DE1595842A1 - Polymer molding compound - Google Patents

Description

PATENT LAWYERS

DR.-ING. H. FlNCK MUNICH S ₁

DIPL.-ING. H. BO HfJ MCIIerstroße 31

DIPL.-ING. S. STAEGER

Telephone: 224941

M 20 660

Oasis P ₀ 18 273

Specimen copy

Must not gtündc; t ν :: dcn

Description for Fatentgeauch

from IMPEBIAL CHEMICAL INDUSiERIES LIMISED ,, London, England
concerning

"Foil molding compound ⁿ

Priorities: April 15, 1965 and

Mar. 15, 1966 - Great Britain

The invention relates to polymer molding compounds.

According to the invention is a polymer molding compound with a content of at least 55 wt .-% propylene monomer units, monomer units of a linoarea 1-olefin with 4 to 18 carbon atoms (hereinafter referred to as a further component) in an amount of up to 35 gene and bisijraeinfceiten an ofr-olefin (hereinafter referred to as the third component) whose homopolymer? has a crystalline Sohmelaptznfct of above 180 ⁰ O _1, preferably above 260 ⁰ C, in an amount

009820/1615 ORIGINAL BATHROOM

from to ssu 10% by weight, preferably less than 5 $ ** · - £> dispersed or distributed in the whole cash register. The ilasse preferably contains at least 2% by weight of the other component.

Further, a polymerization process which comprises bringing propylene, the second component and the third component into contact with a polymerization catalyst for olefins and recovering a solid copolymer mass containing at least 55% by weight propylene monomer units. Oils comprising 25% by weight of monomer units of the second component and polymar units of the third component in an amount of up to 10% by weight are provided.

The compositions according to the invention generally have a better transparency compared to the polypropylene homopolymer. In some cases the transparency is very improved; for example have in cuts or pieces of 1.59 ram (1/16 "section) most of the natural masses have a permeability of at least 40% and certain of the masses have a light transmission. 80%. You average Spherical body or spherulite size of compacts produced from the compositions according to the invention, respectively Pressed parts are generally below 5 f * and often below 1 ^ t in the case of quenched pressings. The inventive masses can also show better compression molding behavior than the polypropylene homopolymer, with voids or gaps and depressions or depressions being reduced.

BATH ORIGINAL

009820/1615 " ³ "

The physical properties of the polymers according to the invention, for example the stiffness, hardness or strength and toughness, are dependent on the relative proportions of the 5 monomer components in the Hasse aries manner in which they were incorporated. In general, the flexibility increases respectively elasticity of the old hatred increasing content of the second component.

Butene- (is particularly suitable for use as the second component because of its cheapness and ready availability; octene- (1) also gives good results. The third component are 3-methylpentea- (1), 4,4-diaethylp «nten - (1) [both result in ^{homopolymers melting above 35O 0} C »], vinylcyclohexane (the homopolar * mar melts at 34-2 ⁰ C) and 3-methylbutene- (1) [the homopolymer melts at 31Q ⁰ C] particularly suitable *

Mixtures of two or more second components or two or more third components or both can be used; it is also possible to incorporate or incorporate small amounts of ethylene units, for example up to 10% by weight, into the copolymer composition.

They function of dispersing polymer units of the third The component is the reduction of the average spherical body size of the Hasse in the compression molding! and therefore the improvement in their molding properties and optical properties compared with those of polymer compositions with only propylene and the wide component. Surprisingly, there is little of the third component for this one

009820/1615

Purpose sufficient. The ultra-red analysis of copolymer compositions is not effective if the concentration of the third component is below, for example O ₁ ; up to 1% by weight; Cash register oil; However, better properties can be obtained if the third component was present during the polymerization reaction in amounts which are insufficient to give, inter alia, 0.5% by weight of third component in the final product. From this it is clear that it is not practically feasible to specify a quantitative lower limit for the amount of the third component required in Hasse.

