CA2077411A1 - Polymer blends of cycloolefin polymers and polyacetals - Google Patents

Abstract

Abstract of the disclosure HOE 91/F 275K

Polymer blends of cycloolefin polymers and polyacetals Polymer blends are prepared from cycloolefin polymers or cycloolefin copolymers and polyacetals by kneading or extruding these together. The cycloolefin polymer prefer-ably comprises structural units which are derived from a monomer of the formula I

Description

HOECHST A~TIENG~SELLSC~T HOE 91/F 275K Dr. SP/pe Description Polymer blends of cycloolefin polymer~ and polyacetal~

Cycloolefin polymers are a class of polymexs which have an outstanding property profile and are distinguished, inter alia, by hydrolytic stability, low absorption of water, resistance to weathering, high heat distor~ion temperature and transparency.

Polyacetals have also been employed for a long time as multi-purpose materials, above all in the engineering sector. Because of their good mechanical properties, such as high rigidity, hardness and strength, as well as the possibility of producing moldings and shaped articles within narrow tolerance limits and the good resistance to many chemicals, they are often suitable as a substitute for metals. In addition to good electrical and dielectric properties, they exhibit favorable slip and wear proper-ties. Because of the good resistance of polyacetals to many organic solvents, they show only ~light æwelling and a slight drop in their mechanical properties on contact with solvents. In practice, the resistance to automobile gasoline (including that containing methanol), mineral oil and heating oil is of particular importance, this not being guaranteed with cycloolefin polymers.

Both polymer classes, cycloolefin pol~mers and poly-acetals, are proces ed as thermoplastics. Exposure to high temperatures over an exkended period leads to decom-position products and vxidation products in the case of the cycloolefin polymers. Shorter intervals of exposure to heat during extrusion and injection molding, i.e.
higher output rates by improving the flow propsrties, would therefore be of advantage. Furthermore, for some uses of polyacetals, for example as matrix materials for 2 - 2 ~ 7 ~ 41 1 composites, their mechanical properties, for example the modulus of elas~ici~y or the shear modulus/ are in need of Lmprovement. In this conneckion, absorption of water by polyacetals is problematic, since the dimensional stability is not guaranteed at a high ambient humidity.
A lower absorption of water would therefore be of advant-age.

It is now known that important properties of polymers, such as those mentioned above, can be changed by blending polymers with other polymers. However, the possibility of reliably predicting the properties of a polymer blend from the properties of the individual components is as yet a long way off.

The object of the present invention is therefore to provide polymer blends of cycloolefin polymexs and polyacetals having increased flow properties, improved mechanical properties and a lower absorption of water.

The invention relates to polymer blends comprising at least two components (A) and (B), wherein (A) is at least one cycloolefin polymer and (B) is at lea~t one polyacetal, ths blends containing (A) in amounts of 1 to 99% by weight and (B) in amounts of 9g to 1% by weight, and the relative amounts of (A) and (B) making up 100% by weight with respect to the total blend.

Cycloolefin polymers ~A) which are suitable for the blends according to the invention comprise structural units which are derived from at least one monom~r of the formulae I to VI or VII
"~L ~ Rl X~
¦¦ R3-C-R- I (I) 3ic 1 ~ ~;
~Y / - R~

2 ~

C:~ ~ ~2 ~

li R3- C R~ I C'~2 .iC l / C~: /

.~:C--I--C~
¦¦ R3-C-R4 ¦ R5~ 6 ¦ (~II), HC ¦ ~ eH ¦~ ~H ~

F~ ¦ ~
!1 2~ R~ ¦ -R6 ¦ R7-C-R~ ¦ ( IV), -~ / ¦ ~ C'.i ~ -- CH ~ Rl li ?~; ~ p~ l l (V), r:~ ! c c.~ R2 ~6 C.-'-- --'~u~ ¦ ~ ~Rl C r~ ¦ ¦ 7~ R~ ~ ~2 ~6 _.. -- _..
`\ / f~) ( C~2 ) n in which Rl RZ R3 R4, R5, R6, R7 and Ra are identical or different and are a hydrogen atom or a Cl--C8-alkyl radical, it being possible for the 5am~ radicals to have different 2 ~ 7 ~

meanings, in the various formulae and n is an integer from 2 to 10.

The cycloolefin pol~ners (A) can comprise, in addition to the structural units which are derived from at least one monomer of the formulae I to VII, other structural units which are derived from at least one acyclic l-ol~fin of the formula VIII
P~9 RlC
(VIII) in which R9, Rl, Rl1 and Rl2 are identical or different and are a hydrogen atom or a Cl-C8-alkyl radical.

Preferred comonomers are ethylene or propylene. Copoly-mers of polycyclic olefins of the formula I or III and the acyclic olefins of the formula VIII are employed in particular. Particularly preferred cycloolefins are norbornene and tetracyclododecene, which can be substi-tuted by Cl-C6-alkyl, ethylene/norbornene copolymers being of particular Lmportance. Of the monocyclic olefins of the formula VII, cyclopentene, which can be substituted, is preferred. Polycyclic olefins, monocyclic olefins and open-chain olefins are also to be understood as meaning mixtures of two or more olefins of the particular type.
This means that cycloolefin homo- and copolymers, such as bi-, ter- and multipolymers, can be employed.

It is known that cycloolefins can be polymeri~ed by means of various catalysts. The polymerization proceeds via ring opening ~US-A-3 557 072, US-A-4 178 424) or with opening of the double bond (EP-A-156464, EP-A-283164, E-A-2gl208, EP-A-291970, DE-A-3922546), depending on the catalys~.

2 ~ ?;7 r~

The cycloolefin polymerizations which proceed with open-ing of the double bond can be catalyzed using more recent catalyst systems (DE-A-39 22 54~, EP-A-02 03 799) and also with a conventional Ziegler catalyst sys~em (DD-A-222317, DD-A-239409).

