DE2062735A1 - Process for the production of poly oxymethylene mixtures - Google Patents

Description

DR.-ING. BY KRESSLER DR.-ING. SCHÖNWALD DR.-ING. TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISLER DIPL-CHEM. CAROLA KELLER DR.-ING. KLÖPSCH

COLOGNE 1, DElCHMANNHAUS

Cologne, December 18, 1970 Ke / Ax

Celanese Corporation,

522 Fifth Avenue, New York, N.Y. 10036 (U.S.A.).

Process for the production of polyoxymethylene mixtures

The invention relates to mixtures based on modified polyoxymethylenes which are an oxymethylene polymer and a Polymer with terminal isocyanate groups (-NCO) or isothiocyanate groups (NCS) included. The invention is particularly directed to modified polyoxymethylene blends, which is an oxymethylene polymer which contains a terminal or pendent group, which according to the Zerewitinoff method contains certain active or acidic hydrogen, and a polymer with terminal isocyanate or Isothioc.yangruppen contain, the two polymers by the reaction between the active or acidic hydrogen and the isocyanate or isothlocyane groups are coupled.

Oxymethylene polymers which contain recurring units of the formula -CH ₂ O- have been known for many years. You can by polymerization of a compound providing oxymethylene units, for example anhydrous formaldehyde or. Trioxane, which is a cyclic trimer of formaldehyde,

Oxymethylene polymers with improved thermal stability are iztSrniGti produced by incorporating structures that are resistant to thermal separation into the polymer chains

imported- ·; or added to the ends of the polymer chains, the polymers can be scattered Oxy & Iky! hsIlvsD with neighboring C-Atorsun, preferably Ox ^ QlzikjitQn , as described in the 138A patent specification>vOf> 32. Copölyras ·? '^ Of this type 3iit!

at least one chain containing oxymethylene units (- {(usually at least 85 mol ~ $) in the units of the formula -OR- are interspersed, in which R is a divalent radical which. at least two-interconnected and ir. the chain contains carbon atoms between the two valences, any substituent in the radical R being inert is.

As interspersed monomer units occur in single Zin ™ units in question, which are derived from lactones, carbonates, cyclic acid anhydrides or ethylenically unsaturated compounds such as styrene, divinyl ether, vinyl acetate, Vinylaethylketon or acrolein _o The polymers may be end-blocked, for example by acylation or etherification after Polymerization or during the polymerization by using selected. Chain transmitter _{or similar}

As used herein the term "Oxyraethylenpolymere ^113" homopolymers and copolymers containing at least 60 ^ recurring oxymethylene units contain _s and further comprising Oxymsthylenpolymere substituted "in which the inert Substitueaten -sinä _g ö.h" not participate in undesired Nehesareaktionen ₀

Young . The scope of the Irfiadöög also includes osymethylempolymers with twisted chains. (SeB _5. Serpolyraere tana Polyasre with rmhr als 3 Qom & nowsTQn) _Q Polymers öiessr Jksi -can iiarch Gi © ri © atloii ψοώ. ϊγίίοχδβ with glass? sociable crowd

. ι 'c ι ^e £ ^rt

't »ct ^f ι oQ ^ iir-a ^ f ^ - _: " 323 ζΐ ^ Ω polymers

BATH

1) cyclic ethers with at least two cyclic ether rings, in particular Vei'bindungen, the a) at least two epoxy rings, b) at least two dioxacyclo rings or c) contain at least one epoxy ring and at least one dioxacycloring, and 2) compounds containing at least contain two oxo groups, e.g. dialdehydes and diketones with preferably 3 to 20 carbon atoms.

For certain purposes, a modification of the Molecule of oxymethylene polymers desired to make polymers with modified pestibility properties, flow properties, modified solubility, crystallinity, thermal stability, etc. This modification of the molecule is particularly desirable when a change in properties by mixing two polymers for example as a result of incompatibility of the polymers is impossible.

It has been found that such modified oxymethylene polymers by reaction of a terminal isocyanate groups (-NCO-) or isothiocyanate groups (-NCS -) - containing polymer with a polymer that contains a terminal or pendent G group, which according to the Zerewitinoff method contains certain active or acidic hydrogen.

