A COMONOMER, AND A POLYMER STABILIZED WITH IT DURING POLYMERIZATION

COMONOMERE, ET POLYMERE STABILISE AU MOYEN DE CE COMONOMERE PENDANT LA POLYMERISATION

English Abstract

The invention concerns an E-vitamin derivative or a compound analogous with
it, having formula (I), where X is an oxygen or sulfur atom, p is an integer 0
or 1, and R3 - R11 are identical or different groups selected from hydrogen,
C1-6alkyl or .alpha.-alkene having formula (II), where n, m and o are integers
0 - 4 independent of each other and R1 and R2 are identical or different
groups selected from hydrogen or C1-6alkyl or C1-6alkene, which may be
substituted with an aromatic ring, or R7 and R8 are together an oxygen atom
and/or R4 and R5 and/or R10 and R11 form together with the carbon atoms to
which they are bonded a benzene ring, which may be substituted with groups
selected from hydrogen, C1-6alkyl or .alpha.-alkene. The invention also
concerns the use of a derivative consistent with formula (I) as a stabilizing
comonomer, and a stabilized copolymer and a method for the production of a
stabilized copolymer.

French Abstract

La présente invention concerneun dérivé de vitamine E, ou un composé analogue, représenté par la formule générale (I). Dans cette formule générale (I), X est atome d'oxygène ou de soufre, p est un entier valant 0 ou 1, et R¿3? à R¿11? sont des groupes identiques ou différents tels qu'hydrogène, C¿1-6? alkyle ou .alpha.-alcène représenté par la formule particulière (II). Dans cette formule particulière (II), m, n et o sont des entiers valant 0 à 4 indépendants l'un de l'autre, R¿1? et R¿2? étant des groupes identiques ou différents tels qu'hydrogène, C¿1-6? alkyle ou C¿1-6? alcène pouvant être substitués par un cycle aromatique. Toutefois, R¿7? et R¿8? peuvent également être ensemble atome d'oxygène et/ou R¿4? et R¿5? et/ou R¿10? et R¿11? peuvent former ensemble avec les atomes de carbone auxquels ils sont liés un cycle benzène pouvant être substitué par des groupes tels qu'hydrogène, C¿1-6? alkyle ou .alpha.-alcène. L'invention concerne également, d'une part l'utilisation d'un dérivé correspondant à la formule générale (I) comme comonomère de stabilisation, et d'autre part un copolymère stabilisé et un procédé de production d'un copolymère stabilisé.

Claims

25
CLAIMS
1. E-vitamin derivative or a compound analo-
gous with it, having the formula (I)
<IMG>
where X is an oxygen or sulfur atom, p is an
integer 0 or 1, and R3 - R11 are identical or different
groups selected from hydrogen, Cl-6alkyl or .alpha.-alkene
having the formula (II)
-(CH2)n-(CR1R2)m-(CH2)o-CH=CH2 (II)
where n, m and o are integers 0 - 4 independ-
ent of each other and m + n + o is an integer 1 - 6,
and R1 and R2 are identical or different groups se-
lected from hydrogen or C1-6alkyl or C1-6alkene, which
may be substituted with an aromatic ring,
or R7 and R8 are together an oxygen atom
and/or R4 and R5 and/or R10 and R11 form together with
the carbon atoms to which they are bonded a benzene
ring, which may be substituted with groups selected
from hydrogen, C1-6alkyl or .alpha.-alkene.
2. Derivative as defined in claim 1, c h a r -
a c t a r i z e d in that it has the formula (III)
<IMG>

26
or the formula (IV)
<IMG>
where X is an oxygen or sulfur atom and R3 -
Rll are identical or different groups selected from hy-
drogen, C1-6alkyl or .alpha.-alkene having the formula (II).
3. Derivative as defined in claim 1, c h a r -
a c t e r i z e d in that it has the formula (V)
<IMG>
where R3 - R11 are identical or different
groups selected from hydrogen, C1-6alkyl or .alpha.-alkene
having the formula (II),
or R7 and R8 are together an oxygen atom
and/or R4 and R5 and/or R10 and R11 form together with
the carbon atoms to which they are bonded a benzene
ring, which may be substituted with groups selected
from hydrogen, C1-6alkyl or .alpha.-alkene.
4. Derivative as defined in claim 1 or 2,
c h a r a c t e r i z e d in that one of groups R3 and R4
or one of groups R5 and R6 is hydrogen or a C1-6alkyle
and the other an .alpha.-alkene consistent with formula (II)
and R7 - R11 are hydrogens or C1-6alkyls .
5. Derivative as defined in any one of claims
1, 2 or 4 , c h a r a c t e r i z e d in that R1 and R2 are
hydrogens.

27
6. Derivative as defined in claim 1, 2 or 4 -
5, characterized in that it has formula
(III), where X is oxygen, one of groups R3 and R4 is a
methyl group and the other is an .alpha.-alkene consistent
with formula (II), where n + m + o equals 1 or 2 and R1
- R2 and R5 - R8 are hydrogens and R9 - R11 are methyl
groups.
7. Derivative as defined in claim 1, 2 or 4 -
5, characterized in that it has formula (IV),
where X is oxygen, R1 - R4 are hydrogens, one of groups
R5 and R6 is an .alpha.-alkene consistent with formula (II),
where n + m + o equals 4, and R9 - R11 are methyl
groups.
8. Derivative as defined in claim 1 or 2,
characterized in that one of groups R9 - R11
is an .alpha.-alkene consistent with formula (II) and two of
the groups are hydrogens or C1-6alkyls, and R3 - R8 are
hydrogens or C1-6alkyls.
9. Derivative as defined in any one of claims
1, 2 or 8, characterized in that R10 and R11
are hydrogens or C1-6alkyls, R9 is an .alpha.-alkene consis-
tent with formula (II), where n is 0 or 1, m is 0 or 1
and o is an integer 1 - 4 and R1 - R2 are hydrogens or
C1-6alkyls.
10. Derivative as defined in any one of
claims 1, 2 or 8 - 9, characterized in that
it has formula (III), X is oxygen, R1 - R4 and R10 - R11
are methyl groups, R5 - R8 are hydrogens and R9 is an .alpha.-
alkene consistent with formula (II), where n is 0, m
is 1 and o is 3.
11. Derivative as defined in any one of
claims 1, 2 or 8 - 9, characterized in that
it has formula (III), X is oxygen, R3 - R4 and R10 - R11
are methyl groups, R5 - R8 are hydrogens and R9 is an .alpha.-
alkene consistent with formula (II), where m is 0 and
o + n equals 1.