The cycloolefin homo- and copolymers which comprise structural units deri~ed from monomers of the formulae I
to VI or VII are preferably prepared with the aid of a homogeneously soluble catalyst comprising a metal~ocene, the central atom of which is a metal from the group comprising titanium, zirconium, hafnium, vanadium, niobium and tantalum and which forms a sandwich structure with two mono- or polynuclear ligands bridged to one another, and an aluminoxane. The bridged metallocenes are prepared in accordance with a known reaction scheme (cf.
J. Organomet. Chem. 28B (1985) 63-67 and EP-A 320762).
The aluminoxane ! which functions as a cocatalyst, is obtainable ~y various methods tcf. S. Pasynkiewicz, Polyhedron 9 (19~0) 429 and EP-A-302424). The structure and also th~ polymerization of these cycloolefins are described in detail in DE-A-3 922 546 and in the earlier-priority bu~ no~ a~ yet published patent applications D~ A-40 36 ~64, DE-~-41 06 107 and DE-A-41 07 682. These are cycloolefin copolymers which differ in their chemical uniformity and their polydispersity.

Cycloolefin polymers having a viscosity number greater than 20 cm3/g (measured in decalin at 135C in a concen tration of 0.1 gtlOO ml) and a glass transition tempera ture (Tg) of between 100 and 200C are preferably employed.

The polymer blends can also comprise cycloolefin poly~ers which have been polymerized with ring opening in the pre-sence of, for example, cataly~ts containing tungsten, molybdenuml rhodium or rhenium. The cycloolefin polymers obtained by this process have double bonds which can be ~7~

removed by hydrogenation (US-A-3 557 072 and US-A-4 178 424).

The cycloolefin polymers employed for the polymer blends according to the invention can also be modified by grafting with a~ least one monomer chosen from the group comprising (a) ~,~-unsaturated carboxylic acids and their derivatives, (b) styrenes, (c) organic silicone compon-ents containing an unsaturated, preferably olefinic, bond and a hydrolyzable group and (d) unsaturated e~oxy compo-nents. The resulting modified cycloolefin polymers haveexcellent properties similar to those of the unmodified cycloolefin polymers, and can be employed for the alloys according to the invention either by themselves or together with the unmodified cycloolefin polymers. The modified cycloolefin polymers moreover specifically have a good adhesion to metals and synthetic polymers. The good compatibility with other pol~mers is to be singled out. It is even possible to prepare, by reactions carried out in solution or in melts, graft copolymers of cyclo-olefin polymers with polyacetals, which can act as compatibilizers.

Polyacetals (B) which are suit~ble for the polymer blends according to the invention comprise oxymethylene struc-tural units [-CHz-O-], preferably in an amount of 80-100%
by weight, preferably 90-100% by weight. Such polyacetals (B) are described, for example, in EP-A-0 156 285.
Preferred polyacetals (B) are linear, unbranched homo-and copolymers of formaldehyde or it cyclic oligomers, such as trioxane or tetroxane, copolymers being under-6tood as meaning both bi- and multipolymers.

Suitable comonomers are a) cyclic ether6 having 3, 4 or 5, preferably 3, ring members, b) cyclic acetals other than tri- or tetroxane and having 5 to 11, preferably 5, 6, 7 or 8, ring members snd c) linear polyacetalsl in each case in amounts of 0.1 to 20% by weight, preferably ~77~

O.5 to 10% by weight. Particularly preferred copolymers contain 99.5 to 95% by weight of oxymethylene structural uni~s and 0.5 to 5% by weight of structural unit~ deri~ed from one of the abovementioned comonomersO

Homo- and copolymer~ of formaldehyde or its cyclic oligomers are to be understood as those polymers who e terminal groups have been converted into ~table groups after the polymerization.

The polyacetals (B) are prepared by ionic polymerization.
The homopolymer of polyoxymethylene can be prepared by anionic suspension polymerization of formaldehyde.
Esterification with ace~ic anhydride at about 140C is then carried out for stabilization of ~he unstable hemi-acetal end groups. For the preparation of copolymers, trioxane is first prepared from an approximately 60%
strength aqueous formalin solution in the presence of sulfuric acid. The monomeric ~rioxane, which has ~een carefully purified by distillation, can then be polymer-ized cationically in bulk in the presence of a few percent by weight of ethylene oxide or 1,3-dioxepane Ibutanediol formal) at about 70C. ~he unstable hemi-acetal end groups of the resulting eopol~mer are finally converted into stable alcoholic end group~. An overview of the essential process steps and evaluation of the numerous patents and publications is given in Process Economic Program (G.~ Haddeland, Report No. 69, Acetal Resins, Stanford Research Institute, Menlo Park, California 1971).

The inherent viscosity of the polyacetals (B) is in general 0.3 to 2.0 dl/g, preferably 0.5 to 1.5 dl/g (measured in butyrolactone, stabilized with 2~ by weight of diphenylamine, at 140C in a concentration of 0.5 g/
100 ml) and the melt volume indices (MVI), determined in accordance with DIN 53~35-B, are in general 0.02 to 70 cm3/10 minute~, measured at 190C under a load of 2~77~

2.16 kg. The cry6talline melting point (Tm) is in general 140-180C, preferably 150-170C.

The polyacetals employed for the blends according to the invention can al~o be modified by grafting with sui~able functional compounds comprising diisocyanates, as coup-ling agents, and corresponding functional masking agents.
The term "functional masking agents" is understood as meaning monomeric or polymeric compounds having one or two functional groups per chain, or e~ample hydroxyl, carboxyl or amino groups, which can undergo addition reactions with diisocyanates. Suitable functional masking agents are, for example, mono- and difunctional poly-al~ylene oxides, polyesters, polyamides, polyolefins, polydienes and polysiloxanes. Polyacetals modified by grafting are described in EP-A-0 397 ~93~

These block or graft copol~mers can be employed as engineering resins per se or as compatibilizers with other polymers.

