Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
HOECHST ~RTIENGESELLSCHAFT HOE 92/F 390 Dr.SP/wo
Description
Glass fiber-reinforced cycloolefin polymer material and
proces~es for its preparation.
The present invention relates to a glass fiber-reinforced
cycloolefin polymer mate.~ial, proce~ses for its prepara-
tion starting from glass fibers and a cycloolefin poly-
mer, and shaped articles made of the material.
Cycloolefin polymers are a class of polymer with an
outstanding level of properties. They are distinguished
inter alia by a ~ometimes high heat distortion point,
transparency, stability to hydrolysis, low ab~orption of
water, resistance to weathering and high rigidity.
It is known that cycloolefins can be polymerized by mean~
of variou~ cataly~ts. The polymerization here proceed~
via ring opening or with opening of the double bond,
depending on tha catalyst.
It is knowm that fibrous or particulate reinforcing
substances can be incorporated into cycloolefin polymer
blends.
, ,,
Japanese Preliminary Published Specification
JP 03,207,739 refer~ to a thermoplastic combination which
comprises glass fibers and a random copolymer of cyclo-
olefin and ethylene. It comprises 1 to 100 part~ of
¦ 25 copolymer per 100 parts of glasq fibers. Injection-molded
components have a high heat di~tortion point, rigidity,
resistance to scratching, re3istance to cracking, resist-
I ance to water and low shrinkage, and a low coefficient of
I linear thermal expansion. Copolymers which have been
¦ 30 modified with maleic anhydride are ~ometimes used.
The cycloolefin polymer composite~ described have no
~ l 3 IJ 1 ~
- 2 - -~
transparency, since various fillers are used in the
composites. To prepare transparent cycloolefin polymer
composites which are also suitable for optical applica-
tion~, a high minLmum transparency to light i~ requlred.
The object of the present invention i8 therefore to
provide composites of cycloolefin polymers and glas~
fibers which have good mechanical properties and at the
same time the highest po3sible tran3parencies to light.
The present invention achieve~ this object.
A glass fiber-reinforced cycloolefin polymer material
comprising 1 to 9~% by weight of at least one cycloolefin
polymer and 99 to 1% by weight of glass fiber has now
been found, in which the absolute differenca in refrac-
tive index (the refractive index of the glass of the
glass fiber minus the refractive index of the cycloolefin
polymer) i~ not mora than 0.015 for each cycloolefin
polymer, and the refractive index of the glass fiber is
in the range from 1.510 to 1.560. The material preferably
comprises 10 to 90% by weight of cycloolefin polymer and
90 to 10% by weight of glass fiber.
Massive shaped articles which are made of the material
according to the invention have a direct tran~mission
(in-line transparency to light) of at least 40%. The
direct tran~mi~sion i8 mea~ured on a pre3~ed 3heet 1 mm
25 thick using a ~pecially constructed apparatus. Only the - -
light emerging through the sheet in the direction of the
beam of light i8 taken into account here, and not the
scattered light.
':; .,.' :~
The cycloolefin polymers employed preferably have a - refractive index in the range from 1.525 to 1.545. Poly~
norbornene has a refractive index of 1.534 (Xirk-Othmer,
Encyclopedia of Chemical Technology, Volume 11, 303).
Cycloolefin polymers which aan be employed for the
, ., . ~, . .: . ~ : :; ,. . i ~ . . ~"h; '
5 1 ~ -:
. . - 3 -
material~ according to the invention comprise ~tructural
unit~ which are derived from at least one monomer of the
formulae (I) to (VI) or (VII):
HC ~ CH~~----___cH /
¦¦R3 - C - R~
HC \ I / CH
CH R
C H ~ C H 2
HC~¦ ----CH
I
¦ R3 - C - R~ CH2
/ (II)
H C~ ~ H / \ C H 2
~ ~R
H C ~ j ----CH j \CH
¦¦ R3-- C -- R4 ¦ R5--C--R~
HC ¦ CH~ I /CH~
\C H / C H R 2
, , ~ . : ` " .- ~.. .. ,.,.. `~ "; ,.,.. ` ~: ``.. , `~, ,., - "
2 1 1 ~
CH-----CH '~ j \CH j CH ~R1
¦l R~-- C -- R4 ¦ RS--C_RC ¦ R7--C R~ ¦ (IV)
HC ! CH ¦ /CH~¦ ~C~\
R5
HC ~ CH_______ ~ CH \
¦1 ~3 - C - R4 ¦ ¦ (V)
HC \ I / CH / \ R2
CH f H
R6 1~
uc 7 --CH --CU j CU
\l / \ ~ \Ir
!6
CH CH
(CH2~ (VII)
S In the formulae (I) to (VI), the radical~
Rl, R2, R3, R4, Rs, R6, R' and R8 are identical or differ~nt
radicals chosen from hydrogen and a C1-C3-alkyl
radical.
The index n in the cycloolefin of the formula (VII) i8 an
integer from 2 to 10.
' :~
- 5 -
In the various formulae, the 6ame radicals R1 can have a
different meaning. In addition to the structural units
derived from at least one monomer of the formulae (I) to
(VII), the cycloolefin polymers can compri~e further
structural units which are derived from at lea~t one
acyclic 1-olefin of the formula (VIII)
R9 ",R19
C _ C (VIII)
R11~ \R12 ,,,
In the formula (VIII), the radical~ Rg, R', R1' and Rl2 are
identical or different radical~ chosen from hydrogen and
C,-CB-alkyl radicals or C6-C12-aryl radicals. Preferably,
Rl, Rl1 and Rl2 are hydrogen.
