initiator ComPonents of a) General Formula (II) MXY2Z where Z is a PolYmer Radical b) General Formula (II~ MXZ3 where X is a Polymer ;
Chain ~ ;
a) PreParation of DOlV (N-dimethYlcarbamoYl-N-hexYlaminomethylsilyldimethvlsilylpropyl methacrYlate) Analogously to Description 1, N-hexyl-N~,N'-dimethylurea is N-lithiated, and the product treated with chloro-(3-methacryloxypropyl)methylsilane to give ~-the above monomer.
The monomer is polymerised conventionally to give the desired product (E.63).
b) Preparation of PolY(N-trimethYlsilyl-N'-l-~ropylbutylene-N'-methylurea (E.64) An polyurea, poly(N-1-propylbutylene-1-methylurea) is N-lithiated in T~F solution at -70C, and the product is treated with chlorotrimethylsilane to give the desired product (E.64).

DescriDtions 9 and 10 - PreDaration of Initiator Components i) of General Formula (IIIL_MXZ3.
: - .
Descri~tion 9 - Preparation of 1,6-bis-(9-trimethYlsilylcarbazol-2-yloxy)hexane (E.71) To a solution of 1,6-bis(carbazol-2-yloxy)hexane (30 g) in dry THF (200 ml) was added butyllithium (56 ml; 1.6M in hexane). Once the butyllithium addition was completed, the solution was heated to reflux for 1.5 hours and then allowed to cool. Chlorotrimethyl-silane (12 ml) was added dropwise to the cooled mixture and then heated to reflux for 4 hours.

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- _ 40 -Toluene (150 ml) was added to the cool mixture which was then filtered to remove LiC1. The filtrate was collected and the solvent removed under vacuum leaving a crude gray compound. The crude product was further purified by vacuum distillation to give a white compound (E.71) in an 84X yield.
It could be further purified by recrystallisation ln hexane.
The following compounds were prepared analo~ously from the corresponding diamine or ;~
diphosphine and chlorosilane~
1,6-bis(1-trimethylsilylimidazolid-2,4-dion-3-yl)hexane (E.72) 1,3-bis(phenyltrimethylsilylphosphino)propane (E.73) Descri~tion 10 The following compounds are prepared analogously from the corresponding diamine and chlorosilane:
1,6-bis(3-trimethylsilylimidazolyl)hexane (E.74) 1,6-bis(3-trimethylsilyloxazolid-2-onyl)hexane (E.75) 1,6-(N-trimethylsilyl-N-cyclo-hex-1-enylamino)hexane (E.76) 1,6-bis-(N-trimethylsilylpiperazino)hexane (E.77) 1,6-bis(9-tribenzylsilylcarbazol-2-yloxy)hexane (E.78) 1,6-bis(9-triethoxysilylcarbazol-2-yloxy)hexane (E.79) .~, .;, - , :-~ . ~: . . . .

:,:. . . - : , : ., 2023~46 Descri~tion 11 - Pre~aration of Initiator Com~onents comprising Moieties of General Formula (III) MXZ3 where X ls a Polymer Chain Pre~aration of ~oly(N-trimethYlsilylacrYlonitrile) ~E.80) Analogously to Description 1, acrylonitrile is N-lithiated, and the product treated with chlorotri-methylsilane to give the above monomer.
The monomer is polymerised conventionallY to give the desired product (E.80).

Example 1 - Bulk Polvmerisation of Acrvlic Monomer catalysed by Various Com~onents (i) and Various Tetrabutylammonium Fluoride (TBAF) ComPlexes (ii) The following method is generally applicable:
The reaction is preferably carried out under dry, oxygen-free N 2.
To initiator (50 micromole) and monomer (20 mmole) in a dry glass reaction vessel (Schlenk tube), was added a solution of co-catalyst precursor (TBAF) and complexing agent (molar 1:1; 100 mmole in tetra-hydrofuran, [THF]) whilst stirring, using a microlitre syringe.
The polymerisation rate was followed by monitoring the temperature using a thermocouple.
For several minutes there was no significant temperature rise indicating minimal polymerisation.
There was then an exponential temperature rise to over over the next few seconds to minutes when geerally >70% and often >85% of the monomer was converted to polymer.
When the polymerisation was complete, the polymer was dissoived in methylene chloride and precipitated into methanol or hexane.