The blends according to the invention preerably comprise 5 to 95% by weight, particularly preferably 10 to 90% by weight, of the cycloolefin polymers (A), and conver6ely 95 to 5~ by weight or 90 to 10% by weight of the poly-acetals ~B), the relative amounts of components A and B
making up 100% by weight with respect to the total blend.
The blends according to the invention can contain one or more cycloolefin polymers and one or more polyacetals, as well as modified cycloolefin polym2rs, modified poly-acetals and/or block and/or graft copolymers of these.

Blends which comprise modified cycloolefin polymers, in addition to unmodified cycloolefin polymers and poly-acetals, exhibit, for example, a finer dispersion, ie.
smaller particle sizes. Extremely fine dispersion occurs in blends in which the total content of cycloolefin polymers i9 modified. The~e blend~ al~o have ~urprisingly 2~7~
g good mechanical pxopertie~.

The blend~ according to the invention are prepared and processed by standard methods known for thermopla6tics, for example by kneading, extrusion or injection molding.

The blends according ~o the invention can comprise additives, for example heat stabilizer~, W ~tabilizers, antistatics, flameproofing agenc~, plasticizers, slip agents and lubricants~ pigments, dyestuffs, optical brighteners, processing auxiliarie~ and inoryanic and organic fillers, ie. in particular also reinorcing additives, such as glass fibers, carbon fiber6 or high modulus fibers.

The blends can advantageously be employed as a matrix material for composite material6. Moreover, they are suitable for the production of shaped articles, for example in the form of sheets, fibers, films and tubes, by the injection molding or extru~ion process.

The following polymers were prepared by standard methodss Cycloolefin copolymer Al [COC A1]

A) Preparation of diphenylmethylene-(9-fluorenyl)-cyclo-pentadienyl-2irconium dichloride (metallocene ~) All the following working operations were carrled out in an inert ga~ atmosphere using absolute solvent~ (Schlenk technique).

12.3 cm3 (30.7 mmol) of a 2.5 molar solution of n-butyl-lithium in hexane were slowly added to a solution of 5.1 g (30.7 mmol) of fluorene in 60 cm3 of te~rahydrofuran at room temperature. After 40 minutes, 7.07 g (30.7 mmol) of diphenylfulvene were added to the orange solution, and the mixture wa~ ~tirred overnightO 60 cm3 of water were ~0~7~

added to the d~rk red solution, whereupon the solution became yellow in color, and the solution was extracted by shaking with die~hyl ether. The ether phase was dried over MgS04 and concentrated, and the residue was left to crystallize at -3~C. 5.1 g (42% by weight) of 1,1-cyclopentadienyl-(9-fluorenyl)-diphenylmethane were obtained as a beige powder.

2.0 g (5.0 mmol) of the compound were dissolved in 20 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 stirred at room temperature for 15 minutes, the solvent was removed under reduced pressure, and the xed residue was dried under an oil pump vacuum and washed several tLme~ with hexane. A~ter the red powder had been dried under an oil pump vacuum, it was added to a sus~ension of 1.16 9 (5.00 ~mol) of ZrCl~in 20 ml CH~12 at -78C. After the mixture had been warmed up slowly, it was stirred at room temperature for a further 2 hours.
The pink-colored 6uspension was filtered over a G3 frit.
The pink residue was washed with 20 cm3 of CH2Cl2, dried under an oil pump vacuum and extracted with 120 cm3 of toluene. After the solvent had been removed under reduced pressure 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 crystalline powder.

The orange-red filtrate of the reaction mixture was concentrated and the residue was left to crys~allize at -35~C. A further 0.45 g of the complex cry~tallizes from CH2~l2 -Total yield 1.0 g (36% by weight). Correct elemental analyses. The mass spectrum showed M~ = 556. lH-NNR
spectrum (100 MHz, CDCl3) 6.90-8.25 (m, 16, Flu-H, Ph-H), 6.40 (m, 2, Ph-H), 6.37 (t, 2, Cp-H), 5.80 (~t 2, Cp-H).

2~7~11 11 ~
B) Preparation of COC A1 (ethylene/norbornene copolymer) A clean and dry 75 dm3 polymerization reactor with a stirrer was flushed with nitrogen and then with ethylene, and 30 1 of an 85% strength by weight toluene ~olution of norbornene (Nb) were introduced. The reactor was ~hen brought to a temperature of 70C, while stirring, and ethylene wa~ passed in until ~ pressure of 3.5 bar was established.

580 cm3 of a toluene solution of methylaluminoxane (10.1%
by weight of methylaluminoxane having a molecular weight of 1300 g~mol according to cryoscopic determination) were then metered into th~ reactor, and the mixture was stirred at 70C for 15 minutes, the ethylene pressure being kept at 3.5 bar by topping up. In parallel with lS this, 500 mg of metallocene L were dissolved in 500 cm3 of a toluene solution of methylaluminoxane (for the concentration and quality, see above) and were preacti-vated by being left to stand for 15 minutes. The solution of the complex (catalyst solution) was then metered into the reactor. Hydrogen may be used to regulate the mole-cular weight. Polymerization was then carried out at 70C
for 140 minutes, while stirring t750 revolutions/minute~, the pressure in the reactor being kept at 3.5 bar by topping up with ethylene. The contents of the reactor were then drained rapidly into a stirred ve~sel, into which 200 cm3 of isopropanol (as a stopper) had been introduced. The mixture was precipitated in acetone and stirred for 10 minutes, and the suspended polymeric solid was filtered off.

A mixture of two parts of 3 N hydrochloric acid and one part of ethanol was then added to the polymer which had been filtered off, and the mixture was stirred for 2 hours. The polymer was filtered off again, washed neutral with water and dried at 80C under 0O2 bar for 15 hours.
An amount of product of 4500 g was obtained.

7, o ri 7 ~

Cycloolefin copolymer~ A2 [COC A2] and A3 [COC A3]

A) Preparation of rac-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride (metallocene A) All the following working operations were carried out in an inert gas atmosphere usin~ ab~olute ~olvents (Schlenk techni~ue).