The compositions according to the invention can be produced in the most varied of ways. In general, the formation of Polymer units of the third component polymerize these during a period of time in the substantial absence of other monomers will. This can be done before the polymerization of propylene as well as the «wide component or after the polymerization of one or done by both; it can be done more than once, although no benefit is found. It is particularly expedient that Third component to polymerize on a small scale before any of the other components odor the bulk of the other Components has been polymerized. This is because of the slow polymerization rate of the direct component in comparison also the other two and the small amount of the same amount required in the finished copolymer composition; it can be high Catalyst concentration can be used to increase the rate of polymerization, running the process on a small scale makes a longer polymerization time more economical and the extraction of unreacted third component

009820/1615 - - - Γ ⁵ "

8AD ORIGINAL

(if at all) is lighter on a small scale and in the absence of other monomers. Another possible way of carrying out the invention, however, is to add all three components together to the catalyst and polymerize during the process an extended or longer time. In this way the third component polymerizes the slowest and such it is the last monomer to be discharged or discharged; thus form in the last polymerisation stages 'Polyyne purities from the third component are largely absent from other monomers "

It is advisable to use an ötereepeaifischen catalyst su for the polymerization. A “stereospecific catalyst” is understood to mean one which, under appropriate or equivalent conditions, polymerizes propylene in the absence of other monomers is solid polypropylene which is at least 70 ° insoluble in boiling n-heptane. Numerous catalysts that do this are known in the Seclinik; for example, many useful catalysts are described in the book "Linear and StereOregular Addition Polymers" by Gaylord and Hark, Intersoienoe, 1959. In general, they include a compound activated by an organometallic compound or a metal hydride of a transition metal from groups XV to VI of the periodic table

ο mea. Most will be those catalysts which ο

^ an OrganoaJ.aluminium compound, for example an Aluainiu »-

o trialkyl or -alky! halide, in which each AUtyl group

- »pe has 1 to 8 carbon atoms, activated titanium triochloride

^ included, used. Bq is preferred because «material which»

by, reaction of titanium tetrachloride with an aluminuBaUcyl- <

BATH ORIGINAL

sesquichloride in a tormented alkane solution at about ^{0 0} O, preferably by gradually (for example dropwise) adding a solution of the sesquichloride to a solution of sesquichloride using a grammatical ratio of aluminum; Sitan yon 0.4 to 4.0 was obtained to use. The product thus obtained may be washed before use with hydrocarbon and / odor 1 or more heat treatments are subjected to from 60 to 15O ⁰ C. The use of a dialkylalurainium chloride is preferred as the activator for this material. ■

The polymerization takes place in the absence of air and water or in the presence of only limited amounts of the same, since in other than low concentrations both air as. water also deactivates the catalyst. Appropriately an inert hydrocarbon diluent is used as the polymerization medium. Nitrogen is often used to clean the device beforehand. A pressure above atmospheric pressure can be used. It can water off to lower the molecular weight and increase it of the melt flow index of the copolymer can be used.

Free-flowing Polymeraufsohläramungen in Verdünnungsaiit- _/ stuffs are easier to handle and (deash) to ash as polymer solutions or sticky viscous gels "slurries are formed at lower temperatures more easily; the copolymerization has a tendency towards the formation of gels. It was found that the conditions at the beginning of the polymerization

009820 / 161S ***>

8th are indicative of whether or not slurries are formed. Deρhalb it is preferable to start 1 of the components in the absence of jegliohem other monomer, preferably eieren at a relatively low temperature, for example below 30 ⁰ C to homopolymer! Until calibration least 1 Cfew.-ji of the final polymer composition has been formed. In polymerizations of this type, there is less tendency to form skin lesions or gels, even if the temperature is increased at a later stage in the polymerization. Bs can be advantageous to up to 10 wt _e ~ ji the total amount of Oopolymermasse to form in this way * before any other! Component is sugegeben. The component used with caution at the beginning of the polymerization is propylene} a particularly expedient procedure for carrying out the process according to the invention comprises the polymerization of propylene at the beginning and the subsequent homopolymerization of the third component in the presence of a high catalyst concentration, the addition of diluent to reduce the Catalyst concentration and the subsequent polymerisation of propylene and the second component.

An aqueous ashing can be used, for example by treating the polycer slurry with 1 to 5% by volume of an alcohol and subsequent washing with water, can be used to obtain copolymer compositions of the highest transparency however, the ashing is preferably carried out under substantially anhydrous conditions using dry reactants carried out. The non-aqueous process can expediently