28
12. derivative as defined in claim 1 or 3,
characterized in that one of groups R9 - R11
is an .alpha.-alkene consistent with formula (II) and the
other groups are hydrogens or C1-6alkyls, and R3 - R8 are
hydrogens or C1-6alkyls or R7 and R8 are together an oxy-
gen atom and/or R4 and R5 form a benzene ring together
with the carbon atoms to which they are bonded.
13. Derivative as defined in any one of
claims 1, 3 or 12, characterized in that R10
is an .alpha.-alkene consistent with formula (II) where n is
0 or 1, m is 0 or 1 and o is an integer 1 - 4 and R1
and R2 are methyl groups, R9 is a C1-6alkyl, R11 is a hy-
drogen, R7 and R8 are together an oxygen atom and R4 and
R5, together with the carbon atoms to which they are
bonded, form a benzene ring.
14. Derivative as defined in any one of
claims 1 - 13, characterized in that it is 6-
hydroxy-2,5,7,8-tetramethyl-2-(but-3-enyl)-chromane,
6-hydroxy-2,5,7,8-tetramethyl-2-(prop-2-enyl)-
chromane, 6-hydroxy-2,2,7,8-tetramethyl-5-(1,1-
dimethyl-hex-5-enyl)-chromane, 6-hydroxy-2,2,7,8-
tetramethyl-5-(prop-2-enyl)-chromane, 5-hydroxy-4,6,7-
trimethyl-3-(hex-5-enyl)-benzofurane or a hydroxythi-
oxanthone derivative.
15. Method for producing an E-vitamin deriva-
tive or a compound analogous with it, which has the
formula (Ia), characterized in that
(A) a hydroquinone derivative is allowed to react
with a suitable unsaturated alcohol or thiol, or
(B) a hydroquinone derivative is allowed to react
with a suitable unsaturated alcohol or thiol and
an .alpha.-alkylene is added to the fused heterocyclic
derivative thus formed.
16. Use of an E-vitamin derivative or a com-
pound analogous with it, having the formula I

29
<IMG>
where X is an oxygen or sulfur atom, p is an
integer 0 or 1, and R3 - R11 are identical or different
groups selected from hydrogen, C1-6alkyl or .alpha.-alkene
having the formula (II)
-(CH2)n-(CR1R2)m-(CH2)o-CH=CH2(II)
where n, m and o are integers 0 - 4 independ-
ent of each other and R1 and R2 are identical or dif-
ferent groups selected from hydrogen or C1-6alkyl or C1-
6alkene, which may be substituted with an aromatic
ring,
or R7 and R8 are together an oxygen atom and/or R4 and
R5 and/or R10 and R11 form together with the carbon atoms
to which they are bonded a benzene ring, which may be
substituted with groups selected from hydrogen, C1-
6alkyl or .alpha.-alkene
as a stabilizing comonomer for the production of sta-
bilized copolymer.
17. Stabilized copolymer, comprising at least
one monomer variety, which is an olefin and/or a cy-
clic and/or aromatic compound containing an .alpha.-alkene
chain, and a stabilizing comonomer, character-
ized in that the comonomer is an E-vitamin deriva-
tive or a compound analogous with it, which has the
formula (I)

30
<IMG>
where X is an oxygen or sulfur atom, p is an
integer 0 or 1, and R3 - R11 are identical or different
groups selected from hydrogen, C1-6alkyl or .alpha.-alkene
having the formula (II)
-(CH2)n-(CR1R2)m-(CH2)o-CH=CH2 (II)
where n, m and o are integers 0 - 4 independ-
ent of each other and R1 and R2 are identical or dif-
ferent groups selected from hydrogen or C1-6alkyl or C1-
6alkene, which may be substituted with an aromatic
ring,
or R7 and R8 are together an oxygen atom
and/or R4 and R5 and/or R10 and R11 form together with
the carbon atoms to which they are bonded a benzene
ring, which may be substituted with groups selected
from hydrogen, C1-6alkyl or .alpha.-alkene.
18. Stabilized copolymer as defined in claim
17, characterized in that the comonomer has
the formula (III)
<IMG>

31
or the formula (IV)
<IMG>
where X is an oxygen or sulfur atom and R3 -
R11 are identical or different groups selected from hy-
drogen, C1-6alkyl or .alpha.-alkene having the formula (II).
19. Stabilized copolymer as defined in claim
17, characterized in that the comonomer has
the formula (V)
<IMG>
where R3 - R11 are identical or different
groups selected from hydrogen, C1-6alkyl or .alpha.-alkene
having the formula (II),
or R7 and R8 are together an oxygen atom
and/or R4 and R5 and/or R10 and R11 form together with
the carbon atoms to which they are bonded a benzene
ring, which may be substituted with groups selected
from hydrogen, C1-6alkyl or .alpha.-alkene.
20. Stabilized copolymer as defined in any
one of claims 17 - 19, characterized in that
the olefin is ethylene, propylene, butylene and/or
pentene.
21. Stabilized copolymer as defined in any
one of claims 17 - 20, characterized in that
the the aromatic compound is styrene.
22. Stabilized copolymer as defined in any
one of claims 17 - 21, characterized in that
the copolymer consists of one olefin or styrene mono-

32
mer and comonomer consistent with formula (III), (IV)
or (V).
23. Stabilized copolymer as defined in any
one of claims 17 - 22, characterized in that
the copolymer has a substantially regular structure.
24. Method for the production of stabilized
copolymer, wherein at least one monomer variety, which
is an olefin and/or a cyclic and/or aromatic compound
containing an .alpha.-alkene chain, and a stabilizing co-
monomer are copolymerized in the presence of a cata-
lyst by a polymerization technique known in itself,
characterized in that the comonomer used is
an E-vitamin derivative or a compound analogous with
it, having the formula (I)
<IMG>
where X is an oxygen or sulfur atom, p is an
integer 0 or 1, and R3 - R11 are identical or different
groups selected from the set hydrogen, C1-6alkyl or .alpha.-
alkene having the formula (II)
-(CH2)n-(CR1R2)m-(CH2)o-CH=CH2 (II)
where n, m and o are integers 0 - 4 independ-
ent of each other and R1 and R2 are identical or dif-
ferent groups selected from hydrogen or C1-6alkyl or C1-
6alkene, which may be substituted with an aromatic
ring,
or R7 and R8 are together an oxygen atom
and/or R4 and R5 and/or R10 and R11 form together with
the carbon atoms to which they are bonded a benzene