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 (0.23 mol) of indene (industrial grade, 91%), which had been filtered over aluminum o~ide, in 200 cm3 of diethyl ether, while cooling with ice. The mixture was stirred at room temperature or a further 15 minuteæ, and the orange-colored solution was passed via a cannula into a solution of 13.0 g (0.10 mol) of dimethyldichlorosilane (99~ pure) in 30 cm3 of dieth~l ether in the course of 2 hours. The orange-colored suspension was stirred over-night, and extracted three times by shaking with 100-150 cm3 of water. The yellow organic phase was dried twice over sodium sulfate and evaporated in a rotary evapora-tor. The orange oil which remained was kept at 40C under an oil pump vacuum for 4 to 5 hours and freed from excess indene, a white precipitate being obtained. A total of 20.4 g ~71% by weight) of the compound (CH3)2Si(Ind)2 could be isolated as a white to beige powder by addition of 40 cm3 of methanol and crystallization at -35C.
Melting point 79-81C (2 diastereomers).

15.5 cm3 ( 3~.7 mmol~ of a 2.5 molar solution of butyl-lithium in hexane were slowly added to a solution of 5.6 g (19.4 mmol) of (CH3)2Si(Ind)2 in 40 cm3 of tetra-hydrofuran at room temperature. One hour after the addition had ended, the deep red solution was added dropwise to a suspension of 7.3 g (19.4 mmol) of ZrCl4-2-tetrahydrofuran in 60 cm3 of tetrahydrofuran in the course of 4 6 hours. After the mixture had been ~tirred for 2 ~

2 hours, the orange precipitate was filtered off with suction over a glass frit and recrystallized from OEI2Cl2.
1.0 g (11% by weight) of rac-(CH3) 2Si ( Ind~ 2ZrC12 was obtained in the form of orange cry~tals, which gradually decompose above 200C. Correct elemen~al analyses. The mass spec~rum showed ~ = 448. lH-NMR spectrum (CDCl3):
7.04-7.60 (m, 8, aromatic H~, 6.90 (dd, 2, ~-Ind H), 6.08 (d, 2, ~-Ind H), 1.12 (s, 6, SiCH3).

B) Preparation of COC A2 and COC A3 (e~hylene/norbornene copolymers) COC A2 and COC A3 were prepared analogou~ly to COC Al, some of the conditions summarized in Table 1 being changed.

~07~

. ~ _" _ .
o o o o o ~D
o _. ~ ~

.0 o o N E3 ~ OD t`~
_l .
,, ~ ,, o o a) ~ ~ ~ U~ O
u~ _ h g ~ ~ ~ o ~r .
. _ _ _ S~

U~ ~1 N
Ul t~l ~`I Il~ _~
~ ~ _ _l C~l ~: .. _ 1~:
~ ~ U~ O
O _i Q
~1 _ . e _I
h 0 ~ la o o ~
~ ,~ t- ~
- -- -_~
O _~~1 t~) N~
U'~
h _ 1::
I ~ ~
_l O ~1 ~ ~
~ ~3 ~ _1 ~0~ _ E~

2~77~ ~

The physical parameters of the three cycloolefin copoly-mers which comprise structural units of the formula Fl and F2 CH2 - CH~ ~ ~ CH CH ~
HC CH

Fl ~2 can be seen from Table 2.

~able 2 . . _ Cyclo- Incorporation ~N <Mw> <Mn> <~w> Tg 0 ole:Ein of copoly- Ethyl- Nor- 10 5 1o~4 . ~ . . [ oC]
mer ene bornene [mol %] [mol %] [cm3/g] ~g/mol] [g/mol] ~Mn>
_ A1 49 51 166 2.25 10.2 2.2 178 _ _ A2 55 45 91 0.92 4.5 2.0 143 A3 59 41 83 0.82 3.5 2.3 114 determined ~y 13C nuclear magnetic resonance spectro-scopy VN: ~iscosity number determined in accordance with DIN

~Mw>, ~Mn>: gel permeation chromatography: 150-C ~LC
Millipore Waters Chromatograph Column set: 4 Shodex columns AT-80 M/S
Solvent: o-dichlorobenzene at 135C

2~7~

Flow rate: 0.5 ml/minute, concentration 0.1 g/dl RI detector, calibra~ion: polyethylene (901 PE) 0 Heating up and cooling down rate: 20/minute Other charac~eristics of the cycloolefin copolymers A1, A2 and A3 can be seen from the examples.

Cycloolefin graft copolymers ~3-Pl CCOC ~3 P1] and A3-P2 [COC A3-P2+3 and A3-P3 [COC A3-P3]

1. Preparation of COC A3 (A3-P1 and A3-P2+), grsfted with maleic anhydride 20 g (108.1 g/l) of COC A3 were dissolved in 150 ml of toluene (thiophene-free, absolute) in a clean and dry 500 ml two-necked flask connected to an inert gas ~upply (consisting of an oil pump for generating a high vacuum, and an argon feed for aeration). When the copolymer had dissolved completely, 8 g (438.6 mmol/l) of maleic anhydride (MA, 99% pure) were added and dissolved, before 2 g (2701 mmol/l) of dilauroyl peroxide (dissolved in 35 ml of toluene (thiophene-free, absolute~) were added.
The contents of the flask were dega~sed completely at -196C (four freezi~g/degassing cycles). Argon was then applied and the reac~ion solution wa~ introduced into an oil bath preheated at a controlled temperature of 80C.

Free radical qr~fting of MA onto COC A3 wa~ ended after ~ hours by precipitation in 2 l of acetone. For working up, ie. purification of the polymer, thi~ was reprecipi-tated in acetone four times r 16.3 g of MA~grafted cyclo-olefin polymer A3 (A3-Pl~ being obtained after drying at 130C (72 hours/oil pump vacuum).