^009820/1615 badori ^ nal "

can be carried out by 2 main procedures. One is a small amount of Verasohungsiaittel sur reaction mixture in the addition (when the Reaktionsmieohung is a solution, this sur generally precipitation serves polymer from it), the digestion over a period at moderate temperature »for example, from 20 to 6O ⁰ C, and then filtering and washing with more solvent or hydrocarbon or mixtures of the two. The other consists in the separation of the first taking place throughout the polyme t rl eat ionövQrdünnung8jait tele or the greater part of the PoIymerisationsverdUnnungsmittels from the produced polymer and the subsequent 1- or multiple resuspension of the polymer in Veraschungamittel. In the first procedure, the most suitable types of ashing agent are the hydrocarbon-miscible alcohols, such as isopropanol, n-butanol, isobutanol or the higher alcohols such as 3,5,5-trimethylhexanol and isodecanol, and higher acids and amines such as n-Nonaj -iB.lure or pelargonic acid (n-nonoic aoid) and 3,5,5-trimethylhexylamine. Mixtures of alcohols with complex-forming carbonyl compounds, such as iopropanol mixed with acetylacetone, are particularly effective. In the second procedure, it is particularly advantageous to use the lower alcohols, for example methanol and ethanol, because of their cheapness. Using procedures such as the above can easily result in low ash levels, e.g. below 0.02 Sew. ~ # to be received.

The copolymer compositions according to the invention can by known Process for plates or foils, rods, films and

^009820/1615 SA

· ■ 9 -

Threads or fibers are processed. You can through a wide variety of known processes, for example injection molding, compression molding, extrusion »blow molding (blow molding) and rotational casting (rotational casting) ι eu various objects are processed · those "Relatively high permeability have many uses in the field of packaging, for example when packaging films or bottles. The mechanical properties of the Copolymerraassen can to a certain extent tailored to the application for which they are required will; the flexibility or elasticity is through Increase in the proportion of the large component in the mass increases, higher 1-olefins [for example decene (1) I increase the Flexibility or elasticity more than lower ones 1 ^ olefins for example Bu.ten- (1) j «

The copolymer materials according to the invention can be used with additives of all kinds, for example heat and idothatabilizers, Fillers, antioxidants, agents to prevent static electricity, soot, pigments, fire retardants Agents, slip agents and the like or compounded. You can also be with others Polymers such as low density polyethylene, polyethylene high density, polypropylene and butyl rubber.

In the following examples, the molded articles were produced in the following manner:

009 8 20 / 161S

- 10 -

The dried polymer obtained was placed in a Vorfora of 30.8 to 50.8 mm χ χ 1.59 ■ »(2 χ 2 χ Vi6 'preforn) under a pressure of 3 kg 14-9,4- / ca ² (20 tons / square inch) 5 minute foragepreßt long. the temperature used in compression molding was 25O ⁰ C. the compact was then removed from the cress and immediately quenched by immersion in cold water or slowly in the press allowed to cool. It was found, that the average spherical particle sizes of the copolymers of the invention generally do not vary greatly (often by no more than a factor of about 2) depending on the manner in which they are pressed, unless the compact is intentionally cooled very slowly or for a long time Time is kept at a temperature close to below the melting point.

The Pölymermasßon were pressed, as this is an easy one The way to manufacture small polymer samples is, in some cases it is however, it is possible, in the case of objects produced by a melt homogenization process, for example by extrusion molding, a achieve better transparency.

Average spheroidal sizes were measured by photomicrography of the sample using polarized light. The average human body size was taken from measurements of the diameters of approximately 100 spherical bodies. The permeabilities were measured by IS ¹ Ol East D. 1 746-62T and the opacities were measured by ASTM Test D. 1 003-61, the samples being "dipped in diaethylphtaalate" to remove the surface smear.

009820/1615 "bad original ~ ^ ~

In the following examples, the low temperature sprays point or that lowering temperatures are predicted with the help of ASXM Test B. 74S-57T using τοη around a Born with a Radius of 0.4 cm curved unnotched specimens with dimensions of 2.0 cm 0.2? approx χ 0.16 cm through a 2.13 m (7 feet) per Second moving hammer measured "

The flexural modulus was determined after aging for 14 days by a simple beam bending method at 20 ^° C.

Bas titanium chloride used in the examples was prepared by reacting _{TiCl 4} and Alutdjiiumäthylsesquichlorid in a purified hydrocarbon fraction. Etae solution of the equichloid in this diluent was gradually added dropwise to a solution of TiCl ₄ in the same diluent over a period of several hours, the temperature being kept at ⁰ ° C 1.6. Bie resulting TiCl containing slurry was then heated over a period at 95 ⁰ C. It was introduced in the form of a slurry in a hydrocarbon in the Bolymerisationsgefäfi "

The invention is based on the following not all BesehrSnktSBg based on examples explained in more detail.