Preferred comonomers of the formula (VIII) are ethylene
or propylene. Copolymers of polycyclic olefins of the
fsrmula (I) or (III) and acyclic olefin~ of the formula
(VIII) are employed in particular. Particularly preferred
cycloolefins are norbornene and tetracyclododecene, which
can be substituted by Cl-C6-alkyl, ethylene/norbornene
copolymer~ being of particular importance.
¦ The ethylene/norbornene copolymer~ particularly prefer-
¦ 20 ably employed comprise 25 to 75 mol% of norbornene and 30
to 75 mol% of ethylene.
Of the monocyclic olefin~ of the formula (VII), Gyclo-
j pentene, which can be substituted, i8 preferred.
Mixtures of two or more olefin~ of the particular type
can al~o be used as the polycyclic olefin~ of the
formulae (I~ to (VI), polycyclic olefins of the formula
(VII) and open-chain olefins of the formula (VIII). Both
cycloolefin homopolymers and cycloolefin copolymer~, such
a~ bi-, ter- and multipolymers, can therefore be employed
for the preparation of the gla~s fiber-reinforced
materials according to the invention.
-" 2~
-- 6 --
The cycloolefin polymerizations which proceed with
opening of the double bond can be catalyzed by newer
catalyst 8yBtems (EP-A-0407870, EP-A-0203799), and also
by a conventional Ziegler cataly~t system (DD-A-222317,
5 DD-A-239409) .
The cycloolefin homo- and copolymers which compri~e
structural units derived from monomer~ of the formulae
(I) to (VI) or (VII) are preferably prepared with the aid
of a homogeneou~ catalyst compri~ing a metallocene, the
central a~om of which is a metal from the group compri~
ing titanium, zirconium, hafnium, vanadium, niobium and
tantalum, which forms a ~andwich structure with two mono-
or polynuclear ligands bridged to one another, and an
aluminoxane. The bridged metallocene is prepared in
accordance with a known equation (cf. J. Organomet.
Chem. 288 (1985) 63 to 67 and EP-A-320762). The alumin-
oxane which funetions a~ a cocataly~t is obtainabl~ by
various method~ ~cf. S. Pasynkiewicz, Polyhedron 9 (1990)
429). Both the structure and the polymerization of the~e
cycloolefins are de~cribed in detail in EP-A-0407870,
EP-A-0485893, EP-A-0501370 and EP-A-0503422.
Cycloolefin polymers having a viscosity number of greater
than 20 cm3/g (measured in decalin at 135C in a concen-
tration of 0.1 g/100 ml) are preferably proce3sedO
Glas~ fibers are usually employed aB reinforcing
material~ in the plastic~ industry. Industrial glass
fiber~ have sizes which provide protection again~t
mechanical ~tress as glass filaments and join spun
threads of glass loosely to one another.
The main constituents of ~izes are, according to
WO 86tO1811, film-forming polymers and lubricant# and, if
required, adhesion promoters and other additive~. The
film-forming polymer~ are di~persible, soluble or emulsi-
fiable in aqueous medium, as is the reaction product with
the process auxiliaries. The content of water in the
211~
,
-- 7 --
aqueous-chemical combination of the Yize constituents i8
designed such that these give the effective content of
solid on the glass fiber.
It has now been found that, for the preparation of
transparent, gla6s fiber-reinforced cycloolefin polymer
material, it i~ advantageous for the glass fibers
employed to be desized beforehand. This pos~ibly lie~ in
the fact that the various constituents of a size on the
one hand and the glass fiber on the other hand usually
display widely differing refractive indices, which leads
to the transparency of a gla~s fiber-reinforced ~haped
article to light being greatly reduced. It i~ known, for
example, from Int. Encyclopedia of Composites (Verlag
Chemie, New York), Volume 6, p. 225 that transparent
compo~ite material~ can be obtained if the refractive
indices of inorganic gla6ses and polymers coincide.
The glass fiber i~ preferably heated to 500C in an
oxygen-containing atmosphere to remove the size. All the
organic materials applied to the glass fiber by the
manufacturer are removed by thi~ operation.
The invention furthermore relates to a proces~ for the
preparation of a gla~s fiber-reinforced cycloolefin
polymer material, in which glass fibers and a cycloolefin
polymer are mixed in a mixing ratio of gla~s fiber/cyclo-
olefin polymer of 1:99 to 99:1. This process comprise~freeing commercially available glass fibèrs, the gla~s of
which has a refractive index in the range from 1.510 to
1.560, from the ~ize and then mixing them with a cyclo-
olefin polymer. Mixing can also be carried out by mixing
a ~olution of the cycloolefin polymer in an organic
I ~olvent with the gla~s fiber~ and removing the 301vent by
¦ evaporation or pouring the mixture into an exces~ of a
¦ ~econd solvent which is miscible with the first eolvent
I but in which the cycloolefin polymer is insoluble, 80
¦ 35 that the cycloolefin polymer is precipitated on the gla~s
~ fibers. Mixing can furthermore be carried out by mixing
3~11
- 8 -
a melt of the cycloolefin polymer with the glass fiber.