. -.: --- - - .
,.. . -- . . .
. .
~;' ~ ,. . . , : ~ .

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.

The yield was calculated and GPC performed (calibrated against polystyrene).
Specific reactions are summarised in Table 1.
The initiators (i) used were selected from~
9-trimethylsilylcarbazole (E.1) 3-trimethylsilyloxazolid-2-one (E.6) diphenyl(trimethylsilyl)phosphine (E.30) N-trimethylsilyl-N-methyl-N'- -- -.
trimethylsilyl-N'-methyl-urea (E.54) The uncomplexed precursor of co-catalyst (ii) in each case was tetrabutylammonium fluoride (C.1).
The complexing agents were selected from:
hexamethylacetylacetone (A.1) acetylacetone (A.2) 4-cyanophenol (A.3) uracil (2,4-hydroxypyrimidine) (A.4) triphenylcarbinol (A.5) 1,2-diphenylethane-1,2-dioxime (A.6) :~-1,2-diacetylethane-1,2-dioxime (A.7) :
The polymerised monomers were selected from methyl methacrylate (MMA) and ethyl acrylate (EA).
All the foregoing numbered initiators and ~ :
complexing agents may be used similarly.
All the foregoing complexing agents and co-catalyst precursors listed more generally hereinbefore may also be used similarly.

init- quant- complexing quantity mono- yield iator ity, mg agent microlitre mer %
(E.1)12 (A.3) 10 MMA 80-90 (E.1)12 (A.4) 20 MMA 80-90 (E.1)12 (A.S) 25 MMA 80-90 (E.1)12 (A.6) 10 MMA 80-90 (E.1)12 (A.7) 15 MMA 80-90 (E.1)12 (A.3) 10 MMA 80-90 tE.1)12 (A.3) 10 EA 53 : ; . . :
(E.6)8 (A.3) 15 MMA 73 (E.6)8 (A.4) 25 MMA

(E.30) 13 (A.3) 15 MMA
(E.30) 13 (A.4) 10 MMA
(E.54) 11 (A.3) 20 MMA
~E.54) 11 (A.4) 25 MMA

(E.1)12 (A.1) 10 MMA 80-90 (E.1)12 (A.2) 10 MMA 80-90 (E.1)12 (A.1) 10 EA 76 (E.6)8 (A.1) 10 MMA 73 (E.30) 13 (A.1) 10 MMA

(E.30) 13 (A.1) 10 EA

(E.54) 11 (A.1) 10 MMA

, 2a23~4~

Example 2 - Solution Polymerisation of Acrylic Monomer catalysed by Various Components (i) and Tetrabut~l-ammonium Fluoride (TBAF) Complexes (ii) The following method is generally applicable:
The reaction is preferably carried out under dry, oxygen-free ~.
The same quantities of initiator and monomer as in Ex~mple 1 were used, but in a dry aprotic solvent (5 ml). (Suitable solvents include solvents such as tetrahydrofuran [THF] and toluene.) Reaction was again carried out in a dry glass reaction vessel (Schlenk tube3, adding a solution of co-catalyst precursor (TBAF) and complexing agent (molar 1:1; 100 mmole total in THF) to the initiator and monomer by microsyringe, whilst stirring,.
The polymerisation rate was also followed by monitoring the temperature using a thermocouple.
Specific reactions are summarised in Table 2.
The same initiators, co-catalyst precursors, complexing agents and monomers as in Example 1 were used.
All the foregoing numbered lnitiators and complexing agents may be used similarly.
All the foregoing complexing agents and co-catalyst precursors listed more generally hereinbefore may also be used similarly.

. . . .... ., . ~ . . . . : .

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init- quant- complexing quantity mono- solvent iator ity, mg agent microlitre mer (E.1) 12 (A.3) 10 MMAtoluene (E.1) 12 (A.1) 10 MMA THF
(E.1) 12 (A.2) 10 MMAtoluene (E.30) 12 (A.1) 10 MMAtoluene (E.30) 12 (A.1) 10 EAtoluene The following are carried out analogously.