33
ring, which may be substituted with groups selected
from hydrogen, C1-6alkyl or .alpha.-alkene.
25. Method as defined in claim 24, char-
acterized in that the comonomer used is a co-
monomer consistent with formula (III), (IV) or - (V).
26. Method as defined in claim 24 or 25,
characterized in that the copolymerization is
performed using a metallocene catalyst or its deriva-
tive.
27. Method as defined in any one of claims 24
- 26, characterized in that the catalyst used
in copolymerization contains a .pi.-cyclo-pentadienyl
transition metal compound and an alumoxane compound.
28. Method as defined in any one of claims 24
- 27, characterized in that the catalyst used
in copolymerization contains a .pi.-cyclo-pentadienyl
transition metal compound and a compound containing
boron.
29. Method as defined in any one of claims 24
- 28, characterized in that the comonomer has
been complexed to the catalyst.
30. Method as defined in any one of claims 24
- 29, characterized in that the olefin is
ethylen, propylene, butylene and/or pentene.
31. Method as defined in any one of claims 24
- 30, characterized in that the aromatic
compound is styrene.
32. Method as defined in any one of claims 24
- 31, characterized in that the amount of
monomer and stabilizing comonomer supplied into the
process is exactly defined.

Description

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A COMONOMER, AND A POLYMER STABILIZED WITH IT DURING
POLYMERIZATION
The present invention relates to an E-vitamin
derivative or a compound analogous with it as defined
in the preamble of claim 1, to a method for the pro
duction of the aforesaid derivative, to its use as de
fined in claim 16, to a stabilized copolymer as de
fined in the preamble of claim 17 and to a method for
the production of a stabilized copolymer as defined in
the preamble of claim 24.
In prior art, specification FI 92212 presents
a method for the production of a stable a-olefin poly-
mer using a Ziegler-Natta type catalyst in which the
a-olefin reacts with a complex comprising a metal of
group I-IV of the periodic system and an a-alkenyl
substituted stabilizer co-ordinated to it with a het-
eroatom as a ligand. The catalyst is attached to a
magnesium carrier, and a chain of at least 5 carbons
is needed between the stabilizer residue of the stabi-
liter ligand and the polymerizing functional unsatu-
rated bond.
Further, specification DE 1947590 describes
how a component containing a hydrocarbon based, steri-
cally protected hydroxyl group and linked to an a-
vinyl group situated at a distance of at least two
carbon atoms is copolymerized in the polymerization
conditions of olefins in the presence of an old-
generation Ziegler-Natta catalyst. The problem is a
low polymerization activity.
A generally known practice is to polymerize
polyolefins using Ziegler-Natta type catalysts. The
catalyst consists of a metalorganic compound in which
the procatalyst is typically an at least partially re-
duced compound of a transition metal of group IV, V,
VI or VI I , usually a compound of a . g . titan or zirco-
nium, while the cocatalyst is an organometallic com-
pound of an alkali metal, alkaline earth metal, zinc

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2
or aluminum, e.g. triethylaluminum and diethylmagne-
sium. An example of such a catalyst is a combination
of titan chloride and triethylaluminum. The activity
increases considerably when the above-mentioned compo-
nents are attached to a fixed carrier; e.g. MgCl2.
Ziegler-Natta catalysts are characterized by an abil-
ity to give the polymer the particle form of the cata-
lyst during polymerization, thus producing polymer
particles of 0.2 - 5 mm. The polymer particle thus
produced is porous, and without an additive increasing
the stability, it is chemically dissolved during use.
A known practice is to use a stabilizer hav-
ing a large molar mass, e.g. derivatives of tert-butyl
phenol and pentaerythritol, as an additive. Another
known practice is to use polymer-based and oligomeric
molecules. A limitation is, however, a lower solubil-
ity in polymer. Substituted phenols and aromatic
amines are widely used antioxidants. Usually the poly-
mer product obtained after the polymerization reaction
is melted in a so-called extruder stage, and additives
improving stability are added to the molten product,
whereupon the product is granulated.
Further, the use of so-called metallocene
catalysts is known in industry. Such catalysts have
been used since the early 1990's in polymerization
processes beside or instead of Ziegler-Natta cata-
lysts. Metallocene catalysts are based on a so-called
sandwich structure, in which a metallic center, e.g.
zirconium, is placed between two cyclopentadienyl
rings (bischloro-zirconocene), and on derivatives of
that structure. Metallocene catalysts have in some
cases increased the polymerization activity even with
comonomers that have previously been difficult to co
polymerize. Therefore, metallocenes are increasingly
used in various industrial applications.
A problem with previously known methods is
that the stabilizing additive is added to the product

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at the extruder stage, which is why it has not been
possible to utilize a catalyst producing a particle
product and a polymerization process because of the
stability problem.
A further problem is that the additives in
the polymer product vanish during use. One of the rea-
sons for this is that the additives improving stabil-
ity drift to the surface of the product, with the re-
sult that the stabilizing effect is diminished and
disappears with time and that the additives may get
into contact e.g. with foodstuffs. In addition, it has
been established that some additives have estrogenic
effects. The loss of additives in the product may also
be partly due to evaporation taking place during proc
essing or dissolution occurring during washing.
Another problem is irregular distribution of
additives in the polymer product. Irregular distribu-
tion may result e.g. from an incompatibility of the
stabilizers with paraffin-type hydrocarbon-based poly-
mers due to a high polarity. In addition, the amount
of stabilizer added to polyolefins has to be limited
because of the tendency of the stabilizers to crystal-
lize.
Further problems are a poor product yield and
an atacticity of the product in polymerization carried
out using a ziegler-Natta catalyst.
The object of the invention is to eliminate
the problems referred to above and to disclose a new
usable comonomer having a stabilizing effect. A fur-
ther object of the invention is to disclose a copoly-
mer stabilized during polymerization.
The E-vitamin derivative or the compound
analogous with it, its production method and the sta-
bilized copolymer and its production method according
to the invention are characterized by what is pre-
sented in the claims.