The modified oxymethylene polymers can also be prepared by the coupling reaction of polymeric segments, at least one of which is an oxymethylene polymer, in the presence of a bifunctional coupling agent, preferably a coupling agent containing at least one isoyane group or isothiocyanate group. In such a reaction system, an isocyan or isothiocyan prepolymer can be formed in situ if reaction with one polymer segment is preferred over another, or the coupling can take place by virtually simultaneous reactions of the coupling agent with the polymeric material «

109828/1714

_ 4 -

The copolymers can thus by coupling the polymer chains in the reaction with a bifunctional compound, which contains at least one isocyanate group or isothiocyanate group, 'or by reacting one separately prepared prepolymers, the terminal isocyan groups or contains isothiocyanate groups, with another polymer chain containing an active or acidic hydrogen Terminal or pendent group contains formed will.

The presence of acidic water s only of-f can after the Zerewitinoff's method by taking advantage of the reaction of such

"Compounds that contain active or acidic hydrogen, with Grignard compounds, where RH is released according to RMgX. For example, if a Compound containing acidic hydrogen atoms with methyl magnesium iodine id is implemented, methane is released. i.e. the test is positive. The amount of methane released can be collected and measured and the number of active hydrogen atoms per mole can be determined if the molecular weight is known. A further description of the Zerewitinoff method including modifications of the method for various applications can be found in "Grignard Reactions of Non-Metallic Substances" by MoS.Kharasch and

fc O. Reinmuth (Prentice-Hall, Inc _c , New York, 1954), pages 1166-1174.

Suitable substituents which contain active hydrogen atoms are, for example, amino groups, amido groups, hydroxyl groups, carboxyl groups, mercapto groups, thiocarbonyl groups, groups of the formula -CSNH ₂ , -SO ₂ NH ₂ and SO ₂ OH. Substituents containing active or acidic hydrogen atoms are generally polar in that they contain atoms such as oxygen or nitrogen that are more electronegative than carbon atoms'ο

T0 98 2B / 171 /,

Substituents containing active hydrogen react with the isocyanate groups or isothiocyanate groups as follows:

¹ i ²

¹ i ti 2 HX

The copolymers thus contain the structure

R,

rn

L H

X
• i - R.

Here, R stands for an oxyethylene polymer segment, X stands for

-Jx.

an oxygen or sulfur atom, R ^ for an organic radical derived from the coupling agent, preferably for a divalent aliphatic, cycloaliphatic or aromatic component including their substituted derivatives with up to about 20 carbon atoms, R for any suitable organic polymer segment and m and η for integers from 1 to 2, the sum of m + η = 2 or 3. The copolymers can of course contain one or more such block structures. This is indicated by the subscript "z" which is an integer from 1 to about 100. R and R represent the remainder of a polymer containing functional groups with active hydrogen atoms, which was formed by withdrawing the active hydrogen atoms from the above-mentioned functional groups which form the end group of said polymer segment. In the context of this description, the polymer segments R and R _x thus include the pendant or terminal group via which the polymer segment is attached to the group

of the coupling means is bound.

Worm beisr-ielaweioe the terminal group of the polymerGg

109R2R / 17U

ORIGINAL

ments is a hydroxyl group, the structure is created by reaction with a diisocyanate

(Polymer) -0-0-N-R - NGO

wherein R or R
* y

—HfPolymer) · 0

would represent.

Likewise arises in cases where the terminal group is an amino group by reaction with a diisocyanate

the structure

H H

• - (• Polymer -) - N - C - H R NCO

R or R in this case became ~ H

(• polymer) -N-

represent.

In the case of a terminal carboxyl group, the structure of the formula arises

* 9 ^H.

- (• Polymer) -G ~ 0 C n_r_nco

here R and R

.-— f polymer) -—— G —-- o + ». —I

represent.

Given the wide variety of groups, the-active Contain hydrogen atoms and the direct bond between the polymer segment and the bifunctional coupling agent

1 0 9 8 2 B / 1 7 1

form, a representation is preferred in which the polymer segments include the substituent group, however, a more limited class of block copolymers can pass through the following structure can be represented:

H -W-C-N-

-R.