(E.30) 12 (A.3) 10 MMAtoluene (~.30) 12 (A.4) 10 EAtoluene (E.54) 12 (A.5) 10 MMAtoluene (E.54) 12 (A.6) 10 EAtoluene Example 3 - Polymerisation of methYl methacrylate (MMA) catalYsed by initiator 1) of the invention and tetrabutYl ammonium fluoride/ acetYlacetone comPlex ( ii ) .
3 mls of MMA (28.1 mmol) and any one of (E.1) to (~.80) (4.95 x 10-' mM) are added to a dry glass reaction vessel under N.. Whilst stirring, 5 ~l of TBAF/AcAc in THF (0.05 mmol/ml) are added using a microlitre syringe. The polymeriæation rate is followed by monitoring the temperature using a ~ -thermocouple.

. . . , ~ . . . , . ~ . , -:

~ : . . . , : : : . ',, ' , 2023~4~

The mixture gradually increases from room temperature up to 90C over several 8 minutes. The polymerisation is allowed to proceed for a further 10 mins when the mixture is quenched in moist methylene chloride and preciDitated into hexane.

Example 4 - Polymerisation of methvl methacrYlate (MMA) catalysed by initiator i) and tetrabutyl ammonium fluoride~acetyl acetone com~lex (TBAF/AcAc) in the ~resence of dimethyl malona~e (DMM) 4 x 10~3mM TBA/AcAc and 10 ml MMA (93.6 mmol) are added to a dry glass reaction vessel under N2. DMM
(0.012 mmol) is now added followed by any one of (E.1) to (E.80) (0.0488 mmol). The polymerisation rate is followed by monitoring the exotherm.
There is an initial induction time of several mins after which the reaction is very fast with a consequential exotherm to above 100C.

ExamPle 5 - Polvmerisation of MMA catalvsed bY
initiator i) and TBAF/AcAc in the Dresence of dimethyl sulPhoxide (DMSO) TBAF/AcAc (2.5 x 10-' mmol), MMA (28.1 mmol) and 1 ~1 DMSO (0.0141 mmol) are added to a dry reaction vessel. The same amount of lnitiator as in Example 2 is then added.
An induction time is noted followed by a very rapid polymerisation rate.
: , ExamPle 6_- Polymerisation of MMA catalYsed bY
initiator i) in the Dresence of dimethvl formamide (DMF) 2.5 x 10-~ mmol TBAF/AcAc, 28.1 mM MMA and 1 ~
of DMF (0.013 mmol) are added to a dry reaction vessel.

.. . ..

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- `:

After addition of 10 ~l MTS (0.0494 mmol). an induction time is noted.

Example 7 - Polvmerisation of MMA catalYsed bY
initiator i) and TBAF/AcAc in the ~resence of water.
2 x 10-' mmol TBAF/AcAc, 46.8 mM MMA and 0.0139 mm of H20 were added to a reaction vessel under N~.
After the addition of 0.0494 mmol of inltiator, an induction time is noted.
A vigorous exotherm then occurs yielding polymer.

Exam~le 8 - Polymerisation of ethyl acrylate ~EA) catalysed bY initiator (i) and comelex co-catalYst (ii) selected from a) tris(dimethvlamino)sulPhonium difluorotrimethYl- -silicate/4-cyano~henol (A.3) comPlex~
b) tris(dimethylamino)sulphonium azide/1,2-diphenyl-ethane-1,2-dioxime (A.6) com~lex, and c) tetraethvlammonium azi~ =s~kl~s~lethane-1,2-dioxime (A.6) com~lex in the ~resence of dimethvl malonate (DMM) 4 x 10~3mM complex and 10 ml EA (93.6 mmol) are added to a dry glass reaction vessel under N2. DMM
(0.012 mmol) is now added followed by any one of (E.1) to (~.80) (0.0488 mmol). The polymerisation rate is followed by monitoring the exotherm.
There is an initial induction time of several mins after which the reaction is very fast with a consequential exotherm to above 100C.