Shaped articles can be produced from the cycloolefin
polymer material according to the invention by meltin~ or
pressing at el0vated temperature, for example injection
molding.
~ .
The materials of glass fiber-reinforced pla~tic which
belong to the prior art have the problem that the glass
fibers sometimes adhere poorly to the polymer - especi-
ally to non-polar polymer~ - and the mechanical resist~
ance of shaped articles is therefore not the optimum. In
this connection, adhesion promoters have therefore
already been employed for better coupling. ~he~e adhesion
promoters are either applied to the glass fiber by the
aqueous chemical treatment to produce a size, or are
applied subsequently in a separate step via solution~.
, " ~,
It is furthermore possible for the adhesion promoters to
be incorporated into the melt of the polymers. Thi~
method has the advantage that no solutions have to be
processed. The adheæion promoters can also advantageously
be incorporated into the compositea by providing master-
batches which utilize the dilution principle, as i8
possible with the other additive~
This addition of adhesion promoter i~ also advantageous
in the two processes according to the invention for the
preparation of glass fiber-reinforced pla~tics. According
to the invention, therefore, either a polymer melt
adhesion promoter can be added or the glass fiber can be
coated with adhesion promoter.
~ .
The adhesion promoter - either according to the invention
30 or according to the prior art - can be cho~en from the -~
group compri~ing vinylsilane~, methacrylo~ilanes, amino-
silanes, epoxysilanes and methacrylate/chromium chloride
complexes.
- 9 -
Organic adhesion promoters based on polymers, in
particular those which comprise a functionalized cyclo-
olefin polymer, are preferred. The cycloolefin polymer
which is the constituent of the composite material i8
advantageously functionalized here.
The functionalized cycloolefin polymer i~ preferably
prepared by grafting a cycloolefin polymer with a polar
monomer. It is particularly advantageous if the polar
monomer used for the grafting i9 cho~en from the group
comprising a,~-unsaturated carboxylic acids, a,~-unsat-
urated carboxylic acid derivative~, organic silicon
compounds having an olefinically unsaturated and hydro-
lyzable group, olefinically unsaturated compounds having
hydroxyl groups and olefinically unsaturated epoxy
¦ 15 monomers.
I Cycloolefin polymer composites comprising such cyclo-
j olefin polymer adhesion promoters additionally display
¦ good mechanical properties, in addition to the high
transparency to light of more than 40%, according to the
above definition. These adhe3ion promoters can be applied
or incorporated by the above proce~6es. Incorporation via
the melt i3 particularly preferred here.
The invention furthermore relates to an adhesion promoter
which i~ prepared by grafting a cycloolefin polymer with
a polar monomer and ha~ a content of grafted polar
monomer of 0.01 to 50% by weight.
The glass fiber employed preferably comprises magne~ium
alumo-silicate having a refractive index of 1.510 to 1.560,
in particular 60 to 68% by weight of SiO2, 23 to 29% by
weight of Alz03 and 8 to 12~ by weight of MgO. ~atching of
the glas~ fiber/cycloolefin polymer refractive indice~ is
particularly easy in thi~ range. The resulting protucts
are particularly useful.
~he invention will be illustrated in more detail by the
-` 2~
- 10
Examples.
The following polymer~ were prepared by ~tandard method~
Cycloolefin copolymer A1 and A2 [COC A1, A2]
A) Preparation of rac-dimethylsilyl-bis-(1-indenyl~
zirconium dichloride (metallocene A)
All the following working operations were carried out
under an inert gas atmosphere using abeolute ~olvents
(Schlenk technique).
80 cm3 (0.20 mol) of a 2.5 molar solution of n-butyl-
lithium in hexane were added to a solution of 30 g
(O.23 mol) of indene filterad over alumlnum oxide
(technical grade 91~) in 200 cm3 of diethyl ether, while
cooling with ice. The mixture was ~tirred at room temper-
ature for a further 15 minutes and the orange-colored
solution was introduced via a cannula into a ~olution of
13.0 g (0.01 mol) of dimethyldichloro~ilane (99% pure) in
30 cm3 of diethyl ether in the course of 2 hours. The
orange-colored suspension wa~ stirred overnight and
extracted three times by shakins with 100 to 150 cm3 of
water. The yellow organic phase wa~ dried twice over
~odium sulfate and evaporated in a rotary evaporator. The
orange oil which remained was kept at 40C under an oil
pump vacuum for 4 to 5 hours and freed from exces3
indene, a white precipitate ~eparating out. A total of
20.4 g (71%) of the compound (CH3)2Si(Ind)2 could be
isolated a~ a white to beige powder by addition of 40 cm3
of methanol and crystallization at -35C. M.p. 79 to 81C
(2 diastereomers).
46.5 cm3 (116.1 mmol) of a 2.5 molar hexane solution of
butyllithium were 810wly added to a ~olution of 16.8 g
(58.2 mmol) of (CH3)2Si(Ind)2 in 120 cm3 of tetrahydrofuran
at room temperature. One hour after the addition had
ended, the deep red solution wa~ added dropwi~e to a
,~
,~
21i~
suspension of 21.9 g (58.2 mmol) of ZrCl4~2 tetrahydro-
furan in 180 cm3 of tetrahydrofuran in the course of 4 to
6 hours. After the mixture had been stirred for 2 hours,
the orange precipitate wa~ filtered off with suction over
a glas~ frit and recrystallized from CH2C12. 3.1 g (11%)
of rac-(CH3)2Si(Ind)2ZrCl2 were obtained in the form of
orange crystals which gradually decompo~e above 200C.