-C-Vi

Here W stands for oxygen, sulfur,

0 It -C-O- or -N-

wherein Rp represents a hydrogen atom, an alkyl radical with 1 to 5 carbon atoms or a halogen atom; P stands for

P for any ge »

an oxymethylene polymer segment,
suitable organic Polyraersegmentj and all other members have the meanings given above.

Representative organic polymers which are suitable for the mixed * · polymer block are, for example, those which contain hydroxyl groups, amino groups, azido groups, carboxyl groups, mercapto groups, thiocarbonyl groups or other active hydrogen-containing substituents, for example the polyethers, for example polymers and copolymers which contain of ethylene glycol, propylene glycol, butylene glycol, pentamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decanediol, 1,2-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, methylhexanediol, 1,4-butenediol and 2,2-dimethyl 1,3-propylene glycol are derived, polystyrene glycol, polyacetals, such as _o those polyoxymethylenes which Polyätherpolyacetale, for example, the copolymers of ethylene oxide and trioxane ·, cellulose and its derivatives, eg. B, the cellulose esters, polyesters (which contain both hydroxyl groups and carboxyl groups), e.g. polyethylene terephthalate, poly (I ^ -cyclohexanedicarbinyl terephthalate), polytetramethylene sebacate, the polycarbonates, e.g.

109828/1714

Poly / 2 ", 2-propane bis (4-phenylcarbonate) 7, polyamides ₉ 2. ^. D Polysulfonamides, polycarbonamides, for example Polyhexamethylene ™ diamine adipate and the corresponding N-methoxylated polymers, polymers containing mercapto groups, for example the polythiorethylene, the polyurethanes and aggregates and copolymers of the above-mentioned compounds. Of course, all of the above-mentioned polymers may contain hydroxyl groups, amino groups, etc. as substituents at the ends of the poles; contain.

Suitable Mischpolymerblöckerf are thus, for example those which comprise a polymer backbone consisting of repeating atoms from the group oxygen, sulfur, carbon and nitrogen, including saturated and unsaturated polymers of hydrocarbons Oxakohlenwasserstoffen _s Thiokohlenwasserstoffen and Aminokohlenwasserstoffen, and to aliphatic, cycloaliphatic contain and aromatic groups bonded active V / on Hydrogen containing G _r uppen including such groups which contain heteroatoms from the group nitrogen, oxygen and sulfur (for example containing polyethylene glycol hydroxyaliphatic terminal groups; polyethylene terephthalate contains aromatic carboxyl groups and Hydroxyaralkylreste; containing polythio methylene terminal Mercaptoalkyl radicals; Polyäthylenediarain contains aminoaliphatic groups; the cellulose esters contain glucopyranose units with hydroxyl groups attached to a heterocyclic alk y! component are bonded (where the heteroatom is an oxygen atom) and hydroxyl groups which are directly bonded to the heterocyclic component; the polycarbonates contain aromatic hydroxyl groups).

In the most preferred embodiment, the oxymethylene polymer block is an oxymethylene copolymer having "at least one chain" the oxymethylene moieties

10982 8/171 / «

(-CHpO-) (usually at least 85 mol ~ $) contains, in dia up to about 15 mol- # (-OR-) units are interspersed, where R is a divalent radical containing at least two carbon atoms that are directly connected to one another and are irider Chain stand between the two valences, any substituent in the radical R being inert. Appropriate haheri these copolymers have a number average molecular weight of about 1,000 to 80,000 or more, the Inherent Viscosity between about 0.2 and 1.5 or higher lies. Depending on the type and extent of the desired modification of the properties, the low molecular weight (about 1,000 to 10,000) or the high molecular weight (30,000 to 80,000) oxymethylene copolymers are preferred.