:

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Example 9 - Polvmerisation of EA catalysed bY initiator i) and complex co-catalvst (ii) selected from a) tris(dimethYlamino)sulPhonium cYanide/uracil (A.4) complex, b) lithium cYanide/1,2-diphenylethane-1,2-dioxime (A.6) comDlex, and c) sodium fluoride/crown ether/1,2-diphenyl-ethane-1,2-dioxime (A.6) com~lex, in the ~resence of dimethyl sulphoxide (DMSO) The complex (4.5 x 10-' mmol), EA (28.1 mmol) and 1 ~l DMSO (0.0141 mmol) are added to a dry reaction vessel. The same amount of initiator as in Example 2 is then added.
An induction time is noted followed by a very rapid polymerisation rate. -Example 10 - Polymerisation of monomers selected from MMA and EA catalysed by initiator (i) and comPle co-catalvst (ii) selected from a) tetra~henvlarsonium cYanide/triphenYlcarbinol (A.5) complex, b) tetramethYlammonium fluoride/triphenvlcarbinol (A.5) complex in the presence of dimethvl formamide (DMF) 2.5 x 10-~ mmol complex, 28.1 mM monomer and 1 ~l of DMF (0.013 mmol) are added to a dry reaction vessel. The same amount of initiator as in Example 2 ls then added.
After addition of 10 ~l MTS (0.0494 mmol), an ~
induction time is noted. ;;
..~

... . ~. .. .....

Claims (10)

1. A polymerisation process which comprises contacting at least one polar acrylic type or maleimide monomer under polymerisation conditions with a catalyst comprising (i) and (ii):
(i) a tetracoordinate organosilicon, organotin or organogermanium initiator having at least one initiating site in which a silicon, tin or germanium atom is bound by a nitrogen or phosphorus atom to a nitrogen- or phosphorus-containing group which is devoid of any reactive hydrogen atom, and (ii) a co-catalyst which is a complex of a) a source of fluoride, bifluoride, cyanide, cyanate, aliphatic or aromatic mono-sulphonate or azide ions or a Lewis acid, which ion source or Lewis acid is available in the polymerisation medium, with b) a complexing agent.

2. A polymerisation process according to claim 1, characterised in that the co-catalyst is an isolable complex of an ion source salt with a complexing agent which is an active hydrogen compound.

3. A polymerisation process according to claim 2, characterised in that the complexing agent is one selected from aromatic nuclei, substituted by one or more hydroxy, amino, mercapto or phosphino groups, and also substituted by one or more cyanide, cyanate, ester or azide groups;
heteroaromatic keto-enol tautomers and analogues thereof, substituted in the heteroaromatic nucleus by one or more hydroxyl, amino, mercapto or phosphino groups, and also optionally substituted in the heteroaromatic nucleus by one or more cyanide, cyanate, ester or azide groups;

saturated aliphatics (including cyclo- and polycycloaliphatics), substituted by one or more hydroxy, hydroxyimino, amino, mercapto or phosphino groups, and also substituted by two or more aromatic nuclei in turn optionally substituted by one or more cyanide, cyanate, ester or azide groups, or one or more carboxylic acyl groups.

4. A polymerisation process according to claim 2, characterised in that the complexing agent is an aliphatic ketone substituted by carboxylic acyl.

5. A polymerisation process according to claim 1, characterised in that an agent is present to delay the polymerisation.

6. A polymerisation process according to claim 5, characterised in that the agent is a complexing agent, dimethyl sulphoxide, dimethyl malonate or dimethyl formamide.

7. A polymerisation process according to claim 1, characterised in that the complexing agent is present in a molar ratio of from 0.5 to 100 relative to the uncomplexed co-catalyst precursor.

8. A catalyst comprising the componemts (i) and (ii) recited in claim 1, for use in the process of claim 1.

9. The co-catalyst (ii) recited in claim 1, for use in the process of claim 1.

10. A process according to claim 1, characterised in that a polymerised monomer is of the formula:

CH2=C(Y)X, or wherein:
X is CN, -CH=CHC(O)X' or -C(O)X';
Y is -H, -CH3,-CN or -CO2R, provided, however, when X' is -CH=CHC(O)X', Y is -H or -CH3;
X' is -OSi(R1)3, -R, -OR or -NR'R"; each R1 independently is H or a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, provided that at least one R1 group is not H;
R is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic aromatic radical containing up to 20 carbon atoms, or a polymeric radical containing at least 20 carbon atoms, any of said radicals optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally containing one or more functional substituents that are unreactive under polymerizing conditions, and optionally containing one or more reactive substituents of the formula:
-Z'(O)C-C(Y1)=CH2 wherein Y1 is H or CH3 and Z' is O or NR';
and each of R' and R" is independently selected from C1-4 alkyl.