A3-P2~ was prepared analogously, 2.8 g (38.0 mmol/l) of dilauroyl peroxide being employed. Yield: 15.9 g ~7~

FT-IR [cm 1] 5 1865 ss / 1790 ss ~C=O, anhydride) VN [ cm3 / g ]: in ac c ordance with D IN 5 3 7 2 8 A3-Pl : 85 . 7; A3~P2+ : 84 . 2 2. Prepara~ion of COC A3 (A3-P3), grafted with maleic anhydride A clean and dry 2 1 two-necked ~lask was ~illed with argon. 70 g (90.0 g/l) of COC A3, dissolved in 700 ml of toluene (absolute, were introduced in an argon counter-current. 19.0 g (250.3 mmol/l) of maleic anhydride (M~, 99% pure) were then added in countercurrent to the inert gas and dissolved, before 6.68 g (21.8 mmol/l) of dilauroyl p~roxide (dissolved in 70 ml of ~oluene (abso-lute)) were likewise added in a coun~ercurrent of argon.
~he reaction solution was introduced into an oil bath, preheated at a controlled temperature of 80~C, and stirred vigorously with a precision glass stirrer. Free radical grafting of N~ onto COC A3 was ended after 5 hours by precipitation in 5 1 of acetoneO For working up, ie. purification of the polymer, the latter was repre-cipitated four times in acetone, 66 mg of MA-grafted cycloolefin copolymer A3 (A3-P3) being obtained after drying at 130C (72 hours/oil pump vacuum).

FT-IR tcm~1]: 1865 ss / 1790 ss tC-O~ anhydride) VN [cm3/g]: in accordance with DIN 5372 A3-P3 : 86.7 The absolute contentE of MA in the graft copolymer were determined by means of potentiometric titration.

2~77~

Table 3 Sample~A contentAvarage n~mber of MA/
t4 by weight]polymer chain A3 A3-Pl 1.07 4 A3-P2+ 1.95 7 A3-P3 0.64 Polyacetal B having structural unit~ of the formula F3 and F4 H H H
---C ~ --C ---C --O--in which the content of oxymethylene struc~ural units is 98% by w~ight and the content of oxyethylene structural units is 2% by w~ight.

Such a polyacetal B is commercially avail~ble. It is marketed, for example, as Hostaform C 2521 (~ = registered trademark) by Hoechst AG, Frankfurt am Main.

The polymers described above wsre first dried (130~C, 24 hours, vacuum) and then kneaded or extruded under a protective gas (Ar~ in a measuring kneader (HAAKE
(Karlsruhe), Rheocord Sy tem 40/Rheomix 600) or measuring extruder (HAAKE (Karlsruhe), Rheocord System 90/Rheomex TW 100). The resulting ground or granulated blends were dried (130JC, 24 hours, vacuum~ and then pres~ed (vacuum pre~s: Polystat 200 S, Schwabenthan (Berlin)) to give ~7~ ~

sheets (120 x 1 mm). The ground or granulated blends were introduced into the press, which had been preheated to 230C (blends with A1 and A2) or 190~C (blends with A3 and graft copolymers A3-Pl* and A3-P2~ or blends with graft copolymer A3--P3), a vacuum was applied and the blends were melted in the course of 10 minutes. The material was pressed together under a pressure of 150 bar at the above temperature, this pressure was maintained for 5 minutes and the shee~s were then cooled to room temperature in ~he course of 10 minu~es. The resulting melt-pressed sheets were investigated in respect of their physical properties.

The following apparatus was used for this:

A differential scanning calorLmeter (DSC-7) from Perkin-Elmer (~berlingen) for measurement of, for example, glass stages, melting points and heat~ of fusion.

A torsion pendulum machine from Brabender (Duisbur~) for measurement of the shear modulus, damping and linear expansion.

A tensile stress-elongation test machine (type: Instron 4302) from Instron (Offenbach).

A melt index tester MPS-D from Goettfert (Buchen) for measurement of flow properties in accordance with DIN
53735-MVI-B (plunger loadttemperature variable; barrel:
internal diamter 9.55 (+ O.01) mm, length at least 115 mm, discharge nozzle ~.095 (+ 0.005) mm, melting tLme 5 or 10 minutes).

The water content was determined in accordance with AS~M
D 4019-81.

~7~

Example 1.

The cycloolefin copolymer (Al~ and the polyacetal ~B) were kneaded together, after intensive drying, in various weight ratios under an argon a~mosphere ~y means of -the measuring kneader. The follow.ing tables show~ the thermal properties determined on the blends.

COC Al POM B Cooling 2nd Heating t% by weight] [~ by weight] ~m AHm Tm ~Hm Tg POM B POM B COC
[C] [J/g] [C] [J/g] [~C
_ .
100 __ __ __ __ 17g 1~143.~ 16837.7 179 _ 14088.7 168 75-9 *
_ 141125.5 167114.7 *
100 ~42168.~ 168171.2 - ;

Heating up and cooling down rate: 20/minute not measurable (sensitivity of the apparatus too low) Example 2:

The cycloolefin copolymer (Al) and the polyacetal (B) were mixed together, after intensive drying, in various weight ratios under an argon atmosphere by means of the measuring kneader, and the mixture was then ground. Aftex intensive drying, the ground products w~re used to measure the flow properties.

207r~

_ COC Al POM B MVI
[% by weight~ [% by weight~21.6 kg/230C
~cm3/10 minutes]
Melting tLme 5 minutes _ _ ._ 100 0 23.5 110.6 305.7 391.1 100 74.4 Example 3:

The cycloolefin copolymer (A2) and the polyacetal (B) were extruded together, after intensive drying, in various weight ratios under an argon a~mosphere by means of the twin-screw extruder, and the extrudate was granu-lated. After intensive drying, the granules were used to measure the flow properties.

2 ~

[% by weight] [% by weight]21.6 kg/220C
[ cm3 / 10 minutes]
Nelting tLme 5 minutes 100 0 1 14.2 198.9 445.4 _ not measurable (~ 450) 0 100 62.0 Example 4:

The cycloolefin copolymer (A2) and the polyacetal ~B) were extruded together, after intensiv~ drying, in various weight ra~ios under an argon atmosphere by means of the twin-screw extruder, and the extrudate was granu-lated. After intensive drying, the granule~ were th~n pressed to give pressed sheets. The following table shows the mechanical data determined on the blends in the tensile stress/elongation e~perLment.