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The E-vitamin derivative of the invention or
the compound analogous with it, i.e. a compound having
a corresponding structure, has the following formula
(I)
R~ Rs R7
H ~s
(I)
R5
1 o R4
R.
R11
where X is an oxygen or sulfur atom, p is an
integer = 0 or 1, and R3 - Rll are identical or differ-
ent groups selected from hydrogen, C1_6alkyl or a-
alkene having the formula (II)
2 0 - ( CH2 ) n- ( CR1R2 ) m- ( CHz ) o-CH=CH2 ( I I )
where n, m and o are integers 0 - 4 independ-
ent of each other and R1 and RZ are identical or dif-
ferent groups selected from hydrogen or C1_6alkyl or C1_
6alkene, which may be substituted with an aromatic
ring, e.g. a styrene derivative
or R~ and Ra are together an oxygen atom
and/or R4 and RS and/or Rlo and R11 form together with
the carbon atoms to which they are bonded a benzene
ring, which may be substituted with groups selected
from hydrogen, C1_6alkyl or a-alkene.
C1_6alkyl or C1_6alkene means a branched or
non-branched hydrocarbon chain containing 1 - 6 carbon
atoms.
In an embodiment of the invention, the de-
rivative has the formula (III)

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H ,6
R5 (III)
5 R4
R
R11
or the formula (IV)
h R5
R4 ( Iv)
R ~3
R11
where X is an oxygen or sulfur atom and R3 -
Rll are identical or different groups selected from hy-
drogen, C1_6alkyl or a-alkene having the formula (II).
In an embodiment of the invention, the de-
rivative has the formula (V)
H Rs
R4 (V)
F R3
R11
where R3 - R11 are identical or different
groups selected from hydrogen, C1_6alkyl or a-alkene
having the formula ( I I ) ,
or R-, and R8 are together an oxygen atom
and/or R4 and RS and/or Rlo and R11 form together with
the carbon atoms to which they are bonded a benzene

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ring, which may be substituted with groups selected
from hydrogen, C1_6alkyl or a-alkene .
The E-vitamin derivative of the invention or
the compound analogous with it preferably has a struc
ture containing at least one fused benzene ring and a
ring containing a heteroatom, and an a-chain linked
with them. The heteroatom, such as an oxygen or sulfur
atom, and the hydroxy group are preferably bonded to
opposite sides of the benzene ring of the heterocycle,
with the result that an effect stabilizing the com-
pound is produced.
One group of E-vitamin derivatives according
to the invention is formed by compounds consistent
with formula (III) or (IV), where one the 2-position
groups R3 and R4 or 3-position groups RS and R6 is hy-
drogen or Cl_6alkyl and the other an a-alkene consis-
tent with formula ( I I ) , R~ - R11 are hydrogens or C1_
6alkyls and the sum of integers m, n and o is 1 - 12
and R1 and Rz are as specified above.
A preferred group of compounds according to
the invention are compounds (III) or (IV) in which one
of the heterocycle 2-position groups R3 and R4 or of
the heterocycle 3-position groups RS and R6 is a hydro-
gen or C1_6alkyl while the other is an a-alkene consis-
tent with formula (II), where n + m + o is an integer
1 - 6 and R1 and RZ are hydrogens and R9 - R11 are C1_
6alkyls. In an embodiment, the derivative is a com-
pound consistent with formula (III), where X is oxy-
gen, one of groups R3 and R4 is a methyl group and the
other is an a-alkene consistent with formula (II),
where n + m + o equals 1 or 2 and R1 and Rz are hydro-
gens, RS - R8 are hydrogens and R9 - R11 are methyls . R3
or R4 may alternatively be a hydrogen instead of a
methyl group. In an embodiment, the derivative is a
compound consistent with formula (IV), where X is oxy-
gen, R1 - R4 are hydrogens, one of groups RS and R6 is

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an a-alkene consistent with formula (II) , where n + m
+ o equal s 4 , and R9 - Rll are methyl groups .
Another group of E-vitamin derivatives ac
cording to the invention consists of compounds consis
tent with formula ( I II ) or ( IV) where one of groups R9
- Rll in 5, 7 and 8-position (formula III) or 4, 6 and
7-position (formula IV) in the heterocycle is an a-
alkene consistent with formula (II) and two of the
groups are hydrogens or C1_6alkyls, and the sum of the
integers m, n and o is in the range of 1 - 12 and Rl
and RZ are as specified above.
A preferred group of compounds according to
the invention consists of compounds (III) or (IV) in
which R9 in 5-position (formula III) or 4-position in
the heterocycle is an a-alkene consistent with formula
( I I ) where the integer n is 0 or 1, m is 0 or 1 and o
is 1 - 4 and Rl and Rz are hydrogens or C1_6alkyls . Rlo
and Rll are hydrogens or C1_6alkyls . In a preferred
case, in a derivative consistent with formula (III), X
is oxygen, R1 - R4 and Rlo - Rll are methyls, RS - Ra are
hydrogens and R9 is an a-alkene consistent with for-
mula (II) where n is 0, m is 1 and o is 3. In an em-
bodiment, the derivative is a compound consistent with
formula (III) where X is oxygen, R3 - R4 and Rlo - Rli
are methyl groups, RS - R8 are hydrogens and R9 is an
a-alkene consistent with formula (II) where m is 0 and
n + o is 1.
E-vitamin derivatives consistent with formula
(III) include e.g. 6-hydroxy-2,5,7,8-tetramethyl-2
(but-3-enyl)-chromane, 6-hydroxy-2,5,7,8-tetramethyl
2-(prop-2-enyl)-chromane, 6-hydroxy-2,2,7,8-
tetramethyl-5-(1,1-dimethyl-hex-5-enyl)-chromane and
6-hydroxy-2,2,7,8-tetramethyl-5-(prop-2-enyl)-
chromane. E-vitamin derivatives consistent with for-
mula (IV) include e.g. 5-hydroxy-4,6,7-trimethyl-3-
(hex-5-enyl)-benzofurane.

