CA2110611A1

CA2110611A1 - Glass fiber-reinforced cycloolefin polymer material and processes for its preparation

Info

Publication number: CA2110611A1
Application number: CA002110611A
Authority: CA
Inventors: Ulrich Epple; Michael-Joachim Brekner
Original assignee: Individual
Current assignee: Hoechst AG
Priority date: 1992-12-04
Filing date: 1993-12-03
Publication date: 1994-06-05
Also published as: AU5212593A; KR940014597A; NO934409L; EP0601456A1; NO934409D0; JPH06256604A; ZA939066B; DE4240784A1

Abstract

Abstract Glass fiber-reinforced cycloolefin polymer material and processes for its preparation.

A glass fiber-reinforced cycloolefin polymer material comprises 1 to 99% by weight of at least one cycloolefin polymer, in particular a norbornene/ethylene copolymer, and 99 to 1% by weight of glass fiber. The absolute difference in refractive index (the refractive index of the glass of the glass fiber minus the refractive index of the cycloolefin polymer) is not more 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 materials have good mechanical properties and a high transparency to light. The glass fibers employed prefer-ably comprise no size.

Description

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~\

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.
' :~

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~

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~
, 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 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.

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~

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 ~

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 ~

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.

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 .

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 ~

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.

i~
~.~ ~ j ~ , o~ ~ ~ ~
:
.
~1 ~ ~r o o~ ~ ~ ' V X ~, ~ ~ .,1 _ ~ -~X~ ~
.. - U~XI`O ~
o ~ U~ D 1` O ~ ~ ~
c u~ ~ o 1~
~ I ~H U~ ~ C
. , ~
u .c ~ ~ 2C ~ a) Cl. U~ OC,) Rl _l Ei ~ o o 1~ S ~ D ~ D
O~ dOt~
8 ~ ~, C a~
E~l ~ 1` co ct~ a~ ~ o N ~ O
_. ~ t~ ~ o r~ ~ o O 3 /~
~1 ~ ~ I x .a .1 ~
C: 1 ~ ~`0 h ~ h ~ ,q ~:: ~ ~a ,4 o o o R dP ~ r~ h ~ ~ U :
~ td 91 tJ~ Ul rl ~ O
o ~ R a~ .~ o ~. o U ~
~ R ~ 8 ~ -- ~ ~ ~ u O ~ o U ~ Q
,~ 'a ~ I ~ 3 ~
~ ~ ~ ~ ~ Rd .rl ul O O _i H
O _I ~ U~ r~
O ~ R t~ ~ . ~ ~ .,1 ~
R i~ R It~ U ~i H 1.1 Ul rl 11~ V
~ U ~1 ~-1 _l 0-~ ~ ~
_~ ~ ~ r ~ U ~ ~ol ~
.a o ~ .. O'' ~ :
E~ g ~

- -- 2l.la~l~

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 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.

~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

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~

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 ~

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~

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 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 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 ~

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 ~
,, ~

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 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 ' ~

,.

Claims

1. A glass fiber-reinforced cycloolefin polymer material comprising 1 to 99% by weight of at least one cycloolefin polymer and 99 to 1% by weight of glass fiber, wherein the absolute difference in refractive index (the refractive index of the glass of the glass fiber minus the refractive index of the cycloolefin polymer) is not more 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.

2. A material as claimed in claim 1, wherein the cyclo-olefin polymer is a norbornenetethylene copolymer.

3. A material as claimed in claim 2, wherein the norbornene/ethylene copolymer comprises 30 to 75 mol% of ethylene and 25 to 70 mol% of norbornene.

4. A material as claimed in claim 1, 2 or 3, which comprises 10 to 90% by weight of at least one cyclo-olefin polymer and 90 to 10% by weight of glass fiber.

5. A shaped article made of the material as claimed in claim 1 or 2.

6. A process for the preparation of a glass fiber-reinforced cycloolefin polymer material in which glass fibers and a cycloolefin polymer are mixed in a mixing ratio of glass fiber/cycloolefin polymer of 1:99 to 99:1, which comprises freeing commercially available glass fibers, the glass of which has a refractive index in the range from 1.510 to 1.560, from the size and then mixing them with a cyclo-olefin polymer.

7. The process as claimed in claim 6, wherein a solu-tion of the cycloolefin polymer in an organic solvent is mixed with the glass fibers and the solvent is removed by evaporation, or the mixture is poured into an excess of a second solvent which is miscible with the first solvent but in which the cycloolefin polymer is insoluble, so that the cyclo-olefin polymer is precipitated on the glass fibers.

8. The process as claimed in claim 6, wherein a melt of the cycloolefin polymer is mixed with the glass fiber.

9. The process as claimed in claim 6, wherein the glass fiber is heated at 500°C in an oxygen-containing atmosphere to remove the size.

10. The process as claimed in claim 6, wherein the glass fiber freed from the size is coated with an organic adhesion promoter.

11. The process as claimed in claim 10, wherein the glass fiber is treated with a melt of the organic adhesion promoter or a solution of the organic adhesion promoter.

12. The process as claimed in claim 10, wherein the organic adhesion promoter is a functionalized cyclo-olefin polymer.

13. The process as claimed in claim 12, wherein the functionalized cycloolefin polymer was prepared by grafting a aycloolefin polymer with a polar monomer.

14. The process as claimed in claim 13, wherein the polar monomer used for the grafting is chosen from the group comprising .alpha.,.beta.-unsaturated carboxylic acids, .alpha.,.beta.-unsaturated carboxylic acid derivatives, organic silicon compounds having an olefinically unsaturated and hydrolyzable group, olefinically unsaturated compounds having hydroxyl groups and olefinically unsaturated epoxy monomers.

15. The process as claimed in claim 10, wherein the adhesion promoter is chosen from the group compris-ing vinylsilanes, methacrylosilanes, aminosilanes, epoxysilanes and methacrylate/chromium chloride complexes.

16. A material as claimed in claim 1, wherein the glass fiber employed comprises magnesium alumo-silicate having a refractive index of 1.510 - 1.560.

17. A material as claimed in claim 16, wherein the glass fiber comprises 60 to 68% by weight of SiO2, 23 to 29% by weight of Al2O3 and 8 to 12% by weight of MgO.

18. A material as claimed in claim 17, wherein the glass fiber employed comprises 64 % by weight of SiO2, 26%
by weight of Al2O3 and 10% by weight of MgO and has a refractive index of 1.5234.

19. A material as claimed in claim 16, wherein the cycloolefin polymer is a cycloolefin/.alpha.-olefin copolymer.

20. A material as claimed in claim 19, wherein the cycloolefin polymer is a norbornene/ethylene copolymer.

21. An adhesion promoter prepared by grafting a cyclo-olefin polymer with a polar monomer, wherein the functionalized cycloolefin polymer has a content of grafted polar monomer of 0.01 to 50% by weight.

22. The use of a cycloolefin polymer which has been grafted with a polar monomer such that the grafting product comprises 0.01 to 50% by weight of grafted polar monomer, as an adhesion promoter for glass fiber/cycloolefin polymer material.