~7~ ~ ~

COC A2 POM B Modulus of Yield stress elasticity [~ by weight] ~% by weight~ [GPa] [MPa~
_ 100 ~ 3.2 6~

3.0 59 _ 10 50 50 2.8 58 _ 2.9 58 ~_ 0 100 2.8 58 Example 5:

The cycloolefin copolymer (A3) and the polyacetal (B) were kneaded together, after intensive drying, in ~arious weight ratios under an argon atmosphere by means of the measuring kneader. The following table shows the thermal properties determined on the blend~.

~7~ ~ ~

CoC A3 POM s Cooling 2nd Heating [% by weight] [~ by weight] Tm ~Hm Tm ~Hm Tg POM s POM B COC
5lC~ [~/g~ [oc] ~J/g] [C]
_ 10~ 0 __ __ __ - 114 _ 142 ~ 168 x114 .
141 x 167 x *
r__ _ 142 x 168 x *

0 100 142 168.4 168 171.2 ~

Heating up and cooling down rate: 20C/minute x Separation not possible (melting point, gla~s stage) * not measurable tsensitivity of the apparatus too low~

Example 6:

The cycloolefin copolymer (A3) and the polyacetal ~B) were kneaded together, after intensive drying, in various weight ratios under an argon atmosphere by means of the measuring kneader. The ground products were dried inten-sively and, after storage at 23C and 85~ relativehumidity for at least 240 hours, the absorption of ~ater was determined.

2 ~ ',J~
~ 25 -COC A3 POM B Water content ~ by weight] [% by weight] [% by weight]

100 0 0.01 _ ~.10 0.16 0.29 ~ . _ 0 100 0.41 _ Example 7:

The cycloolefin copolymer (A3) and the polyacetal (B) were kneaded together, after in~ensive ~rying, in various weight ratios under an argon atmosphere by means of the measuring kneader. The ground products were dried inten-20 sively and pressed to give pressed heets. The followingtable shows the mechanical data of the blends during the torsion pendulum test.

2 0 7 7 ~ ~ 1 __ _ _____ o al I~ co ~r i I ~ ~D ~r o l l ~ ,~ o~
_l l l _ _~ U~ U~ o~ o C~
~1 c:~ ~ r~ ~ ~
_l U~ ~ ~ ~
F _I u~ ~ ~D D CD
_l a~
~1 _J ~` U~ U~ d' r~
~o ~ _J ~ O~ ~ I`
a~ c~ cO O ~r I~
0~ U:~ D Ln ~~) o o o ~7 _~ CO U~
.~ _. o ,~ ~ s~ ~ t~
o~ r~ ~o ~9 In o ~ h x ~ ~ _l r~
D ~t Q~ ~ In O~
~n cn r` I~ r ~ ~, o ~ ~ cn ~
tn ~ o n ~ ~ co ~D
~r ~n a~ ~o c~ c~
o O co sn _~
o a~ ~ ~ o o s~
o ~ U~
,~ u~ o~ c~ ~r a:~
U~ I ~ o~ o ~ ~

~1 C~ ;- ~D I
~D O O ~ ~ O~
l _l ~ _ _l ~1 ~D U~ ~D r~
er ~ ~ O ~ 0 _~ U~ D ~ r~ S_ _ I ~_ _l ~_ ~_ .~
~d~ O O ~ O O
o~n ~ rr~ U~ r~ o dP
_. _ _ ,_ _ _ .
f¢ ~ ~ o o o 0~ o r u~ ~
d~
_ _ _ _ _ . __ .

2~

Example 8:

The cycloolefin copolymer (A3) and the polyacetal (B) were kneaded together, after intensive drying, in various weight ratios under an argon atmosphere by means of the measuring kneader. ~fter intensive drying, the ground products were u~ed to measure the flow properti2s.
_ _ _ CoC A3 POM s MVI
[% by w~ight] [~ by weight]21.6 kg/190C
0 [ cm3/ 10 minutes]
Melting time 5 minutes 100 0 15.3 . . ~
15 70 30 89.4 _ _ _ _ _ 50159.0 _ _ 70189.3 0 10038.2 Example 9O

The cycloolefin copolymer (A3), the graft copolymer A3-Pa and A3-P2+ and the polyacetal ~B) were kneaded together, after intensive drying, in various weight ratios under an argon atmosphere by means of the mea~uring kneader. The following table shows the thermal properti~s determined on the blends.

~7~

COC A3 COC POM B Cooling 2nd ~eating [% by A3-P1 /2+ [% by Tm AHm Tm ~Hm l'g weight] [~ by weight] weight] POM B POM B COC
[C~ [J/g] [C] [J/y] [C]
_. _ _ _ I
100 0 0 ____ ~ 114 _ _ 10 ~ 1 0 30 142x 167 x 114 56 14~ 30 142~ 167 x 113 . ._ 18 12+ 70 143x 167 x V
_ 15 30 0 70 142x 167 ~ V
: _ 100 142 168.4 16B 171.2 -- .

Heating up and cooling down rate: 20C/minute x Separation not possible (melting point, glass stage) * not measurable (sensitivity of the apparatus too low~

Example 10:

The cycloolefin copolymer ~A3), the graft copol~mer (A3-Pl and A3-Ps+) (compatibilizer) and the polyacetal (B) were kneadad together, after intensive d~ying, in various weight ratios under an ar~on atmosphere by means of the measuring Xneader. After intensive drying, the ground products were used to measure the flow properties.