3AD ORIGINAL 009820/1 61 5

. - 12 - Examples 1 to 5

Ss, a Titantrlchlorid (prepared in the manner described above) and suspended Aluminlumdiäthylmonochlorid in a Holverhältnis of 1 Hol of the former to 2 Hol of the latter containing catalyst under air · and anhydrous conditions in a purified high-boiling Benzinfrafction at 30 ⁰ C and there were 9, 5 Hol propylene added per mole of titanium trichloride. When the polymerization was essentially complete, the temperature was increased to 60 ⁰ O and 2.8 moles of 3-methylbutene- (1) per hol of titanium trichloride were added and allowed to polymerize at this temperature for 18 hours.

Samples of the pretreated catalyst so formed were used to polymerize mixtures of propylene and octene-1. To 500 cm 'of a high-boiling paraffin fraction, a fraction of the sludge containing 6 Hillimol aluminum diethyl chloride and 3 Hillimol titanium trichloride with preformed polymer was added. Propylene was fed in under atmospheric pressure over 2 hours and octene (1) was added steadily over the same period. They Polymerieationstemperatur was 40 ⁰ C. At the end of 2 hours a mixture of dry isopropanol and acetyl acetone was added and the temperature was raised to 60 ⁰ C. After a period at this temperature, the slurry was filtered and the polymer was washed with dry isopropanol until the filtrate was colorless. A comparative experiment A was carried out in exactly the same way, but without using octene (1). Moldings were produced, and the 3-ethylbutene (1) and octene (i) contents were measured by ultra-red analysis; the results are in dor

00 9 820/1615

159584

compiled in the following table I:

Tabel .1

example
refer
hungs
way
Ver
equal
attempt Added
tea oc-
in car -Methyl-
butene (1) Wt% octene Size of by deterrent!
chilled Eugelkö'rporchen in Average Minim A.
1
2
3 nothing
10
20th
40 • y
3
3 nothing
5
13th
17th Mn-jri ΐΏΐιτη 2
1 2

example M-

E3 is a titanium trichloride as in Step Example, to 3 9 but using 60 mol of propylene and 12 -mol \ -Möthylbuten- (I) per mole of titanium trichloride was pretreated.

Fraction of this pretreated catalyst with a contains 10 millimoles of titanium trichloride and 20 millimoles of aluminum: ethyl chloride was dissolved in 1 200 cnr hydrocarbon diluent

medium introduced under air- and water-free conditions "egg the propylene under atmospheric pressure for 3 * l hours at 60 ⁰ C out and octene (1) [80 esrjdie all the time hindurc continuously added" The resulting polymer was as in the games For · 1 to 3 3 processed. A comparative experiment B was carried out in i

009820/1615

Shear procedure carried out except that no octene (1) was added. The mechanical and optical properties of moldings of the polymers are summarized in Table II below:. .

BATH ORIGINAL

009820/1615 -15-

Table II

example Bending module α
jpsi χ 1C? N5.eder- Size of the ab By Mini Translucent i 20th long- Tru Wt% Weight # "refer tempe- terrified Ku- cut mum sity in % I. 64 sam- exercise 3-methyl- Oct'en- (1) hungswei
se ver i;
kg / s ² χ 10 ⁵ ratural
brittle gel corpuscles
in ^ i ge
i cools in % butene (1) equal dig- Maxi, ab search ability must frightens Point refer C. hungs C.
(C. way α Low- C. tempe- ratural 5 cn brittle- <1 32 * [1.94] will [0.78] in ⁰ C O B. 0.136 13.0 <1 64 5 6th 0.055 -7.7 8th 5

CJI CO cn OO

- 16 - Example 5

A titanium trichloride catalyst was used as in the examples up to 5, but using 30 moles of propylene and 6 UoI 3- -Methylbutene- (i) pretreated per mole of titanium trichloride.