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In an embodiment of the invention, the com-
pound analogous with the E-vitamin derivative is a
compound consistent with formula (IV) in which one of
groups R9 - R11 is an a-alkene consistent with formula
(II) and the other groups are hydrogens or C1_6alkyls
and R3 - Ra are hydrogens or C1_6alkyls . Alternatively,
R~ and R8 are together an oxygen atom and/or R4 and R5,
together with the carbon atoms to which they are
bonded, form a benzene ring. In a preferred embodi-
ment, Rlo is an a-alkene consistent with formula (II)
where n is 0 or l, m is 0 or 1 and o is an integer 1 -
4 and R1 and RZ are methyl groups, R9 is a C1_6alkyl, Rll
is a hydrogen, R~ and R$ are together an oxygen atom
and R4 and R5, together with the carbon atoms to which
they are bonded, form a benzene ring. A compound con-
sistent with formula (V) may be e.g. a thioxanthone
derivative, such as a hydroxythioxanthone derivative.
The derivative according to the invention may
naturally have any kind of structure corresponding to
those described above, e.g.
R4
~3
R
An E-vitamin derivative consistent with for-
mula (I) or a compound analogous with it is produced
using suitable synthesizing methods of organic chemis-
try.

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9
The E-vitamin derivative of the invention or
the compound (I) analogous with it can be produced
e.g.
A) by allowing a hydroquinone derivative to react with
a suitable tertiary unsaturated alcohol or thiol.
In method A), a compound consistent with for-
mula (I) can be produced directly by allowing a hydro-
quinone derivative, such as a mono-, di- or trialkyl-
hydroquinone, e.g. dimethyl or trimethyl hydroquinone,
to react with a suitable unsaturated alcohol, such as
alka-dienol, e.g. 2,7-octadien-1-of or 3-methyl-1,6-
heptadien-3-ol, or thiol in a suitable solvent. Op-
tionally, according to method A), in a first stage it
is possible to prepare an intermediate product con-
taming a (halogen-alkyl) group or a corresponding
group by allowing a hydroquinone derivative to react
with a suitable unsaturated alcohol, such as 2-alkyl-
alka-l,x-dien-3-ol, e.g. 3-methylhept-1,6-dien-3-of or
3-alkyl-x-halogen-alk-1-en-3-ol, e.g. 3-methyl-5-
chlor-pent-1-en-3-ol, or thiol in the presence of a
suitable catalyst in a suitable solvent. In a second
stage, a compound consistent with formula (I) is pre-
pared by splitting off a hydrogen halogenide or a cor-
responding compound from the halogen alkyl group or an
equivalent group in the intermediate product in the
presence of an alkali. A suitable catalyst is e.g. a
metal halide, such as aluminum chloride and zinc chlo-
ride. Suitable solvents are e.g. acids, such as formic
acid, sulfuric acid or equivalent, tetrahydrofurane
(THF) and dichloromethane. A suitable alkali is e.g.
1,8-diazabicyclo(5.4.0)undec-7-ene (DBU).
An E-vitamin derivative or a compound (I)
analogous with it as provided by the invention can be
produced e.g.
B) by allowing a hydroquinone derivative to
react with a suitable unsaturated alcohol or thiol and

CA 02379845 2002-O1-18
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adding an a-alkene to the fused heterocyclic deriva-
tive thus formed.
In a first step in method B), a fused hetero
cyclic derivative can be produced by allowing a hydro
5 quinone derivative, such as mono-, di- or trialkylhy
droquinone, to react with a suitable tertiary unsatu-
rated alcohol, such as 3-alkyl-alk-1-en-3-of e.g. 3-
methyl-but-1-en-3-of or thiol, in the presence of a
suitable catalyst in a suitable solvent. A suitable
10 catalyst is e.g. a metallic halide, such as aluminum
chloride and zinc chloride. Suitable solvents are e.g.
tetrahydrofurane (THF) and dichloromethane and acids,
e.g. formic acid. In a second step in the method, an
a-alkene consistent with formula (II) is added to the
heterocyclic derivative in acid conditions.
The E-vitamin derivative of the invention or
a compound analogous with it is preferably used as a
stabilizing comonomer, i.e. as a stabilizer, in co-
polymerization to produce a stabilized copolymer. The
function of the stabilizer is to prevent and reduce
the harmful effects of heat, UV radiation, oxygen
and/or ozone on the copolymer.
The stabilized copolymer consists of at least
one monomer variety and a stabilizing comonomer. The
monomer in question is an olefin and/or a cyclic
and/or aromatic compound containing an a-alkene chain.
The olefin monomer may be e.g. ethylene, propylene, 1-
butene, isobutene and/or 4-methyl-1-pentene or the
like or a mixture of these . The aromatic compound may
be styrene. Naturally, the monomer may be of any type.
The stabilizing comonomer is an E-vitamin derivative
or a compound analogous with it which has the formula
(I) and which has a clearly stabilizing effect and
which can be polymerized under normal polymerization
conditions. The stabilizing comonomer may be e.g. a
derivative of chromane-, benzofurane- or hydroxythi-
oxanthone.

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11
The comonomer, i.e. stabilizer of the inven-
tion, is preferably bonded by its a,-alkene chain to a
copolymer.
In an embodiment of the invention, the co
y polymer comprises one olefin or styrene monomer vari
ety and an E-vitamin derivative according to the in
vention or a compound analogous with it having the
formula (III) , (IV) or (V) .
The copolymer preferably belongs to so-called
addition polymers. When an addition polymer is formed,
no small-molecule side products are generated, i.e.
the structural unit of the polymer has a~monomeric
composition. Monomers may have a linear or a branched
hydrocarbon chain, and they contain at least one dual
bond enabling a polymerization reaction to take place.
In the copolymer, different monomer varieties
may be arranged in different ways, e.g. in a regular
fashion, such as alternately, as a segment or in other
ways like this. The monomers may also be arranged in
an irregular fashion. The structure of the copolymer
is preferably mainly regular, such as isotactic or
syndiotactic, as is typically the case when monomers
are polymerized using metallocene or Ziegler-Natta
catalysts (stereospecific polymerization). A feature
characteristic of especially products obtained via po
lymerization using metallocene catalysts is a syndio
tactic form. The crystallizing properties of the poly
mer depend on the regularity of the structure, among
other things. However, the polymer may also contain
atactic parts or it may completely atactic.
In the method of the invention for the pro-
duction of a stabilized copolymer, at least one mono-
mer variety and a stabilizing comonomer are copolymer-
ized in the presence of a catalyst in a single-stage
or mufti-stage polymerization process known in itself,
using e.g. precipitation, solution or gas phase polym-
erization, which will not be described here in detail.