Optimally, the polymers do not contain any chain extension more than two active hydrogen atoms, which are preferred are at the ends of the polymer chain. However, polymers are also suitable which have several active hydrogen atoms in different Contain positions on the polymer chain. For example, polymers are suitable for chain extension, in which the terminal active hydrogen atoms are more reactive than any active hydrogen atoms between the chain ends «Such polymers are particularly advantageous if a chain-extended block copolymer, that is capable of further networking is desired. Of course, increased functionality contributes to for a given molecular weight an "increase in speed." the crosslinking of the polymer "

Bifunctional compounds are expediently used as coupling agents used which contain at least one isocyanate group (-NCO) or isothiocyanate group (-NCS). Preferred organic diisocyanates,. (OCN-R-NCO), diiaothiocyanates (SCiI-R-NCS) or isocyanate thiocyanates (OCN-R-NCS), however, compounds with a higher functionality (e.g. triaocyanate and polyisocyanates) can also be used.

109828/171 / *

A preferred class of coupling agents is formed by compounds of the general formula R-4 * -NCX) _n , in which X is an oxygen or sulfur atom, η is an integer from 1 to 3 and R is an organic radical from aliphatic, cycloaliphatic and aromatic components (of the type described above) with 1 to 20 carbon atoms and their substituted derivatives, the substituents of which are inert, ie do not take part in undesired side reactions.

Suitable compounds are, for example, aromatic diisocyanates, for example 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate , 3,3'-dimethyl-4j4'-diphenylene diisocyanate (3,3-bitoluene-4,4'-diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate, methane diisocyanate, chlorophenylene-2, ^ -diisocyanate, chlorophenylene -2,4 ~ toluene diisocyanate, 3,3'-dichlorodiphenyl-4,4'-diisocyanate, 4-chloro-1,3-phenylene diisocyanate, xylene-1,4-diisocyanate, dixylylene methane-4,4'-diisocyanate, 1,5 -Naphthalene diisocyanate, 1,4-naphthalene diisocyanate and the corresponding diisothiocyanates and the isocyanate thiocyanates, alkylene _{diisocyanates, Z 0} B. 1, o-hexamethylene diisocyanate, 1,2-ethylene diisocyanate, 1,3 ~ propylene diisocyanate, 1 ^ -tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate and the corresponding diisocyanates and isocyanate thiocyanates, alkylidene diisocyanates, for example ethylidene diisocyanate and propylidene diisocyanate isocyanate and the corresponding diisothiocyanates and the isocyanate isothiocyanates, cycloaliphatic diisocyanates, for example 1,3-cyclohexylene diisocyanate, 1 ^ -cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4i4'-methylenebis (cyclohexyl isocyanate) and the corresponding diisothiocyanates and isocyanate isocyanates such as triphenyl methane triisocyanate, 1,3,5-benzene triisocyanate and the corresponding isothiocyanates and isocyanate isothiocyanates. Also any mixtures of the abovementioned compounds, for example mixtures

109828 / 17U

. The 2,4- and 2,6-isomers of toluene diolocr / onate can be found in be appropriate in certain cases.

The polymers can be used in any molar ratio to modify their Enable properties. For example, a 1: 1 block copolymer of an oxymethylene polymer and a polyglycol have desirable properties, or it It may be useful to produce an oxymethylene block copolymer, sand bound to the outer polyether element, and which requires a different molar ratio for its preparation. The amount of polymeric reactants added can be as early as the initial introduction be varied in the reaction zone, or an additional Amount of an original reactant or even another reactant can be used in the course of the reaction can be added. It is also possible to use additional catalyst and / or additional coupling agent in the course to add to the reaction »

The coupling agent can be used in different amounts (for example to bring about a further reaction or to introduce terminal isocyanate groups or isothiocyanate groups), but this reagent is preferably used in amounts between 0.5 and 3 »0 mol (calculated as isocyan or isothiocyanate groups per mole of active Hydrogen, where 1 g atom of active hydrogen is equated with 1 mol of active hydrogen). For the chain extension, amounts between about 0.8 and 1.2 moles per mole of active hydrogen of the polymer block are preferably used. An excess over the stoichiometric ratio of 1: 1 favors the chain termination of POL3 ^r - · mersegmente prior to the coupling, and at a molar ratio of · 2: 1 (ie, isocyano / active hydrogen) is in the we-'sentlichen no clutch statt.Wenn ie a terpolymer with terminal isocyanate or isothiocyanate groups is to be produced, an excess over the stoichiometric ratio of 1: 1, preferably a ratio

