DE1495907B2 - Thermoplastic molding compounds - Google Patents

Description

30th

The German Auslegeschrift 1145 792 relates to thermoplastics Molding compounds with high impact resistance at low temperatures, which are made from mixtures of polypropylene and alternating ethylene / propylene block copolymers of the formula ... AAAAABBBBBAAAAABBBBB ..., where A and B mean ethylene and propylene. the Making these polymers is complicated and requires a series of polymerizations first one and then the other monomer. Every time a fresh monomer is fed into the reactor must first be flushed with an inert gas. This "constant change of reactants with an interposed rinse takes place many times and makes the process extremely cumbersome overall. To the desired To prepare a mixture, it is also necessary to add the polypropylene to the block copolymer.

It has now surprisingly been found that mixtures of polypropylene (or a copolymer according to the definition below, which is largely made from propylene monomers has been) and a simple copolymer have high impact resistance at low temperatures. In addition, the advantageous compositions obtained can be made from these copolymers and polypropylene form directly in the reaction vessel used to make the copolymer.

The invention accordingly provides a thermoplastic molding composition consisting of

a) Polypropylene or a copolymer of at least 96 percent by weight propylene and up to 4 percent by weight ethylene and / or a C ₄ -, to C ₈ -α-olefin and

b) a polymer of the formulas PC or BPC or a mixture of such polymers, where B and C are each independently a polyethylene chain, a poly (C ₄ to C ₈ α-olefin) chain or a chain of a copolymer mixture represent two or more such α-olefins and P is the chain of a polymer according to the definition given under a) and the chains B and C together make up 1 to 40 percent by weight, based on the total mass, and determine the molecular weight (number average) by measuring the intrinsic viscosity of the polymers in the composition is at least 50,000.

The compositions according to the invention show an improvement over propylene homopolymers Impact resistance at low temperature, while the other desirable properties in the are essentially retained so that they can be used in the same manner as the well-known crystalline polypropylene can be deformed and processed.

The compositions of the invention can be in mono- r, fan manner by reaction of monomeric Pro- (a catalyst and adding pylene in a reaction zone in the presence of propylene prepared in the substantial absence of a comonomer, with a polymeric chain of the comonomer at least one end of the Polypropylene chain is formed when the comonomer is added in amounts of about 1 to 40 percent by weight, based on the total weight of the polymer composition formed in the reaction zone. The comonomer is ethylene, a C ₄ - to C ₈ a- Olefin or mixtures thereof.

In a preferred embodiment of the invention, the average molecular weight is Polymers in the composition about 100,000 to 1,000,000, and chains B and C consist of Polyethylene, which is in amounts of about 3 to 20 weight percent based on the weight of the total Composition. The designation »low-temperature impact-resistant polypropylene mixture« is used in the same sense as that used in numerous patents, for example the USA patent (^ script 3 018 263, the term used is »embrittlement point« and is a measure of the temperature at which the polymer under certain impact conditions described in more detail below, a brittleness failure shows.

For the sake of simplicity, the term "polypropylene chain" is used for the homopolymer or copolymer of propylene, which is described above as component a).

The term "monomeric propylene" is used in a similar way to refer to a monomeric feedstock to identify which leads to the formation of such a polypropylene chain.

The term "essentially in the absence of propylene" means that the propylene from the System is blown off, so that further growth of the polypropylene chain is essentially prevented will. It should be noted, however, that residual amounts of propylene remain in the reaction zone, which before the completion of the reaction by the addition of the comonomer an insignificant one Form amount of irregular copolymer chain.