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12
According to an embodiment, the catalyst used
in copolymerization is preferably e.g. a liquid or
solid metallocene catalyst or its derivative known in
itself, which is formed from derivatives of transition
metals, including lanthanides. Among the best transi-
tion metals for the production of catalysts are tran-
sition metals belonging to groups 3 and 4, and lan-
thanides whose oxidation number is +2, +3 or +4. The
metallocene components contain 1 - 3 anionic or neu-
tral groups having a ~-bond. To improve the activity
of the catalyst, a cocatalyst, which often consists of
methylalumoxane (MAO), is generally used. More pref-
erably, MAO can be replaced e.g. with compounds con-
taining boron, e.g. tri(hydrocarbyl)boron and its
halogenated derivatives. The cocatalyst used may be
e.g. tetraphenyl borate. In the copolymerization
method of the invention, it is possible to use a . g . a
metallocene catalyst of the type described in patent
application FI 941662. Naturally, in the copolymeriza-
tion method in question, it is also possible to use
other catalysts used in this field. The catalyst may
comprise a solid carrier. The carrier may consist of
any carrier material, which will not be described here
in detail.
In an embodiment of the invention, the cata
lyst used in copolymerization contains a ~t-cyclo
pentadienyl transition metal compound and an alumoxane
compound. In an alternative embodiment, the catalyst
contains a ~-cyclo-pentadienyl transition metal com
pound and a compound containing boron.
In an embodiment, the stabilizing comonomer
is chemically complexed a . g . by its heteroatom to the
catalyst, being bound via a chemical bond e.g. to a Zr
atom of the catalyst. The comonomer may naturally also
be used as such or mixed with other monomers e.g. in
the polymerization solution during polymerization.

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13
At the polymerization stage, the stabilizing
comonomer and the monomers, e.g. olefin and/or styrene
monomers, are copolymerized, in which process the co-
monomer of the invention is polymerized substantially
along with other monomers, being simultaneously chemi-
cally bound to the copolymer. The monomer to be polym-
eri zed is bound to an active point , a . g . a Zr atom in
the catalyst, causing faster polymerization. The poly-
mer grows as the structural units of the copolymer are
increasing. The copolymer contains different monomers
in certain proportions.
The copolymer may be e.g. an ethylene/-, pro-
pylene/-, butylene/- or styrene/E-vitamin derivative-
copolymer. The copolymerization product may naturally
consist of more than two monomer varieties. Using dif-
ferent production methods and proportions of different
monomers, it is possible to adjust the properties of
the copolymer.
Copolymers as provided by the invention can
be used either as such or in a mixture with other
polymers. A copolymer stabilized with a comonomer ac
cording to the invention can be used e.g. as packing
material in the foodstuff industry.
The E-vitamin derivative of the invention or
the compound analogous with it has the advantage that
it is able to polymerize in typical polymerization
conditions with a good yield and that it has a good
ability to inhibit oxidation, allowing it to be used
as an oxidation inhibitor in polymer production. Fur
thermore, the comonomer improves the adhesion proper-
ties of polymers e.g. with respect to fillers.
The copolymer of the invention has the advan-
tage that the stabilizing comonomer, i.e. stabilizer,
is chemically bonded to the polymer structure during
polymerization, which means that it is uniformly dis-
tributed in the entire polymer and the chemical bonds
prevent the loss of stabilizer in the product, in

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14
other words, they prevent the stabilizer from drifting
toward the surface of the product during use. Thus,
the stabilizer will not drift e.g. to a foodstuff pro
tected with plastic and is therefore not transferred
to people.
The copolymerization method of the invention
has the advantage that it allows the use of a metallo-
cene catalyst. In polymerization conditions, such a
catalyst works better than other catalysts known at
present. When the metallocene catalyst in question is
used, a polymer product having a syndiotactic struc-
ture and therefore a higher melting point can be manu-
factured.
A further advantage provided by copolymeriza-
tion according to the invention is that stabilization
is performed during polymerization, in other words,
the stabilizer is added as a comonomer to the polym-
erization product essentially during polymerization,
so that the product is directly ready for further
processing, in other words, the product thus obtained
need not be melted again and fed into an extruder.
Thus, a saving is also made in the investment costs of
the extruder, which may amount to several tens of mil-
lions, even over a hundred million FIM.
In the following, the invention will be de-
scribed by the aid of a detailed examples of its em-
bodiments with reference to the drawings, wherein
Fig. 1 presents the results of a mass spec
trometry analysis of a comonomer according to the in
vention, 5-hydroxy-4,6,7-trimethyl-3-(hex-5-enyl)
benzofurane,
Fig. 2 presents the results of an NMR
spectrometry analysis of a comonomer according to the
invention, 5-hydroxy-4,6,7-trimethyl-3-(hex-5-enyl)
benzofurane,
Fig. 3 presents the results of a mass spec-
trometry analysis of a comonomer according to the in-

CA 02379845 2002-O1-18
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vention, 6-hydroxy-2,5,7,8-tetramethyl-2-(but-3-enyl)-
chromane, and
Fig. 4 presents the results of an NMR
spectrometry analysis of a comonomer according to the
5 invention, 6-hydroxy-2,5,7,8-tetramethyl-2-(but-3
enyl)-chromane.
Example 1; preparation of 6-hydroxy-2,5,7,8-
tetramethyl-2-(but-3-enyl)-chromane.
to H \ HCI(g)/ZnCl2
H --,
or AIC13/CH3N02
OH
15 H
DBU
+ isomer
H
H
O
O
Preparation of 3-methylhept-1,6-dien-3-ol:
To 232 g (0.4 mol) of vinyl magnesium chlo-
ride in THF was added a solution consisting of 35 g
(0.36 mol) of 5-hexene-2-one in 150 ml of anhydrous
THF. The reaction mixture was stirred for 20 h at room
temperature, whereupon it was cautiously poured into
450 ml of cold, saturated, aqueous NH4CL solution. The
organic extract was concentrated and diffused with di-
chloromethane, dried using Na2S04 and concentrated. The
residue was distilled, and the yield obtained was 35.5
g (78%) 3-methylhept-1,6-dien-3-ol; t.p. 45 °C/10
mmHg.