A fraction of the pretreated catalyst slurry containing 15 millimoles of titanium trichloride (and other constituents proportionally or proportionally) was added to 3 liters of hydrocarbon diluent in a 5 liter autoclave under air and water-free conditions. It was sugesetzt propylene at 60 ⁰ C until a conversion of 120 g polymer / 1 yielded Verdünnungsaittel; Octene (1) [100 car total] was added steadily over the same retume. The resulting polymer was prepared as in Examples 1 to 3 »

3 comparative tests C, D and E were also carried out. In comparison tests 0 and D, the stage was the pretreatment of the catalyst was omitted and in experiments 0 and B no octene (1) was added to the polymerization medium. Otherwise they were Conditions identical to those used in the sample. The optical and mechanical properties of quenched molded prefilings are summarized in the following table IT1:

⁶⁴⁰

009820/1615

Table III

example Bending module kg / cm χ 10 ^ psi χ OK-Ί
au Down size the dismissed I. 20th Mint Translucent Wt% Weight % refer in
I. tempe- terrified bullet By 15th well sity in % 3-methyl- Octene (I) hungswei
se yer- ratural
brittle corpuscles
in 31 cut <1 butene (1) equal closely- <1 attempt ability
Point Maxi beaie- mum > hungry i way ο Low O
«Α tempe OO
IsJ ratur— 10 σ 0.134 [1.91] brittle-
will 5 -Jl
on
—Λ 0.068 [0.97] in ⁰ C <1 (T C. 0.130 1 ^ k CJ CT I.
II % ^ r ^? I. 2.4 <1 0.62 nothing nothing D. 0.074 [1.05] -11.7 30th 3.0 nothing 5 E. -2.6 25th 26.0 0.5 nothing σ » -9.0 1 40.0 0.5 3 ^ δ
C. <Λ

CD cn OO

- 18 - Example 6

Example 4 was repeated exactly except that 80 cv? Witch- (1) in place of 80 ex? Octene (1). A quenched Fonaprefiling of the resulting polymer contained 5 wt% 3-methylbutene (1) and 8 wt% hexene (1) and had a light transmittance of $ 57, an average spherical size of <1 W, a HiedertemperaturaprÖdigkeitspunkt or a Nlederteaprsprödewerden of "13.1 ⁰ C and a Biegeaodul of 0.055 kg / cm ² ζ (0.50 * χ 1O ⁵ psi).

Enclosed 7 to 17

In 1 liter of purified hydrocarbon diluent under Ziegler conditions, a catalyst as indicated in the following Table IV with a content of 12 lU.13 imoles of titanium trichloride and 36 millimoles of aluminum diethyl chloride was introduced. Die! Temperature was raised to 50 ⁰ C and there were propylene and but ene (1) in the Oefäfi initiated. The partial pressures of propylene and butene- (1) were varied, but their sum was in each case approximately 960 mm Hg. The polymerization was continued at 50 ^° C. for about 6 hours. The ashing was carried out as in Examples 1 to 3; the resulting polymer (generally about 100 to 150 5) was processed into quenched and slowly cooled moldings. The properties thereof and other details are summarized in Table IV below. Comparative experiments V to Γ were also carried out in a similar manner, but no butene (1) added in comparative experiments 7 to H trar.

^ BAD OR-GiNAL 009820/1615 "-

gen, while in the comparison cakes I and J no gate-treated Catalyst was used. The details of the in Table IV specified catalysts are as follows:

Catalyst A was prepared by passing propylene into titanium trichloride and aluminum chloride (the molar ratio of rotors to the latter being 1: 3) under Ziegler conditions for about 5 hours at 50.degree. Then 3 ~ Methyrbuten- (i) was added and polymerization was conducted for 30 hours at 50 ⁰ C. At the used in the Hauptpolynerieation 12 millimole Titantrichloridbruchteil located 3 '' 1 β polypropylene and 2.0 g formed poly-methylbutene-J3 -(1)] ·

The catalyst B was prepared in the same manner as the catalyst A but was found to be 3.1 grams of polypropylene and 2.2 g of poly [3-ethylbutene- (D] per 12 millimoles of titanium trichloride ” bruchtoil contained.

The catalyst 0 was made in the same manner as the catalyst A, but was found to be 4.9 grams of polypropylene and 1.6 g of poly [3-ethylbutene3L ~ (1)] per 12 millimoles of titanium trichloride fractions contained.

The catalyst D was processed in the same manner as the catalyst

A produced except that in place of the propylene treatment Hex- (1) at the beginning for 6 hours be :. 50 ° C was polymerized «, Es it was found that it contains 8.2 g of polyhexene (1) and 1.8 g of poly- [J- -isethylbuten- (i)] jo 12 Millijsol-Tttantrichloridbruchtoil contained.

BATH ORIGl 009820/1615

Catalyst Z did not undergo any polymerization pretreatment subject.