Correct elemental analyses. The mass spectrum showed M~ =
448. '~-NMR spectrum (CDC13): 7.04 to 7.60 (m,8, aromatic
H), 6 90 (dd, 2, beta-indene H), 6.08 (d, 2, alpha-indene
H), 1.12 (s, 6, SiCH3).
B) Preparation of COC A1
A clean and dry 10 dm3 polymerization reactor with a
stirrer was flushed with nitrogen and then with ethylene.
0.75 l of Exxsol and 214 g of norbornene melt were then
initially introduced into the polymerization reactor.
While ~tirring, the reactor was brought to a temperature
of 70C, and 3 bar of ethylene were forced in.
Thereafter, 20 cm3 of a toluene solution of methyl-
aluminoxane (10.1% ~y weight of methylaluminoxane of
molecular weight 1300 gtmol according to cryoscopic
determination) were metered into the reactor and the
mixture was stirred at 70C for 15 minute~, the ethylene
pressure being kept at 3 bar by subsequent metering in.
In parallel, 60 mg of rac-dimethylsilyl-bis~ indenyl)-
zirconium dichloride were dis~olved in 20 cm3 of a
toluene ~olution of methylaluminoxane (for the concentra-
tion and quality, see above) and were preactivated by
being left to stand for 15 minutes. The solution of the
~30 catalyst (metallocene and methylaluminoxane) was then
Imetered into the reactor. Polymerization was subsequently
Icarried out at 70C for 90 minutes, while stirring, the
ethylene pres~ure being kept at 3 bar by sub~equent
metering in. The contents of the reactor were then
drained into a glass beaker and the catalyst was decom-
posed by addition of 20 ml of i~opropanol. ~he clear
2 ~ ~ 0 ~
- 12 -
solution was precipitated in acetone, the mixture waY -
stirred for 10 minute~ and the polymeric solid was then
filtered off. -~
To remove re~idual solvent from the polymer, the polymer
was extracted by ~tirring twice more with acetone and
filtered off. Drying was carried out at 80C in vacuo in
the course of 15 hours.
An amount of ~ g of product was obtained.
Preparation of COC A2
A clean and dry 75 dm3 polymerization reactor with a
stirrer was flushed with nitrogen and then with ethylene.
20550 g of norbornene melt were then initially introduced
into the polymerization reactor. While stirring, the
I reactor was brought to a temperature of 70C~ and 5 bar
¦ 15 of ethylene were forced in.
Thereafter, 1000 cm3 of a toluene solution of methyl~
aluminoxane tlO.1% by weight of methylaluminoxane of
molecular weight 1300 g/mol according to cryo~copic
determination) were metered into the reactor and the
mixture was stirred at 70C for 15 minutes, the ethylene
pressure being kept at 5 bar by subsequent metered
addition. In parallel, 3000 mg of rac-dimethylsilyl-bis-
(1-indenyl)-zirconium dichloride were di~solved in
000 cm3 of a toluene solution of methylaluminoxane (for
the concentration and quality, see above) and were
preactivated by being left to stand for 15 minute~. The
solution of the catalyst (metallocene and methyl-
aluminoxane) wa~ then metered into the reactor.
Polymerization was subsequently carried out at 70C for
130 minutes, while 6tirring, the ethylene pres~ure being
kept at 5 bar by subsequent metering in. The contents of
the reactor were then drained rapidly into a ~tirred
ve~sel in which 40 1 ~xx801 100 and 110 g of ~Celite
J 100 and also 200 cm3 of demineralized water had been
." ~ ~
~ .
6 1 ~
- 13 -
initially introduced at 70C. The mixture was filtered 80
that the filter auxiliary (Celite J 100) was retained,
and a clear polymer solution re~ulted as filtrate. The
clear solution was precipitated in acetone, the mixture
was stirred for 10 minute~ and the polymeric solid was
then filtered off.
To remove re~idual ~olvent from the polymer, the polymer
was extracted by stirring twice more with acetone and
filtered off. Drying wa~ carried out at 80C in vacuo in
the cour~e of 15 hours.
An amount of 6200 g of product was obtained.
Preparation of the cycloolefin copolymers A3 and A4
A) Preparation of diphenylmethylene-(9-fluorenyl)-
cyclopentadienyl-zirconium dichloride - (metallocene B)
All the following working operations were carried out
under an inert ~as atmosphere usins absolute solvents
(Schlenk technique).
12.3 cm3 (30.7 mmol) of a 2.5 molar hexane solution of
n-butyllithium were ~lowly added to a solution of 5.10 g
(30.7 mmol) of fluor~ne in 60 cm3 of tetrahydrofuran at
room temperature. After 40 minute~, 7.07 g (30.7 mmol) of
diphenylfulvene were added to the orange ~olution and the
mixture was ~tirred overnight. 60 cm3 of water were added
to the dark red solution, the solution becoming yellow in
color and this ~olution was extracted with ether. The
ether phase was dried over MgS04 and concentrated and the
residue was left to crystallize at -35C. 5.1 g (42%) of
1,1-cyclopentadienyl-(9-fluorenyl)-diphenylmethane were
obtained as a beige powder.