~7~

COC A3 CO(: POM B MVI
[% by A3-Pl~/-P2~ [% by 21.6 kg/190C
weight [% by weight3 weight] [cm3/10 minutes]
Melting time:
. . 5 / 10 minutes 100 O O 15.3 / 15.5 O 30 89.4 / 96.7 56 1~ 30 64.3 / 71~2 18 12+ 70 171.~ / 181.6 0 70 189.3 / 188.9 _ ~
O ~ 100 38.2 / 37.2 Example 11 t The cycloolefin copolymer (A3), the graft copolymer (A3-Pl and A3-P2+) and the polyacetal tB~ were kneaded together, after intensive drying, in various weight ratios under an argon atmosphere by means of the measur-ing kneader. After intensive drying, the ground productswere pressed to give pressed sheets. ~he following table shows the mechanical data determined on the blends with/without the compatibilizer (A3-P1 and A3-P2+) in the torsion pendulum test.

~7~

. _ ___ ~ ,~--~

o CO ,1 o~
C~ l l l U~ ~ ~
,~ U~ U~ ~ er O O
~ O _~ cr) r~ ~ ,~
_ ~ U~ ~ ~ ~ ~ ~
_~ u~ ~ n u~ ~D OD
, o _l a~ co r~ ~r ,~
~ ~ I~ U~ In d' ~P ~
~o u~ cn r~
~:: ~ ~a 0 a~ o~ ~ r 1:~ CO ~ ~D U~ U~ ~r O ~ ~ O~ ~ ~D
O co r~ r~ ~D ~ U~
D ~ _~ I~ D r~ U~
_l C~ O t` U~ G~
O o ~ r~ CD r I~ u7 _, ~ o o ~ ~n ~ o. ~D
~ ~ ~ U~ ~ 1` O 0~ U:~
c~ X ~ :n o~ c~ ~ o~ c~
~ ~ O rr~ O ~ ~ ~_ ~
co o~ ~ _l o ~
o~ ao o~ c~ o ~o _~ ~
o ~o U~ U~ ~ oo o a~ ~ u~ ~ 1` ,~ ~ c~
~ E~ I o ~n o 5~ _1 ~/ _1 ~ _1 ~ _I ~ r~ ~ o~ o t~
a~ ~ o~ ~ ~ ~ u~ ~r I o o ~ ~ U~
U~ ~I ~ _~ _l _l ~1 ~1 ~D OD ~D ~D I`
~r d' ~ ~ ~1 ~ OD
~D ~ r~ r~ r~
l _I_ _I _l .
t~
. m ~
O
O ~ ~ ~ I~ r~ o dP _ __ _ C ~ rl U ~ ~ +
0 ~ O O ~ N O O

'¢ I¢
. _ _ __ _ __ ~ rl ~ ~ O O ~D CO O O
.~il O 1- In _~
~
_. _ _ _ __ 2 ~
~ 31 -Example 12:

The cycloolefin copolymer ~A3), the graft copolymer tA3-Pl~ and A3-P2+) and the polyacetal (B) were kneaded together, after intensive drying, in various weight ratios under an argon atmosphere by means of the measur-ing kneader. After intensive drying, the ground products were pressed to give pressed ~heets. The following table show~ the mechanical data determined on the blends with/
without a compatibilizer (A3-Pl~ and A3-P2+) in the tensile stress~elongation experiment.

COC A3 COC POM B Modulus of Yield Elongation [% by A3-P1~ [% by ela~ticity stress at break weight3 A3[~P2y weightJ [GPa] [GPa~ [%]
_ _ weight]

100 0 0 3.~ 60 4.9 _ 30 2~9 ~ 5.0 56 14~ 30 3.0 57 3.6 18 12+ 70 ~.g 60 10.~
~ _ _ 0 70 2.8 56 5.4 0 0 100 2.8 58 35.0 Example 13:

The graft copolymer A3-P3 and the polyacetal (B) were kneaded together, after intensive drying, in variou~
weight ratios under an argon atmosphere by means of the measuring kneader. The following table show~ the ~hermal ~7~

properties deter~ined on the blends.
_. _ COC Cooling 2nd Heating A3~P3 POM B Tm QHm Tm aHm Tg 5 [~ by weight~ [% by weight] POM B POM B COC
[~C] [~/g] [C] ~J/g] [C]
. , __ ~ .__~
100 0 __ __ -- -- 113 _ 83/114~ x 162 33 112 143 x 168 x V

0 100 14~ 168.4 168 171.2 -15 ______________ _ _ _ _ Heating up and cooling do~ rate: 20C/minute x Separation not possible (melting point, glass stage) V not measurable (sensitivity of the apparatus ~oo low) + several minLma (2nd main minimum) Example 14:

The graft copolymer A3-P3 and the polyacetal (B) were kneaded together, after intensive drying, in various weight ratios under an argon atmosphere by means of the measuring kneader. After intensive drying, the ground 2S products were used to measure the flow properties.

2~7~ ~

COC POM B MVI
A3-P3 [~ by weight]21.6 kg/190C
[% by weight] rcm /10 minutes3 S Melting time 5 / 10 minutes 100 0 14.6 14.8 7.8 7.9 _ 9.3 7.0 _ _ 0 100 38.~ 37.2 _ _ _ _ _ ~ foam-like mat~rial Example 15:

The cycloolefin copol~mer A3 or the graft copolymer A3-P3 and the polyacetal (B) were kneaded together, after intensive drying, in various weight ratios under an argon atmosphere by means of the measuring kneader. After intensive drying, the ground product~ were pressed to give pres6ed sheet6. The following table shows the mechanical data determined on the blends in the torsion pendulum test.