- 21 009820/1615

Table IY

f Example ■ hsmgs- Comparative I. 9 Kataly gebalt, is | 3-methyl Schmels-I Flavored pellets Average Pr © B- cooled in the press - ling - 2
2 Si ι ϊ * - attempt 7th 10 sator- « "but en ™ ( ¹ O- £ Lo8- % spherical body UN CO Average 2 pp
OO
3 * -
IS *
- 22 - F. -4 8 11 Type salary in index* Light- Chen size © (in pi). % 12th
12th KugGlk3rpei * «liön- · I. G tr J Light- size (in ρ) MH
CX 12th
13th casual- by do
CO 14th
15th 0 speed 1 las sig- 5 KJ
CJ A. 0 1,* 0.08 32 <1 1.7 6th BATH ' A. 0 1.2 1 _t 7 32 2 0.4 3 ORIGINAL A. 14th I ₁ * 24.0 23 10 0.8 ~ X T? 0 0 _s 6 3 <1 ~ P Ad
3 3 14th 1.6 0.7 57 <1 19th 2 B. 12th 1.5 6.4 53 <1 5 * 8 3 B. % 9 11 59 <1 11 i
2 B. 14th 1.8 18th 50 <1 9 B. 23 1.7 30th 54 3 9 X 24
25th 0 1.8 15th <1 A.
A. 24
22nd 1.7
1.8 1 * 9
9.5 44
50 A.
A. 1.6
1.7 ' 16.5
38.0 44
23

example iCafcaly- Butene- (i) - 11 2-methyl Melting Deterred pellets Average 1 In the . % Through cut-1 i- refer sator salary in buten- (1 ^ flow spherical body <.1 Press chilled Light- che spherical body hungs Weight ~% • salary in index" Light- oh size (in u) Pellets by size (in u) way f \ _, .. O /
<J VU β - * / U through ~ I. casual Comparison casual « speed attempt speed 22nd 2 • - - 16 C. 1.0 o _¥ 9 66 17th D. 3.2 69

O GJ O to OO ro O cn

cn

190 ° C / 10 kg, 1% stabilizer

CD cn 00

KJ

Example 18

Ea was a pretreated catalyst by mixing 10 millimoles of titanium trichloride with 20 millimoles of aluminum diethyl chloride under polymerization conditions at 30 ° C and treating with 3- -ltethylbutene- (1) _t so that 60 millimoles of 5-methylbutene- (1) were polymerized on the catalyst, manufactured.

The catalyst obtained in this way was suspended in 1,200 carrons of a high-boiling, purified bensine thinning agent and a mixture of propylene (160 g) and hexene (1) was ^{polymerized at 40 °} C. The resulting polymer was prepared as in Examples 1 to 3; 160 g of a product whose ultrarotanalyae indicated a content of 2% by weight of # 3-methylbutene (1) and 13% by weight of hexene (1) were obtained. Quenched Pormprefllinge: 7% light transmission, 11% haze and a mean spherical size of) 1ii | slowly cooled molded moldings: 54% light transmission, 31% haze and an average spherical body size of 2n »

Examples 19 bJB 2 »

A pretreated catalyst was prepared as in Example 18. It was suspended in 1,200 cm ^ of a purified high-boiling bensine diluent -and xxaa. Polymer! Eggs of a mixture of 160 g of propylene and used amounts of hexene (1) at 60 ^c G. Both monomers became steadily sugeeetzfc throughout the polymerization. The resulting polymer was prepared as described in the structure 1 Με 3 vs \ ä zn Formprofilin ^ en, ¹ Jr> d although see below

009820/1615

Quenched and slowly cooled molded moldings, processed · Analyzes and various preliminary searches, the results of which are in the following table 7 are compiled, - carried out