2.0 g (5.0 mmol) of the compound were dis~olved in 2Q cm3
of tetrahydrofuran, and 6.4 cm3 (10 mmol) of a 1.6 molar
solution of butyllithium in hexane were added at 0C.
- 14 -
After the mixture had been ~tirred at room temperature
for 15 minutes, the eolvent was stripped off and the red
residue was dried under an oil pump vacuum and wa~hed
~everal time~ with hexane. After drying under an oil pump
vacuum, the red powder was added to a su~pension of
1.16 g (5.0 mmol) of ZrCl4 at -78C. After the mixture
had warmed up slowly, it wa~ stirred at room temperature
for a further 2 hours- The pink-colored suspencion was
filtered over a G3 frit. The pink-red residue wa3 wa~hed
with ~0 cm3 of CH2C12, dried und-r an oil pump vacuum and
extracted with 120 cm3 of toluene. ~fter the ~olvent had
been stripped of~ and the residue had been dried under an
oil pump vacuum, 0.55 g of the zirconium complex was
obtained in the form of a pink-red crystalline powder.
The orange-red filtrate of the reaction mixture was
concentrated and the residue was left to crystallize at
-35C. A further 0.45 g of the complex crystallizes from
CH2Cl2 -
Total yield 1.0 g (36%). Correct elemental analyses. The
mas~ spectrum howed M~ ~ 5566. lH-NMR spectrum (100 MHz,
CDCl3): 6.90 to 8.25 (m, 16, Flu-H, Ph-H), 6.40 (m, 2,
Ph-H), 6.37 (t, 2-Cp-H), 5.80 (t, 2-Cp-H).
:
B) Preparation of COC A3
~ :
A clean and dry 10 dm3 polymerization reactor with a
stirrer was flushed with nitrogen and then with ethylene.
560 g of norbornene melt were then initially introduced
into the polymerization reactor. While stirring, the
, reactor was brought to a temperature of 70C, and 6 bar
i of ethylene were forced in.
:.
~hereafter, 20 cm3 of a toluene solution of methyl-
aluminoxane (10.1% by weight of methylaluminoxane of ~-
molecular weight 1300 g/mol according to cryoscopic
determination) were metered into the reactor and the
mixture was stirred at 70C for 15 minute~, the ethylene
.
0 S 11
- 15 -
pre~sure being kept at 6 bar by ~ubsequent metering in.
In parallel, 10 mg of diphenylmethylene-(9-fluorenyl)-
cyclopentadienyl-zirconium dichloride were dis~olved in
20 cm3 of a toluene 801ution of methylaluminoxane (for
the concentration and quality, see above) and were
preactivated by being left to ~tand for 15 minute3. The
~olution of the catalyst (metallocene and methylalumin-
oxane) was then metered into the reactor. Polymerization
was subsequently carried out at 70C for 30 minutes,
while stirring, the ethylene pre~sure be-lg kept at 6 bar
by sub6equent metering in. The contents of the reactor
were then drained into a gla~s beaker and the cataly6t
was decomposed by addition of 20 ml of isopropanol. The
clear ~olution was precipitated in acetone, the mixture
j 15 was stirred for 10 minutes and the polymeric solid was
then filtered off.
To remove re6idual ~olvent from the polymer, the polymer
was extracted by stirring twice more with acetone and
filtered off. Drying was carried out at 80C in vacuo in
the course of 15 hour6.
An amount of 40 g of product wa~ obtained.
Preparation of COC A4
A clean and dry 75 dm3 polymerization reactor with a
stirrer was flu~hed with nitrogen and then with ethylene
and filled with 22000 g of norbornene melt (Nb). While
stirring, the reactor was then brought to a temperature
of 70C, and 6 bar of ethylene were forced in.
Thereafter, 580 cm3 of a toluene 601ution of methyl-
aluminoxane (10.1% by weight of methylaluminoxane of
molecular weight 1300 g/mol according to cryoscopic
determination) were metered into the reactor and the
~ mixture was 6tirred at 70C for 15 minute6, the ethylene
i pre6~ure being kept at 6 bar by ~ub~equent metering in.
In parallel, 500 mg of diphenylmethylene-(9-fluorenyl)-
- --` 2 ~
- 16 -
cyclopentadienyl-zirconium dichloride were dissolved in
500 cm3 of a toluene solution of methylaluminoxane (for
the concentration and quality, see above) and were
preactivated by being left to ~tand for 15 minutes. The
solution of the complex (catalyst solution) was then
metered into the reactor ~in order to reduce the molecu-
lar weight, 1350 ml of hydrogen were fed to the reaction
vessel via a sluice immediately after the catalyst had
been metered in). Polymerization wa~ then carried out at
70C for 140 minutes, while stirring (750 revol tion~/
minute), the ethylene pressure being kept at 6 bar by
subsequent metering in. The contente of the reactor were
then drained rapidly into a stirred ve~sel into which
200 cm3 of isopropanol (as a stopper) had been initially
introduced. The mixture was precipitated in acetone and
~tirred for 10 minutes and the suspended polymeric solid
was then filtered off. A mixture of two parts of 3N ~Cl
and one part of ethanol was then added to the polymer
which had been filtered off and the mixture was ~tirred
for 2 hours. The polymer was then filtered off again,
washed neutral with water and dried at 80C and 0.2 bar
for 15 hours.