The expression »α-olefin with 4 to 8 carbon

3 4

atoms «denotes a comonomer with 4 bis At this point pressure corresponded to that of the pro-

8 carbon atoms, such as B. butene-1, butene-2, pylene monomers in equilibrium. After about one

3-methylbutene-1, pentene-1, hexene-1 or buta hour at 65.5 ° C, the reactor was blown off,

diene-1,3, as well as their mixtures. Purged with argon and cooled to 26.5 ° C. Inner

To carry out the reaction, the propylene 5 half of 5 minutes were in the polypropylene in

and / or the comonomer with the catalyst in the reactor gradually 10 g of gaseous ethylene

any temperature in the range of about. After the addition of ethylene was complete

- 45 to +95 ⁰ C brought into contact. Preferably the pressure 0.35 atü and the temperature 49 ° C. The

wise, the reaction is a little above room residual ethylene pressure was consumed in 2 minutes.

temperature and especially in the temperature range io Then 500 ml of methanol was added to the

carried out from about 20 to 65 ° C. An actuator can be given, the alcoholic slurry of the

any known catalyst, e.g. B. 3 TiCl ₃ · AlCl ₃ polymers stirred for half an hour, in a 2-1-

or TiCl ₃ , transferred in conjunction with an aluminiumorga beaker and brought to the boil with stirring

; niche connection, such as B. aluminum triethyl heated. The hot slurry was filtered, the

: Aluminum triisobutyl, aluminum triisohexyl, aluminum 15 filter cake with a 50:50 mixture for 1 hour

; miniumtrioctyl, dimethylaluminum chloride, diethyl water and alcohol with a content of 0.5 g potassium

slurried aluminum chloride, ethyl aluminum chloride or metal carbonate. After filtering

ethyl aluminum bromide can be used. this washing was done again without potassium carbonate

j Although unmixed in the following examples and washed with the aqueous alcohol

j differentiated polypropylene blends were produced, 20 polymers slurried in 50 ml of acetone. That

can of course also auxiliaries, such as. B. wet polymers was at 2 hours in vacuo

^ ~ Dyes, pigments, fibers or other polymers dried at 80 ° C.

J in the polypropylene blends according to the invention A yield of 116 g of dry,

T be introduced without the low-temperature impact powdery polymer with a mean

j strength of the molecular weight produced from such mixtures from 380,000 to 478,000, one

j to impair molded body significantly. The inventive fundamental molar viscosity of about 3.7 and one

polypropylene mixtures according to the invention can have a melt index of 2.0 at 230.degree. The physical

the same way as polypropylene, for example kaiischen properties of the polymer are in the

by blow molding, injection molding or extrusion, listed in the table.

Utensils such as B. waste baskets, 30.

! Bottles, tubes, foils, etc., processed example la

will. Control attempt

In the examples, unless otherwise stated, in the reactor of example 1 were under one

give all parts parts by weight. The melt index is argon atmosphere 0.3 g 3TiCl ₃ -AlCl ₃ and 4.0 ml

expressed in decigrams per minute, measured as a one molar solution of diethylaluminum

; measured ASTM-D-1238-57 T at a temperature of chloride filled in cyclohexane, the reactor

230 ° C., gave up 0.35 atmospheres of hydrogen and

The molecular weight range of polypropylene- including 400 ml of liquid propylene added. the

ι mixtures of the examples was after the Chaing reaction temperature was within 5 to

Equation for the Bezi ehung between the middle 40 10 minutes 65.5 ° C and increased by one

j Molecular weight Mw and the grand molar visco hour added a further 200 ml of liquid propylene.

; intrinsic viscosity for polypropylene and poly- After one hour, the reactor was blown off

ethylene determined, after which the basic molar viscosity and cooled and the polymer according to Example 1 ge

| _; for polypropylene 1.04 · 10 ~ ⁴ Μ> ν ⁰ · ⁸⁰ and for poly- cleans.

■ ■ Ethylene 6.77 10 ^"4 Mw ^0-67 is (Chiang," Journal 45 A yield of 150 g polymer with

of Polymer Science ", Vol. 31, 1958, p. 453). For an average molecular weight of about 407,000,

j Mood of the average molecular weight range with a melt index of 1.7 and a grand molar

j the average molecular weight is obtained once from a viscosity of about 3.2. The physical

determined on the assumption that the Mi properties of the polymer are listed in the table consists only of polyethylene, and then guided 50.