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16
Preparation of 6-hydroxy-2,5,7,8-tetramethyl-
2-(4-chloro-butyl)-chromane:
A suspension containing 20 g (0.150 mol) an
hydrous A1C13 in 200 ml of dichloromethane was stirred
at 0 °C while at the same time adding 25.8 g (0.42
mol) of CH3N02 under a protective layer of argon. After
the mixture had been stirred for 10 min at 0°C, 30.4 g
(0.2 mol) of trimethyl-hydroquinone was added in
batches. The brown suspension obtained as a result was
cooled to -20 °C and a solution consisting of 3-
methylhept-1,6-dien-3-of in 750 ml of dichloromethane
was added drop by drop during 0.5 h. The mixture thus
produced was allowed to cool down slowly to room tem-
perature, and it was stirred overnight, whereupon it
was poured on ice/water. The organic layer was col-
lected, washed twice using a NaHC03 solution and con-
centrated. The yield thus obtained was 40 g of a raw
product containing insignificant impurities. The raw
product was distilled, and the yield thus produced was
15 g (25 0) of 6-hydroxy-2,5,7,8-tetramethyl-2-(4-
chlorobutyl)-chromane fraction in the form of a light
brown liquid, t.p. 180 °C/1 mmHg, which was crystal-
lized overnight in a cooler mp X °C. 1H NMR: 1.22 (s,
3H, CH3-C (2) ) ; 1.5 (d, 3H, -CHC1CH3) 1. 65 (m, 2H, ArCH2-
CHz-) 1.8 (m, 4H, -CHz-CHZ-) 2.1, 2.12, 2.15 (3S, 9H,
ArCH3) ; 2.62 (t, 2H, CH2Ar) ; 4.1 (m, 1H, CH) and 4.23
(s, 1H, OH). 13C NMR: 11.3, 11.8, 12.2, 20.7, 23.6,
25.2, 31.3, 34.4, 36.7, 59.1, 73.9, 117.1, 118.5,
121.1, 122.5, 144.7 and 145.2.
Preparation of 6-hydroxy-2,5,7,8-tetramethyl-
2-(but-3-enyl)-chromane:
To 14.8 g (0.05 mol) of 6-hydroxy-2,5,7,8
tetramethyl-2-(4-chlorobutyl)-chromane was added 36.3
g (0.24 mol) of 1,8-diazabicyclo(5.4.0)undec-7-ene
(DBU) and the solution was heated to 120 °C and
stirred for 20 h. After that, the reaction mixture was

CA 02379845 2002-O1-18
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17
allowed to cool down to room temperature, poured into
350 ml of dichloromethane and washed repeatedly using
diluted HC1. The organic layer was concentrated, and
the yield thus obtained was 10.2 g of raw product that
was free of DBU. In addition, the material was puri-
fied by distilling, and the result thus obtained was
5g (38 %) of 6-hydroxy-2,5,7,8-tetramethyl-2-(but-3-
enyl)-chromane; t.p. 154 °C/lmmHg.
Example 2; preparation of 5-hydroxy-4,6,7-trimethyl-3-
(hex-5-enyl)-benzofurane:
H
+ HO-CH2-CH=CH-(CH2)3-CH=CH2
OH
HCOOH
H
O
Trimethyl hydroquinone (23.7 g) and 2,7-
octadien-1-of (19.7 g) were weighed and put into a re-
action vessel and 50 ml of formic acid was added into
the mixture. The temperature of the mixture was raised
to the boiling point of formic acid, and the reaction
was allowed to continue for three hours. The reaction
mixture was poured into 150 ml of ice-water mixture,
and the organic phase was recovered in diethyl ether.
The organic solvent was evaporated, whereupon 100 ml
of methanol and 1 ml of hydrochloric acid was added to
the residue. The reaction mixture was hydrolyzed at
the boiling point of methanol for 30 min, whereupon
the solvent was evaporated from the mixture. The mix-

CA 02379845 2002-O1-18
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18
ture was dissolved in diethyl ether, and the organic
phase was washed twice using sodium hydrogen carbonate
and five times using distilled water. The diethyl
ether was evaporated. At this point, the yield was
48.0 g. n-hexane was added to the mixture, which was
then stirred for 30 min at the boiling point of hex-
ane, whereupon the mixture was allowed to cool down to
room temperature. The portion not dissolved in hexane,
mainly consisting of inert trimethyl hydroquinone and
the product, was separated from the mixture by filter-
ing. The solid portion was dissolved in a small amount
of ethanol and precipitated by adding some water into
the solution, whereupon the product (7.5 g) was sepa-
rated by filtering. After that, based on mass spec-
trometry (Fig. 1) and NMR spectrometry (Fig. 2) analy-
ses, the product was identified as 5-hydroxy-4,6,7-
trimethyl-3-(hex-5-enyl)-benzofurane.
Example 3; preparation of 6-hydroxy-2,2,7,8-
tetramethyl-5-(1,1-dimethyl-hex-5-enyl)-chrom---
HO
H H
HCI(g)/ZnCl2
OH
CH3
H+/ /C=CH-(CH2)3-CH=CH2
3o CH3
;(CH;
CH2=~C~H
Dimethyl hydroquinone and formic acid were
mixed together, and 3-methylbuten-3-of was added lit-
tle by little into the reaction mixture during one

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19
hour. The mixture was allowed to react for 2 h at the
boiling point of formic acid, whereupon the reaction
was interrupted by adding some ice-water mixture into
it. The organic phase was recovered in diethyl ether
and washed several times with water. The organic phase
was evaporated, and 75 ml of methanol and 1 ml of con-
centrated hydrochloric acid was added into the resi-
due, whereupon the mixture has hydrolyzed for half an
hour at the boiling point of methanol. The methanol
was evaporated, and the residue was dissolved in di-
ethyl ether, which was washed alternately twice with
sodium hydrogen carbonate and five times with water.
The diethyl ether was evaporated and the residue was
distilled in a vacuum. The intermediate product (1.25
g), 6-hydroxy-2,2,7,8-tetramethyl-chromane, was recov-
ered in conditions as follows: p - 0.2 mbar and T -
110 - 120 °C.
6-hydroxy-2,2,7,8-tetramethylchromane and 7
methyl-1,6-octadiene were mixed together. The reaction
solution was heated, whereupon an acid catalyzes was
added into it. The mixture was allowed to react during
24 hours, and the product, 6-hydroxy-2,2,7,8
tetramethyl-5-(1,1-dimethyl-hex-5-enyl)-chromane, was
separated by the conventional method and purified by
distilling.