109828/1714

BATH ORIGINAL

of 2: 1 or a higher excess is advisable »

It has now been found that the polyoxymethylene mixtures described above can be used successfully to produce molded parts Excellent homogeneity and excellent physical properties when processed with a device is worked that exerts a high shear effect and in a certain temperature range is held. The polymeric reactants are subjected to high shear mixing subjected and can then be extruded through a suitable nozzle, granulated and put into a molding device, e.g. an injection molding machine. The sheared mixtures that take the form of granules or pellets can have, and the molded parts made from them are homogeneous and have excellent physical properties, e.g. high resistance to oil and chemical durability, abrasion resistance and a low coefficient of friction. The preferred degree of homogeneity can often be seen with the naked eye. Mixtures, those that do not have the required degree of homogeneity show a marble-like or pearlescent one Effect on the surface of the molded parts. It can be clearly seen that in the experiments described below, where processing conditions outside of the invention were used, products were obtained • that had not only relatively undesirable physical properties, but also a proportionate one poor homogeneity, recognizable by their surface properties, showed.

The mixture of the polymeric reactants can be prepared in any conventional manner, e.g. by mixing the dry ingredients, coprecipitation, Mixing on the roller mixer, mixing in the drum or separate feeding of dosed quantities of each Be-ί Part in a mixing device that has a high shear

109828/171/4

has an effect. Preferably, however, the mixture is produced by taking the correct amounts of each polymeric reactant, preferably to less than $ 0.04 of water have been dried directly to that with high shear working mixers are fed.

Any commercially available extrusion devices capable of intimately mixing different constituents, for example Banbury mixers with paddles rotating in opposite directions and twin screw presses, preferably with kneading blocks, can be used for the purposes of the invention. Single-screw extrusion presses are also suitable, for example the "Transfermix E-2 ^M " extrusion press (manufactured by Sterling Extruder Corporation), which achieves a high shear effect by using webs arranged on the inner wall of the extrusion press, which engage in the flights of the rotating screw The type of mixer with high shear effect is the two-roll mixer, in which one roll rotates faster than the second roll, which creates the high shear effect. Devices with one or more screws with different outlet nozzles for the hopper (e.g. vertical, inclined ( e.g. 45 °)), or with undercut and with any screw construction with a continuous thread and torpedo-shaped design, e.g. with constant pitch, variable cylinder depth, dosing with rapid transition, different pitch with constant cylinder depth, with constant pitch and smooth torpedo-shaped tip, To rpedoform with different pitch and continuous passageway, etc. The ratio of length to diameter can be about 10 to 60, but a range of about 20 to 50 is preferred. The screw can run at around 50 to 200 rpm. In general, around 50 to 150 rpm are used. Another and perhaps better way of describing the screw speed is to specify its tangential speed. the

10982B / 1714

Tangential speed is the distance _s that a certain point on the screw travels within one minute. The tangential speeds with which the above-mentioned high shear effect is achieved should be in the range from about 3.8 to 15.25 m / minute, preferably in the range Thus, a particular extruder with a large diameter barrel may well have a screw rotating at less than 10 rpm, but the tangential speed would likely be in the range of about ₃₉ 8 fall to 15.25 m / minute. These numbers vary natuer lent to those used various types of operating with high shear mixing devices. the melt temperatures are generally between about 121 and 232 ⁰ C j and the temperature of the nozzle or the outlet temperature of the melt is in the range from about 227 to 243 ^° C

When the organic reactant contains cyanate terminal iso-, as mentioned above, the reaction temperature in the range of about 121 to 232 ⁰ C, should preferably in the range of 149 to about 232 ⁰ C ₀ The Yerarbeitungstemperaturen are to be selected so ,, · that the temperature the melt at the nozzle or at the exit point in the range of about 227-243 ° C _S is preferably in the range of about 232-241 ⁰ C _β atmospheric pressure is desired, but in the context ", the Erfinduag be carried out at suppressing or overpressure ₉ wean is desired ein® corresponding increase or decrease of the reaction temperature, "the residence time of the Senmelze is relatively kurzο SI® is preferably about 1 minute or less (eg, · 30 to 60 seconds) ₉ jeäocfa can also with longer ^or: shorter YerweiXz © LTAA OCE Schmelz® are worked when factors such as Tief® das 2ylioders ₅ tendon revolutions, snail stiffness ₀ different training = "form the Sohneoke and the like The speed of the movement is dia R @ s in all cases