0 0 9 8 2 0/1615 _CÖFi >

\ C. * 19th UgO- kiss the melt-jPak-]] management |
borrowed
jV XU Table V L.
u I. tP.86] üiie- "ι
Qich through- ab
frightens I. 65 Turbidity in % ab
frightens!
I. Ge * .- 9 Hey ■■■ " ι α
σ 20th etz-
it
in cm * Iterative
a-
middle
won
nene luss- J]
19C ⁰ C /
10 kg) Bending moduli [1.05] the- .
tempe
ratur—
brittle
dig- Nonchalance
in % 65 xe. feel-. . iunga-
travel κ
C. J 21 soluble ia
kg / cm ² ac 10'S [i.20] ability- [ long
sam 60 long
sam 5-
-methyl- -C game'
ί for— 22nd che E? .45] Point ge 52 ge but- Ä Carcassic σ 23 Fabrics [1.65] loading cools 52 cools - (D attempt U 24 (in J2.02J target 44 . K G _SW . -% ■ huni? s- in! Ge know OT
α weight Never ο
13th focus the- V. Q tration, tempe Γ " based rature «= · on the brittle Monomer! will ) fö \ w / w in ⁰ C on! mono
I ■ 19th 7th 40 5.42 5.5 ! {• 61 -8th 21 4th 20th 4.00 7.0 480 0.060 -5 41 58 26 .. 5 20th 6f15 6.5 V? 6 0.072 -4.1 54 57 58 4th 10. ^ • 95 ^ i? * 58 0.084 -0.2 55 m. 57 5 cT ■ i 5 4.82 5.1 ^ 56 0.102 +5.7 52 ■ - 44 <o a.5 5.90 2.4 P, 116 +4.4 19th 75 .., 5 OQ nothing *>.? * 1 0.141 H , .Λ Γ ». 20th 72

* ■ * 2ο - ■ ·

example 25th

Ss was a mixture of 95 cw? In a schlämung of Tltantrlchlorid containing 100 Milllmol titanium trichloride in a purified high-boiling Alkanverrtfinnnngirai ttel and 185 cm Ton 1.6 molar Alumlniumdiäthylchlorid in the same Verdünnungemittel (300 millimoles Aluminiumdiäthylchlorid) at 5O ⁰ C for 4 hours, stirred, with propylene (67 car liquid , 40 g) was absorbed. The unreacted propylene was removed under vacuum and there were Fliethylpenten- * 3 (1} is added 30 car (20 g) for BeaktlonsmedLum, which was then stirred at 5O ⁰ C for 72 hours "The excess monomer was removed under vacuum.

The catalyst slurry produced had 1 ifillimole Titanium trichloride 5.5 Hillimol polymerized propylene and 2.15 millimoles of polymerized 3-methylpentene- (1).

A portion of the above catalyst containing 12 Hillimol titanium trichloride (45 cm * "slurry) was used to copolymerize propylene and butene- (1) at 50 ° C according to the procedure of Examples 7-17 over a period of 5 hours the total lionomer charge was 373 cm * of liquid propylene and 50 cm 'of liquid butene- (1). The product was isolated as in Examples 1 to 3, whereby 149.3 g of copolymer with a content of 15% by weight of butene- (1) and 1.5 wt .-% 3-methylpentene (1) yielded · Sine sample was milled at 190 ⁰ C and then compression molded at 250 ⁰ C and quenched from this temperature, resulting in a .Platte of 1, 59 at (V16 ¹¹ ) with a high permeability of

Claims (1)