An amount of 4400 g of product wa~ obtained.
The physical parameters of the cycloolefin copolymers
COC A1, COC A2, COC A3 and COC A4 are to be found in
Table 1.
- 17 -
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- 18 -
Preparation of functionalized cycloolefin copolymer
COC A4 material
1. Preparation of COC A4 adhesion promoter grafted with
maleic anhydride.
a.) Maleic anhydride COC A4-P1
A clean and dry 2 1 three-necked flask with a preci~ion
glass stirrer and condenser wa~ filled with argon.
50 g (89.3 g/l) of COC A4 and 500 ml of toluene
(absolute) were introduced and dissolved completely in
countercurrent with the argon. 20.72 g (377.5 mmol/l) of
maleic anhydride (MA, 99% pure) were then added and
di~solved in countercurrent with the inert gas, before
4.94 g (32.64 mmol/l) of dicumyl peroxide, dissolved in
60 ml of toluene (absolute) were added, likewise in
countercurrent with the ar~on. The reaction solution was
introduced into an oil bath, preheated at 110C, and
stirred vigorou~ly with a precision glass ~tirrer.
After a reaction time of 5 hours, the polymer solution
wa~ diluted with 250 ml of toluene and precipitated in
4 1 of acetone. For working up, i.e. purification of the
poly~er f thi~ was precipitated in acetone three time~,
45.3 g of MA-grafted cycloolefin copolymer A4(A4-P1~
being obtained after drying at 130C (72 hours/oil pump
vacuum).
FT-IR tcm~1]: 1865 88/1790 8$ (C=O, anhydride)
b.) Maleic anhydride COC A4-P2
A clean and dry 2 1 three-necked ~lask with a precision
glass stirrer and condeneer was filled with argon.
50 g (108.4 g~l) of COC A4 and 400 ml of toluene
(absolute) were introduced and dissolved completely in
countercurrent with the argon. 20.0 g (422.1 mmol/l) of
maleic anhydride (MA, 99~ pure) were then added and
-- 19 --
dissolved in countercurrent with the inert gas, before
7.0 g (38.06 mmoltl) of dilauroyl peroxide dissolved in
65 ml of toluene (ab~olute) were added, likewi~e in
countercurrent with the argon. The reaction eolution wa~
introduced into an oil bath, preheated at 80C, and
stirred vigorously with a precision gla~s stirrer.
After a reaction time of 5 hours, the polymer ~olution
was diluted with 250 ml of toluene and precipitated in
4 1 of acetone. Working up as for COC A4-Pl.
Yield: 48.7 g
c.) Maleic anhydride A4-P3
A4-P3 was prepared analogously to A4-P2, the mixture
being shown in Table 2.
d.) Maleic anhydride A4-P4
A4-P4 was prepared analogously to A4-Pl, the mixture
being shown in Table 2.
Table 2
,
Sample Mass AbsoluteMaleic Pe~dde YiPl~
toluenea~rid~
[ml][g] (mmol/l)Iype lg]
i- i ~ ~1
A4-P3 50 550 13 .5 d;15~llr~l 1.69 46 . 8
(90.9) (250.3) p2x~dde (7.72~
A4-P450 460 9.8 d~myl 0.27 47.5
(108.7) ( 210 .1 ) p~ ( 2 .17 ) !
The physical parameters of the functionalized cycloolefin
copolymers COC A4-Pl, A4-P2, A4-P3 and A4-P4 can be found in
~able 3.
- 20 -
~able 3
Sample Content of MA <Mw> <~n> <Mw>
COC t% by weight~ tml/g] 1 o-4 1 o_4 : .
[g/mol] tg/mol] <Mn>
A4-P1 3.70 83.8 7.93 1.69 4.7 : -~
A4-P2 1.58 85.7 14.70 4.18 3.5 -~
A4-P3 0.81 89.2 15.75 5.05 3.1
A4-P4 0.19 91.6 18.85 3.95 4.8 . :
Maleic anhydride content determined by titration
VN: Viscosity number determined in accordance with DIN
53728
GPC: <Mw>, <Mn>;150-C ALC Millipore Waters Chromatograph
Column ~et: 4 Shodex column~ AT-80 M/S
Solvent: o-dichlorobenzene at 135C
Flow rate: 0.5 ml/minute, concentration
0.1 g/dl
RI detector, calibration: polyethylene
(714 PE) ~
' ~:
2. Preparation of COC A4 adhesion promoter grafted with :--- -:
methacrylic acid, triethoxyvinylsilane and glycidyl
methacrylate
~,
a.) Methacrylic acid A4-P5 ~:
~ ~ '
A clean and dry 500 ml two-necked fla~ with a magnetic
stirrer and conden~er is filled with argon. :: :
20 g (108.4 g/l) of COC A4 and 140 ml of toluene (abso-
lute) were introduced and di~solved completely in
countercurrent with the argon. 7.02 g (442.0 mmol/l) of
methacrylic acid (distilled) were then added and dis-
solved in countercurrent with the inert ga~, before 2.8 g
(38.06 mmol/l of dilauroyl peroxide, di~olved in 44.5 ml
of toluene, were likewise added in countercurrent with
- 211~
- 21 -
the argon.