109828/1714

lead "until a high degree of homogeneity has been achieved is as explained in detail above. It should be noted that the melt after reaching this high Degree of homogeneity should be discharged from the extruder because of excessive shear on the necessary high shear effect, thermal degradation of one or more components of the reaction mixture caused. This undesirable effect can be due, in part, to the presence of chemical stabilizers discussed below should be avoided.

Of course, additional chemical compounds can be used in the high shear mixing incorporated or added to the polymer in a known manner after extrusion. As such additional chemical compounds come catalysts (e.g. tertiary amines and tin compounds, e.g. dibutyltin dilaurate and tin (Xi) octoate), stabilizers (e.g. organic phosphites such as tris (dihonyltriphenyl) phosphite, Fillers, hardeners, crosslinking agents, antioxidants, pigments, metal oxides, carbon black, lubricants, dyes, Plasticizers and the like. Further variations of the process can also be made. For example Vents can be provided during extrusion to remove volatile constituents and the like thereby obtaining a product of higher purity.

The polyoxymethylenes made according to the invention can be »processed» into a wide variety of molded parts, e.g. bearings, plates, pipes and hoses

Examples 1 to 6

In all of the experiments in Examples -1 to 6, a reaction mixture was used from 50 Gew.-Jfi one produced by the applicant Molecular weight oxymethylene copolymers of about 35,000 (trade name "Celcon M-90") and 50 wt. 5 & one terminal isocyanate groups

109828/1714

holding polyurethane ("Texin 591", manufacturer Mobäy Chemical Company) into a ZSK extrusion press (manufacturer Werner and Pfleiderer), the two screws, kneading blocks and several cylinder sections one behind the other contained, so that the reaction temperature can be changed from cylinder section to cylinder section could. The reaction mixture was introduced into the ZSK extrusion press through a funnel. The extruded The mass was dried in the oven before the test specimens were pressed * The different reaction temperatures, those listed in Table I represent the various temperatures used in the. different "Sections of the cylinder were applied.

Examples 7-10

In the tests of the next β examples, a reaction mixture was used which contained 50% by weight of a polyurethane containing terminal isocyanate groups (Texin 591, manufacturer Mobay Chemical Comp.). The only difference in the second test series compared to the first test series is that a Qxymethylencopolymeres was used with a different molecular weight in .the various experiments. The various reaction temperatures listed in Table II represent the various temperatures that were used in the various cylinder sections «

Example 11

.45 Grew. * '$ A Oxymethylene © polymer ( "Celcon M-90-01" manufactured by Amaelderin) were mixed with 55 wt .-- j6 of a terminal isocyanate-containing polyurethane ( "Texin .591' ·» Manufacturers Mobay Chemical mixed Comp.) and snails press introduced through a hopper-dryer in a ZSK Doppe!. the reaction temperature was loading in the various barrel sections 129 to 232 ⁰ C Yariiert "the Awstrittstemperatur

carried 246 ^° C. The product obtained had a Shore D hardness of 60, an _{impact strength of 54 f} 9 mkg / square inch and a flexural modulus of 4080 kg / cm. The product had a very uniform appearance.

Example 12

The experiment described in Example 11 was repeated with the difference that 55 wt .- ^ of the oxymethylene copolymer "Celcon M-90-01" and 45% by weight of the terminal Polyurethane "Texin 591" containing isocyanate units were used. The product obtained had a Shore hardness D of 67 "a rupture" of

43.7 mkg / square inch and a flexural modulus of 7030 kg / cm The product looked very even.