Then repeat the same for the assumption that _R. · 1 1 u

the mixture consists only of polypropylene. Since the B e 1 s ρ 1 e 1 1 b

Mixture contains both ingredients, it is clear that control experiment

the average molecular weight in the range between - For comparison, a commercially available see the two values obtained falls. 55 all-purpose polypropylene with a medium MoIe-

. · ■, * gross weight of around 420,000 and a basic

For example, 1 molar viscosity of about 3.2 in the same

Investigated in a manner provided with a stirrer as the polymer of Example 1.

The physical properties of this polymer under an argon atmosphere 0.82 g 3 TiCl ₃ · AlCl ₃ and 60 are shown in the table.

10.7 ml of a 'one molar solution of diethylalu-'. -19

mineral chloride filled in cyclohexane. The Molis pie

the ratio of aluminum to titanium was 2: 1. The Re- The propylene polymerization process of the Beiaktor was sealed, 0.35 atm hydrogen up Game 1 was repeated, but now 0.2 g of and 24 to 38 ⁰ C under stirring, 400 ml of 65 3TiCl ₃ -AlCl ₃ and 2, 6 ml of a one-molar solution of liquid propylene (density: 0.58 g / cm ³ ) are added. The polymerization temperature of diethylaluminum chloride in cyclohexane has been within about det. After two hours of propylene polymer increased to about 65.5 ° C. for 5 to 10 minutes. The reactor was shut down to normal pressure.

blow and within 10 minutes into the polypropylene in the reactor gradually 20 g of gaseous Ethylene introduced. After the addition of ethylene was complete, the pressure and the temperature were 0.35 atmospheres 49 ° C. The residual ethylene pressure was consumed within 2 minutes. After 5 minutes it was the reactor is opened and the polymer obtained according to example 1.

A yield of 175 g of dry, powdery polymer with an average molecular weight was obtained from about 1,000,000 to 1,100,000, an intrinsic viscosity of about 7.1 and one Melt index of 0.2 obtained at 230 ° C. The physical properties of the polymer are in the Table listed.

Example 3

A 0.7 l pressure reactor made of stainless steel and provided with a stirrer was charged under an argon atmosphere with 0.23 g of 3TiCl ₃ -AlCl ₃ and 4.3 ml of a one molar solution of diethylaluminum chloride in cyclohexane. The aluminum to titanium molar ratio was 2: 1. The reactor was closed, 0.35 atmospheres of hydrogen were applied and 400 ml of liquid propylene (density: 0.58 g / cm ³ ) were added at 26.5 to 38 ° C. with stirring. The polymerization temperature was increased within about 5 to 10 minutes at about 65.5 ⁰ C. The pressure at this point corresponded to that of the propylene monomer in equilibrium. After one hour at 65.5 ° C, the reactor was vented, flushed with argon and cooled to 49 ° C. Over a period of 10 minutes, 10 g of gaseous ethylene were gradually introduced into the polypropylene in the reactor. After completion of the Äthylenzugabe the pressure was less than 0.14 atm and the temperature 49 ⁰ C. The Äthylenrestdruck was consumed in less than 5 minutes.

To recover the polymer, 500 ml of methanol were added to the reactor, the alcoholic one Slurry of polymer stirred for half an hour, transferred to a 2-1 beaker and under Stir heated to boiling. The hot slurry was filtered, the filter cake one hour with one liter of a 50:50 mixture of water and alcohol containing 0.5 g of potassium carbonate slurried. After filtering, this washing was repeated without potassium carbonate and the polymer washed with the aqueous alcohol slurried with 50 ml of acetone. The wet polymer was dried in vacuo at 80 ° C. for 2 hours.

It was a yield of 100 g of dry, powdery polymer with an average Molecular weight from about 600,000 to 725,000 an intrinsic viscosity of about 5.1 and obtained a melt index at 230 ° C of 0.7. The physical properties of the polymer are in listed in the table.