The reaction ~olution was introduced into an oil bath
preheated at 80C and stirred vigorously. After a reac-
tion time of 5 hours, the polymer solution was diluted
with 100 ml of toluene and precipitated in 2 l of
acetone. For working up, i.e. purification of the poly-
mer, thi~ was precipitated in acetone three times, 17.8 g
of cycloolefin copolymer A4(A4-P5) grafted with
methacrylic acid being obtained after drying at 1309C
(72 hours/oil pump vacuum).
FT-IR tcm~']: additional band~
1705 a~, 1805 ns (C=O bands)
Methacrylic acid content: titration 0.24% by weight
b.) Triethoxyvinylsilane A4-P6
A4-P6 was prepared analogously to A4-P5, the mixture
being shown in Table 4.
FT-IR ~cm~1]: additional band~
806 B (Si--(CE~) ), 1080 El (Si--O--)
Triethoxyvinylsilane content: elemental analysis for
oxygen 6.98% by weight.
c.) Glycidyl methacrylate A4-P7
A4-P7 was prepared analogously to A4-P5, the mixture
being ehown in Table 4.
FT-IR [cm~']: additional bands
1650 s, 1730 as (C~O bands)
Glycidyl methacrylate: elemental analy~i~ for oxygen
> 0.3% by weight.
2 ~
- 22 -
Table 4
. Sample Weight Ab~. Monomer ¦ Dilauroyl Yield
~g] toluene _peroxide tg]
(g/l) [ml~ Type (mol/l) [g] (mmol/l)
, _ ~
A4-P6 20 184.5 triethoxy 15.52 2.80 (38.06) 14.9
(108.4) vinyl3ilane (442.0)
A4-P7 20 184.5 glycidyl- 11.54 2.40 (32.60) 16.1
(108.4) meth- (440.0) ::
acrylate
, ~ ' ~:
The physical parameters of the functionalized cycloolefin
copolymers COC A4-P5, A4-P6 and A4-P7 can be found in
Table 5.
Table 5
Sample VN <~w>~Mh> <Mw> -;
coc tml/g] 10-' 10-~
[g/mol] tg/mol~ <Mn>
~ .
A4-P5 _ 12.654.06 3.1 : : :
A4-P6 109.5 18.30 4.10 4.5
A4-P7 15.604.06 3.8
V~: Visco~ity num ~er determined in accordance with DIN
, 53728 `:-.
GPC: <Mw>, <Mn>;150-C ALC Millipore Water~ Chromatograph
Column ~et: 4 Shodex column~ AT-80 N/S
Solvent: o-dichlorobenzene at 135C
Flow rate: 0.5 ml/minute, concentration
0.1 g/dl
RI detector, calibration: polyethylene ~-~
(714 PE)
` ~ 2~l0~1~
- 23 -
The gla~s fiber GF1 employed is magnesium alumosilicate
glass, alkali metal content < 0.5%.
The guideline values of the glas~ composition are:
Weiaht content in %- S-qlass
SiO2 64
Al203 26
MqO 10
Density (g /cm3 ) 2.49
~ Weight content below 0.5% not recorded.
The glass fiber GF2 employed is alumo-borosilicate gla88,
alkali metal content < 1%.
The guideline value~ of the glass composition are:
Weiaht content in %~ F-alass
Si~2 53 - 55
Al2~3 14 - 15
CaO
MgO 20 - 24
B203 6 - 9
K20
Na20 < 1
_____ ______
s~ecific density ( q/cm3) 2.61
t Weight contents below 0.6% not recorded.
Characteristics of the glas~ fibers GFl and GF2 employed~
! 25 The glass fiber GF1 employed is an ~Owens-Corning S-2
I gla~s fiber (Owen~-Corning Fibergla~ Deutschland GmbH
I (Wiesbaden)), which ha~ been desized and cut (GFla~
¦ GFlb).
¦ The filament characteristics are:
!, ,~ ~ , ~ ' ,
2 ~
- 24 ~
Value Unit
.
Fiber diameter 9 ~m
5 Thread length GFla 6.5 mm
Thre~d length GFlb 180 ~m
Lo~s on ignition 0.23 t 0.08 %
¦Absorption c moisture0.05 max.
,
The glass fiber GF2 employed is a ~Vitrofil CP 756
(Vitrofil S.p.A., Milan), which ha~ been desized.
The filament characteristic~ are~
:
t-- _ l
Value Unit
_
Fiber diameter 13 ~m
Thread length 4.5 mm
Loss on ignition 0.80 t 0.10 % ~-
Absorption of moistureO.08 max. %
20 , _
The gla~s fibers were freed from all the organic sub-
~tances (desized) by heat treatment (550C) for 3 hour3.
The glass fiber~ desized in this way were used in the
light transparency experiments.
The refractive indices of the gla~8 fibers employed can
be found in Table 6:
2 1 1 U ~ 1 1
- 25 -
Table 6
_
Glass fiber nD20
,
GF1 1.5234 (~ 0.0003)
GF2 1.5599
.
To determine the mechanical propertie~ of the cycloolefin
polymer composite~ ~ th additional adhesion promoter,
functionalized cycloolefin polymers or, for comparison,
a polypropylene grafted with maleic anhydride
[0Hostaprime HC 5 (product number HOAA 155) specification
> 4% by weight of maleic anhydride; commercially obtain-
able from Hoech~t AG, Frankfurt am Main] were employed.