Claims 1.) Polymer molding a with a content of at least 55 wt .- * Propylene monomer units, monomer units of a 1-Olefineβ having 4 to 18 carbon atoms as a "further component in an amount of up asu 35 wt .- #, and polymer units of OUOlefiaes whose homopolymer has a crystalline melting point above 180 ⁰ C, as a third component in a Mange from up to ZSU 10% by weight dispersed or distributed in the goose maize. 2b) Hasse according to claim 1, characterized in that it contains at least 2% by weight of the "broad component" 3.) Hasse according to claim 2, characterized in that the »width Component butene (1), hexene (1) or octene (1) is 4o) Maaöe according to claim 2 or 3> characterized by »that the third component is such that its homopolymer has a crystal Jews melting point above 260 ⁰ C. 5.) Cash register according to claim 4, characterized in that d & £ the third Component 2-Meth7lbuten- (1) or 5-Methylpentene- (1) is. 6 «) mass according to claim 2 to 5» characterized in that it in the compression molded and quenched state, an average -JtI r 0 0 9 8 2 0/1615 _ßAD original lent spherical body size of less than 1 ^ i. Hasse according to claim 2 to 6, characterized in that a in the pressed and quenched state, the cut thereof is 1.59 mm (Vi6 ") and has an Idchtdurchlaßigkeii of has at least 40%. β «) Hasse according to claim 2 to 8, characterized in that it also contains ethylene monomer units. 9 ·) Hasse according to Claims 2 to 8 essentially as described in Examples 1 to 17. 10.) Hasse according to claim 2 to 8 iir. essentially as described above, in particular with reference to Examples 18 to 25th 11.) Shaped object including a plate or polie, a rod, a film, a thread or a fiber, which is made from a Hanse according to claim 2 to 9 or 3W-. 12.) 'A method for producing the hats according to claim 1, characterized characterized in that propylene, the »other component and the third component with a polymerization catalyst in Reference to «(-olefins are brought into contact and a solid polymer mass with a content of at least 55% by weight Propylene monomer units, monomer units of the other , _ - III - 009820/1615 ^BA & original Component in an amount of up to 35% by weight and polya & purities the third component in a set of up to sts 10 wt. ~% Is obtained. 13.) Process for the production of a mass according to. Claim 2 to 8, characterized in that propylene, the »broad component and the third component with a polymerization catalyst in Beavtg on <* - 01ef ine and a solid copolymer composition containing at least 55% by weight of propylene monomers, monomer units of the rei th component in a quantity 3 of 2 to 35 wt. = liquid and polymer units of the third component in an amount of up to en 10% by weight is recovered ) Ancestors according to claim 13, characterized in that the Polymerization catalyst in relation to (^ -olefins a storeo-specific catalyst (as previously determined) is. 15 °) Method according to claim 14, characterized in that the stereospecific catalyst with an organo-aluminum compound aktivertos contains titanium triciloride. 16 ο ) Process according to claim 14, characterized in that the sitane trichloride is obtained by reducing titanium tetrachloride with an aluminum alkyl sesquichloride in a purified alkane medium with stirring in an inert atmosphere at ⁰ ° C. 17 ·) Method according to claim 16, characterized in that 009820/1615. - - \. _BA D ORIGINAL the reduction is achieved by the gradual addition of the aluainlumaliyleeaquichlorides in an alta solution to an alkane solution Titanium tetrachlorides is carried out. 18 ·) The method according to claim 15 can be 17 * thereby, that the organoaluminum facing is DiaUcyiaLumlaiumohlorid. ο) Method according to claim 13 «characterized in that the third component is polymerized before a substantial amount of any other monomer has been polymerized. 20 ·) Method according to claim 15, characterized in that the dxitto component following the polymerization of a other ifonomer is polymerized. 21 «) Method according to claim 20, characterized in that Propylene, the second component and the third component are all added together in the polymerization zone and the polymerization for a time that is sufficient> by substantially all of the propylene and the sweet second Polj-merize component and then at least polymerizing some of the third component is performed. 22.) The method according to claim 19, characterized in that the third component is polymerized in a separate precursor. BAD ORiGiNAL «7 009820/1615 23.) The method according to claim 20, characterized in that on At the beginning propylene or «wide component is polymerized in small amounts, then the third Component is polymerized and then the main mass of propylene is polymerized. Process according to claim 25, characterized in that the initial polymerization of propylene or »white the component and the subsequent polymerization of the third component carried out in a separate preliminary stage. 25 ·) Process according to claim 14 to 24, characterized in that 1 monomer aa is initially homopolymerized in the absence of any other monomer until at least 1 % by weight of the final polymer product is formed. 26 «.) Method according to claim 25 · characterized in that the The temperature of the initial homopolymerization is at or below 50 ⁰ O. · 27) The method of claim 23 or 26, characterized in \ that to below 10 wt .- * of the final & ltigen Polyiaerproduktee is formed in the initial homopolymer! On. 28.) Method according to Anepruch 25 to 27, characterized in that at the beginning propylene is hoaopolyaarieiert and then the third component in the presence of a high catalyst toxicity -VI- BATH ORIGINAL 009820/1615 centration is polymerized, then sw lowering of the Catalyst concentration diluent is added and then polymerizing propylene and the second component. 29.) Method according to claim 15 Ids 28 _? characterized in that the resulting polymer wet is incinerated under substantially anhydrous conditions using dry reactive agents. JO ») Method according to claim 29t, characterized in that as Ashing agent is a mixture of alcohol and acetylacetone is used. 31 «) Method according to claim I3 to 20 * characterized in that during! the polymerization of hydrogen will decompose . 32.) The method according to claim 13 to 31 essentially as in the Examples 1 to 17 described. 33 ·) Method according to claims 12 to 31 essentially as above described, in particular with reference to the examples 18 to 25. Polymeraasee, which by the method according to claim 13 to 33 has been produced. PATENTANWÄLTE DB- (NS +! FIMCKr. DiPl -INC ₃ η 009820/1615