2~77~

_____ ~ ~D
_l l l l l ,~
o t~ ,1 N ~ l l l ~D ~ ~
r~l l l l l ~1 ~1 ~`I
_~ U~ ~I 111 ~O tr~ C~ O
~1 O I~ _l ~1 t~l ~1 ~1 _ ~ u~ r~ ~ ~ ~ ~ r~
_~ Ul U~ ~ ~ ~ ~D ~0 ~ O _l U~ U~ ~ ~ d' r-_l ~ I` ~ U~ ~D ~:P
::1 U~ ~ CO ~ O 0 ~ 1_ ~ CO N O~ Cl:~ ~ OD ~ r~
~1 CO 1` D ~` U~ U~
O O U~ ~ ~ ~ 00 ~D
o~ ~ ~ r~
O c~ c~7 1~ r- ~D U~ U~
ta ~ ~D ~r r~ _l _~ ~ ~ u~
5~ ~1 D C~ Lrl U~ U~ a~
O O o~ co ,~ ao r~ r~
-- E3 o o ~D ~ O- ~ cn u~
r u~ O ~ ~1 O~ ~0 ~D
x S~ cn ~ a~ ~ co OD ~
O~) ~D O O CO i~ t`~
CO d'O~ O~ ~ ~ C~l Z h a~cn c~ o~ o o o ,1 O o U~ o~ ,1 C~ o~
o a) ~ ~ ~ O~ _, a~ ~ o~
~ I O O ~ _~ N ~ ~1 ~ _l ~ rv~ ~` ~ ~ O t-(U ~D tD 1~ ~` ~1 ~0 U') ~r I O ~ O ~ U~ U~ O~
U~ _1 _~ ~1 ~1 ~1 _~ ~1 _l _l t~ ~D ~ Ct~ U~ r~
d~ ~ ~ ~ ~ ~ C~
_l In ~ ~ CO r-l _l ~ ~1 .. . _ _ . _ _ __ .
.C
a:l Q) ~ 3 o o ~ ~ ~ o o P1 ,~ ~1 d~
.. _ . _ , _ _ .~
V ~ ~
O ~ ~ o o l o ~ l o ~¢~ ,1 -y~- _ ,__ _ _ _ _ _ 8 3 o o ~ L o o ~077~1 ~

Example 16:

The graft copolymer A3-P3 and the polyacekal (B) were Xneaded together, after intensive drying, iIl various weight ratios under an argon atmosphere by means of the measuring kneader. After intens iV8 drying, the ground products were pressed to give pressed sheets. The fol-lowing table shows the mechanical data determined on the blends in the tensile str~ss/elongation experiment.

10COC POM B Elasticity Yield Elongation A3 P3 [% by weight] modulus stress a~ break [~ by weight] [GPa] [MPa] [%]
_ _ _ _ . _ _ 100 0 3,1 61 5.0 _ .
2.9 5~ 7.9 2.9 58 17.8 _ 0 100 2.8 58 35.0

Claims (15)

1. A polymer blend comprising at least two components (A) and (B), wherein (A) is at least one cycloolefin polymer and (B) is at least one polyacetal, the blend containing (A) in amounts of 1 to 99% by weight and (B) in amounts of 99 to 1% by weight, and the relative amounts of (A) and (B) making up 100%
by weight with respect to the total blend.

2. A polymer blend as claimed in claim 1, wherein the cycloolefin polymer (A) comprises structural units which are derived from at least one monomer of the formulae I to VI or VII

(I), (II), (IV), (V), (VI), (VII) in which R1 R2 R3 R4, R5, R6, R7 and R8 are identi-cal or different and are a hydrogen atom or a C1-C8-alkyl radical, it being possible for the same radicals to have different meanings in the various formulae, and n is an integer from 2 to 10.

3. A polymer blend as claimed in claim 2, wherein the cycloolefin polymer (A) is modified by grafting with at least one monomer chosen from the group compris-ing (a) .alpha.,.beta.-unsaturated carboxylic acids and their derivatives, (b) styrenes, (c) organic silicone components containing an unsaturated bond and a hydrolyzable group, and (d) unsaturated epoxy components.

4. A polymer blend as claimed in one of claims 2 or 3, wherein the cycloolefin copolymer (A) comprises, in addition to the structural units which are derived from at least one monomer of the formulae I to VII, other structural units which are derived from at least one acyclic 1-olefin 0f the formula VIII

(VIII) in which R9, R10, R11 and R12 are identical or differ-ent and are a hydrogen atom or a C1-C8-alkyl radical.

5. A polymer blend as claimed in claim 4, wherein the cycloolefin polymer (A) is a copolymer of polycyclic olefins of the formula I or III and at least one acyclic olefin of the formula VIII.

6. A polymer blend as claimed in claim 5, wherein the cycloolefin polymer (A) is a copolymer of norbornene and ethylene.

7. A polymer blend as claimed in claim 1, wherein the polyacetal (B) comprises oxymethylene structural units [-CH2-O-] in an amount of 80 - 100% by weight.

8. A polymer blend as claimed in claim 7, wherein the polyacetal (B) comprises, in addition to the oxy-methylene structural units, structural units derived from comonomers selected from the group comprising a) cyclic ethers having 3, 4 or 5 ring members, b) cyclic acetals other than tri- or tetroxane and having 5 to 11 ring members and c) linear poly-acetals.

9. A polymer blend as claimed in claim 8, wherein the amount of oxymethylene structural units is 99.5 to 95% by weight and the amount of structural units derived from the comonomers mentioned is 0 . 5 to 5%
by weight, with the proviso that the various amounts make up 100% by weight.

10. A polymer blend as claimed in claim 9, wherein the polyacetal (B) comprises oxymethylene structural units and oxyethylene structural units.

11. A polymer blend as claimed in claim 1, wherein the cycloolefin polymer (A) is a copolymer having structural units of the formulae and and the polyacetal (B) is a copolymer having structural units of the formulae and

12. A polymer blend as claimed in one of claims 1 or 11, which additionally comprises a cycloolefin polymer (A) modified by grafting with at least one monomer chosen from the group comprising (a) .alpha.,.beta.-unsaturated carboxylic acids and their derivatives, (b) sty-renes, (c) organic silicone components containing an unsaturated bond and a hydrolyzable group, and (d) unsaturated epoxy components.

13. A polymer blend as claimed in claim 11, which additionally comprises a cycloolefin copolymer (A) modified by grafting with maleic anhydride.

14. A polymer blend as claimed in claim 1, wherein the cycloolefin polymer (A) is a cycloolefin copolymer (A) modified by grafting with maleic anhydride, and the polyacetal (B) is a copolymer having structural units of the formula and

15. Use of a polymer blend as claimed in claim 1 as a matrix material for composite materials or for the production of shaped articles.