Example A
A helium-neon laser (Spectra-Phy~ics model 155A-SL;
wavelength 632.8 nm; 0.5 mV) and a ground glass di~k
with a photosensor were in~talled on an optical bench.
The photosensor had a photosensitive area of 5.3 x -~
5.0 mm. The ground glass disk wa~ made of glas~ 1.7 mm
thick and had a milk glass coating 0.6 m~ thick. The
experLmental design is illu~trated in Figure 1.
.,..-.
Preparation of the cycloolefin copolymer compo~ite~
12.5 g of COC A1 (A2, A3) were dissolved in 450 ml of
toluene and 4.17 g of glas~ fiber GFla were added, as
homogeneou~ as pos~ible a dispersion being ensured.
Thereafter, the composite was precipitated in 4 l of
acetone and dried at 80C in a vacuum drying cabinet. A
sheet (60 x 60 x 1 mm) was pressed at 220C /2.5 t and ~ -
the transparency to light was mea~ured with the apparatu~
according to Figure 1.
~ :~
In a ~econd series, 12.5 g of COC Al (A2, A3) were
processed with 4.17 g of glas~ fiber GR2 analogously to :
. ~
h .1 L O ~
- 26 -
the GFla compositeR and the pre~sed sheets ~60 x 60 x
1 mm) were investigated for their transparency to light.
The transparencies to light measured as a function of the
lateral position of the photosen30r are ~hown in Figure~
2, 3 and 4. The transparency to light is calculated from
the quotient of intensity maximum with ~ample/intensity
maximum without sample.
A transparency to light ~direct tran~mission) of more
than 40% resulted at a refractive index difference of
cycloolefin copolymer to gla~ fiber of less than 0.015.
Example B
The cycloole~in copolymer A4 and in some caees the
functionalized cycloolefin copolymer adhesion promoter~
and the glas~ fiber GFlb were first dried (130C,
24 hour , oil pump vacuum) and kneaded in a measuring
kneader (~aake (Karlsruhe), 0Rheocord System 40/
Rheomix 600) under an inert gas at 240C and 40
revolution~ per minute for 15 minutes. The resulting
cycloolefin polymer composites were pre~sed
(260C/150 bar) to ~heet~ (60 x 60 x 1 mm) and the
transparencie~ to light were mea~ured in the apparatus
according to Figure 1.
Compo~ite~ with non-de~ized glass fiber all have tran -
parencies to light of le~s than 40% (at the inten~ity
25 maximum), while those with desized glass fiber and with
additionally functionalized cycloolefin copolymer
adhesion promoter have transparencies to light of greater
than 40%.
The composite with the adhesion promoter ~ostaprime HC 5
30 (polypropylene grafted with maleic anhydxide) as expected
? showed the lowest transparency to light (less than 10%)
because of the large difference in refractive indices.
~ ~ I Q ~
,, ~
- 27 -
The refractive indices and the contents of polar m~nomeri3
in the functionalized cycloolefin copolymerQ can be found
in Table 7.
Table 7
Functionalized n 23
cycloolefin copolymer Refractive index
(adhesion promoter)
, _
- Maleic anhydride
A4-P1 3.70% by wt . 1.5367 (1.5370)
A4-P2 1. 58~ by wt. 1. 5310 ( l . S370) ~ -
A4-P3 0.81% by wt. 1.5311 (1.5370)
A4-P4 0.19% by wt. 1.5310 (1.5370)
~' ~
15 - Methacrylic acid
A4-P5 0.24% by wt. 1.5370 (1.5370)
_ Triethoxyvinylsilane
A4-P6 6.98% by wt. 1.5360 (1.5370)
: -.
¦- Glycidyl methacrylate -
~ A4-P7 ~ 0.30% by wt. 1.5339 (1.5370)
,
'~Hostaprime HC 5 (for comparison) 1.5022 - -
(4.27% by weight of maleic
i anhydride) , ,~
~-
' Refractive index determined with a Zeifi~Abbé refracto-
meter type 64165
The refractive index of non-functionalized cycloolefin -~
copolymer ~tarting material (1.5370) i~ given in paren~
the~es for compari~on.
The pressed ~heet~ were ~ubjected to a tensile stre~s-
elongation experiment (~ensile 6tre~s-elongation tester
from Instron (type: 0In~tron 4302)), the following
', -- 2~:~a~ll
- 28 -
mechanical data resulting for the cycloolefin copolymer
composites (mean values of 10 measurements) (Table 8~. :
Table 8
Cycloolefin plas~ fiber Adhesion promoter Yleld
copolymer GFlb tphr] stress
[% by weight] I[% by wt.] [HPa]
100 _ _ 58.0
_ 48.1
25A4-P3 (maleic
anhydride)
1.58 # 69.5
25A4-P6 (triethoxy-
15 i I ~ vlnyl il n ) +
for comparison:
25-~Hostaprime HC 5
l 1 0.30 # 41.3 ,
t Gla~ fiber with size applied by the manufacturer
# In the composite: same maleic anhydride content
+ Wetted with water before the drying proces3
phr Percent by weight, based on the total weight of the
blend
' ~
,.