As the above examples and the values in the tables show, according to the method according to the invention Obtaining products with very desirable properties for use in pressing and injection molding. About that In addition, the degree of homogeneity is crucial, such as a comparison of the appearance of the products obtained according to Example 1 and 2 on the one hand and the on the other hand, shows the product obtained according to Example 3. A product that has a marble-like and / or pearlescent one Looks, is practically unsalable for aesthetic reasons »

109828/171 / *

Bite · 2

occurs

Ί3 blow »

Tear-out strength ^

Hardness ° 'bending = »appearance module ⁰ )

25 ₉ 4

200
110

138 165 195 210 232 .45.5

155 186 141 227

216. 2 ^ 8 46.5
227 246 '54, 15

246 '243 254 38

177 218 232 294 41.6

65D

66D
65D

66D
69D

6820

5480
7730

7310

very even

strongly marble-like

dto ·

easy

Flow marks

sohwarZ ₁ light pleated markings

fe) © @ ii @ ss © a la ®l £ i / QBa, ö ^ a "(ig @ lI _s " determined. e) Cteme88ea "at 25 ^@ G In Shore D 1706

according to ASSM.D. 79O ₀ tmäB ASSM D 1822

at
game Approx
ferry
Molecu
large
weight
dee oxy
methylenes
c © poly
meren Up
given
lot
kg / hour Snail
know-
rotating
number,
Rpm A
occurs Tabel II 2 3 4th 5 C. 6th 7th the end
occurs Impact
tearing
consolidate
ability 9
mkg / qua
dratzoll ■ Bend
module"
kg / cm
:. ι Appearance 7th 60,000 45.4 140 121, Temperatures » ⁰ »93 213 221 232 204 210 241 50.9 ' 6330 8th 60,000 45.4 140 121 93 213 221 232 204 210 241 60.7 6190 very
same
moderate O 9 35,000 45.4 140 121 93 213 221 232 204 210 241 66.5. 5835 dto. co
00 10 25,000 45.4 140 121 93 213 221 232 204 210 " 241 62 6400 It ro If ' 00
• "Si VO
I. 1714

a) Measured in mkg / nominal square, determined according to ASTM D 1822.

b) Measured in kg / cm ² , determined according to ASTM D 790

O CD ΪΟ

Claims (8)

Claims Process for the production of polyoxymethylene mixtures, characterized in that an oxymethylene polymer with at least 60 mol $ oxymethylene units (-CH ₂ O-) and terminal groups which contain at least one active hydrogen atom determined by the Zerewitinoff method, and another organic polymer, containing a terminal isocyano or Isothiocyangruppe, mixed under high shear at a melt temperature of about 121-232 ⁰ C and the polyoxymethylene "discharges at a melt temperature of about 227-243 ⁰ C as a homogeneous mass 2) Method according to claim 1, characterized in that the melt is discharged ^{at a temperature of about 232 to 241 ° C.} 3) Method according to claim 1 and 2, characterized in that a polyurethane is used as the second organic polymer is used* 4) A process for the preparation of polyoxymethylene mixtures, characterized in that an oxymethylene polymer with at least 60 mol # oxymethylene units (-CH ₂ O-) and terminal groups which contain at least one active hydrogen atom determined by the Zerewitinoff method, another "organic" , Polymer with terminal groups which contain at least one active hydrogen atom determined by the Zerewitinoff method »and a coupling agent of the formula R- (NCX) _n , where X is an oxygen atom or sulfur atom» η is an integer from 1 to 3 and R is a substituted one or unsubstituted divalent aliphatic, cycloaliphatic or aromatic radical with up to 20 carbon atoms, under high shear 109828/1714 Mixes effect at a temperature of the melt of about 121 to 232 ⁰ C and discharges the polyoxymethylene mixture at a temperature of the melt of about 227 to 2.43 ⁰ C as a homogeneous mass, 5) Method according to claim 4, characterized! that polyurethane is used as another organic polymer. 6) Method according to claim 4 and 5, characterized in that that an aromatic diisocyanate is used as a coupling agent. 7) Method according to claim 4 to 6, characterized in that that diphenylmethane-4,4'-diisocyanate as an aromatic Diisocyanate is used. 8) Method according to claim 4 to 7, characterized in that the melt is discharged ^{at a temperature of about 232 to 241 ° C.}