CA 02379845 2002-O1-18
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Example 4; preparation of 6-hydroxy-2,5,7,8-
tetramethyl-2-(but-3-enyl)-chromane
H CH=CH2
5 + HO-C-CH2-CH2-CH=CH2 -'
I HCOOH
OH CH3
HO
to
15 1.02 g of trimethyl hydroquinone, 0.844 g of
3-hydroxy-3-methyl-1,6-heptadiene and 10 ml of formic
acid (98 %) were added into a 50-ml reaction vessel.
The temperature was increased to the boiling point of
formic acid, at which temperature the reaction was al-
20 lowed to continue for 2 h 50 min. The reaction was in-
terrupted by pouring the mixture into an ice-water
mixture, whereupon the organic phase was recovered and
washed in the conventional manner. From the product
were first separated the portions not dissolved in
hexane, whereupon the product was dissolved in etha
nol, precipitated with water and washed using hexane
and diethyl ether. The yield was 1.3 g. The product
was identified via mass spectrometry (Fig. 3) and NMR
spectrometry (Fig. 4) analyses as 6-hydroxy-2,5,7,8
tetramethyl-2-(but-3-enyl)-chromane.

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21
Example 5; preparation of 6-hydroxy-2,2,7,8-
tetramethyl-5-(prop-2-enyl)-chromane
OH
H
O
OH
io
H
0
0
H O
0
Dimethyl hydroquinone and formic acid were
mixed together, and 3-methylbuten-3-of was added lit-
tle by little into the reaction mixture during one
hour. The mixture was allowed to react for 2 h at the
boiling point of formic acid, whereupon the reaction
was interrupted by adding some ice-water mixture into
the mixture. The organic phase was recovered in di-
ethyl ether and washed several times with water. The
organic phase was evaporated and 75 ml of methanol and
1 ml of concentrated hydrochloric acid was added into
the residue, whereupon the mixture was hydrolyzed for
half an hour at the boiling point of methanol. The
methanol was evaporated, and the residue was dissolved
in diethyl ether, which was washed alternately twice
with sodium hydrogen carbonate and five times with wa-
ter. The diethyl ether was evaporated, and the residue
was distilled in vacuum. The intermediate product

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22
(1.25 g), 6-hydroxy-2,2,7,8-tetramethyl-chromane, was
recovered under the following conditions: p = 0.2 mbar
and T = 110 - 120 °C.
The intermediate product (0.5 g) was dis
solved in 10 ml of acetone. KzC03 (0.37 g) was added
gradually and the mixture was stirred for 30 min,
whereupon C3HSBr (0.33 g) was added gradually. A reflux
condenser was used during the reaction. The final
product, 6-hydroxy-2,2,7,8-tetramethyl-5-(prop-2
enyl)-chromane, was obtained by heating the mixture
for 48 h. The product was separated from the mixture
via column chromatography.
Example 6; Preparation of hydroxythioxanthone
OH
COOH
i
SH H2so
O
_. ~oY~o~°~
S
A hydroxythioxanthone derivative was prepared
from 6-tert-butyl-(2-(1,1-dimethylhept-6-enyl))-
phenol, which can be produced e.g. by a method accord-
ing to patent PCT/FI95/00196, and from thiosalicylic
acid in a manner known in itself.
Example 7; copolymerization

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23
A polymerization test was carried out to ex-
periment on copolymerization of 6-hydroxy-2,5,7,8-
tetramethyl-2-(but-3-enyl)-chromane and propylene in
the presence of a metallocene catalyst. The metallo-
cene catalyst consisted of ~-cyclo-pentadienyl transi-
tion metal and alumoxane.
The treatment of the ~-cyclo-pentadienyl
transition metal and alumoxane as well as the comono-
mer was performed in a nitrogen cabinet containing un-
der 2 ppm oxygen and under 5 ppm water. The polymeri-
zation was carried out in an autoclave equipped with a
turbine mixer. The reaction temperature was adjusted
with an accuracy of 0.3 °C.
The dry autoclave was evacuated and rinsed
with water. This was repeated three times. A first
batch of distilled toluene was fed into the reactor by
using nitrogen over-pressure. 5 mg of ansa metallocene
catalyst was dissolved in a second batch of
MAO/toluene solution and pre-activated by letting them
interact with each other at room temperature for 5
min.
The catalyst/activator mixture was fed into
the reactor. Pre-polymerization was started by adding
a propylene monomer. After 3 min., a comonomer diluted
with toluene was added using propylene gas, until the
partial pressure of propylene reached 2 bar. The po-
lymerization activity was monitored by measuring the
propylene consumption while maintaining a constant to-
tal pressure in the reactor by continuously adding
gaseous propylene. After 30 min, polymerization was
interrupted by stopping the supply of propylene and
adding 100 ml of methanol. Polyolefin was filtered and
the catalyst residue was removed by treating the prod-
uct, i.e. the copolymer, with a 1-% methanol/HCl solu-
tion. The product was washed twice with ethanol, dried
in vacuum at a temperature of 50 °C and weighed. The
amount of copolymer obtained was 3 g. The copolymer

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24
was diffused using a Soxhlet device before determining
the concentration of bonded stabilizer. The results of
the polymerization this means that are presented in
Table 1.
Table 1 shows that the OIT temperature rises
as the comonomer content increases, which is an indi-
cation of the effect of the stabilizer. Further, it
can be seen from Table 1 that crystallization of the
product decreases at higher copolymer content levels,
indicating that the comonomer is chemically bonded to
the rest of the polymer.
Table 1. The results of copolymerization of
6-hydroxy-2,5,7,8-tetramethyl-2-(but-3-enyl)-chromane
and propylene.
Test Stabi-Zr A1 Stab Stab/ TM Crys Product OIT
lizer ~mol/1 mmol/1 /Zr A1 C % kg/mol
Mol/ Mol/ Zr h
Mol mol atm
1 42 126 128.4 73.4 5644 210
2 + 44 132 120 0.040 129.1 69.7 3984 229
3 + 44 132 120 0.040 131.0 64.6 3590 230
4 + 44 132 265 0.086 127.2 56.0 2510 244
5 + 44 132 356 0.120 129.0 58.2 2943 248
The E-vitamin derivative of the invention or
the compound analogous with it is suited for use in
different applications, e.g. for the manufacture of
any kind of copolymer. Moreover, the copolymer of the
invention is suited for use as different applications
for any purpose.
The embodiments of the invention are not re-
stricted to the examples presented above; instead,
they may be varied in the scope of the following
claims.

Representative Drawing