Example 4

The procedure of Example 1 was repeated, except that _{0.23 g of 3 TiCl 3 · AlCl 3} and 2.7 ml of a one molar solution of diethylaluminum chloride in cyclohexane were now introduced.

The yield was 115 grams of polymer having an average molecular weight of about 417,000 to 538,000, an intrinsic molar viscosity of about 4.0 and a melt index at 230 ° C of 2.7. The physical properties of the polymer are shown in the table.

Example 5

A 0.7 l pressure reactor made of stainless steel and provided with a stirrer was charged under an argon atmosphere with 0.48 g of 3 TiCl ₃ · AlCl ₃ and 5.7 ml of a one molar solution of diethylaluminum chloride in cyclohexane. The aluminum to titanium molar ratio was 2: 1. The reactor was closed, 0.35 atmospheres of hydrogen were added and 400 ml of liquid propylene (density: 0.58 g / cm ³ ) were added at 54.5 ° C. with stirring. The polymerization temperature was increased to about 65.5 ° C. in about 5 to 10 minutes. The pressure at this point corresponded to that of the propylene monomer in equilibrium. After one hour at 65.5 ° C, the reactor was blown off, flushed with argon and cooled to 38 ° C. Within one minute, 5 g of gaseous ethylene were gradually introduced into the polypropylene in the reactor. After the addition of ethylene was complete, the pressure was about 0.35 atm and the temperature was 65.5 ° C.

The residual ethylene pressure was consumed within 5 minutes.

To recover the polymer, 500 ml of methanol were added to the reactor, the alcoholic one Slurry of polymer stirred for half an hour, transferred to a 2-1 beaker and under Stir heated to boiling. The hot slurry was filtered with the filter cake for 1 hour one liter of a 50:50 mixture of water and alcohol containing 0.5 g of potassium carbonate slurried. After filtering, this washing was repeated without potassium carbonate and that polymers washed with the aqueous alcohol slurried in 50 ml of acetone. The wet polymer was dried in vacuo at 80 ° C. for 2 hours.

A yield of 100 g of dry, powdery polymer with an average Molecular weight from about 270,000 to 370,000, an intrinsic viscosity of about 2.9, and obtained a melt index of 5 at 230 ° C. The physical properties of the polymer are in listed in the table.

Example 6

A 0.7 l pressure reactor made of stainless steel and equipped with a stirrer was charged under an argon atmosphere with 0.27 g of 3TiCl ₃ -AlCl ₃ and 3.6 ml of a one molar solution of diethylaluminum chloride in cyclohexane. The aluminum to titanium molar ratio was 2: 1. The reactor was closed, 0.35 atmospheres of hydrogen were applied and 400 ml of liquid propylene (density: 0.58 g / cm ³ ) were added at 24 to 29.5 ° C. with stirring. The polymerization temperature was increased to about 65.5 ° C. in about 5 to 10 minutes. The pressure at this point corresponded to that of the propylene monomer in equilibrium. After one hour at 65.5 ° C, the reactor was vented, flushed with argon and cooled to 42 ° C. Over a period of 10 minutes, 10 g of gaseous ethylene and 3 g of liquid butene-1 were introduced gradually and together into the polypropylene in the reactor. After completion of the addition of ethylene and butene-1, the pressure was about 0.35 atmospheres and the

7 8

Temperature 59 ° C. The residual pressure of ethylene and hexene (1) addition, the pressure was less than

Butene-1 became 0.7 atmospheric and the temperature 43.5 ° C. within about 5 minutes. The remainder

needs. Hexen- (l) was used within 20 minutes

In order to obtain the polymer it was then necessary.

500 ml of methanol were added to the reactor, the aiko-5 to recover the polymer were then

holic slurry of the polymer half a 500 ml of methanol in the reactor, the alcohol

Stirred hour, transferred to a 2-1 beaker and holic slurry of the polymer a half

heated to boiling with stirring. The hot hour stirred, transferred to a 2-1 beaker and

The slurry was filtered and the filter cake was heated to boiling with stirring for 1 hour. The hot start

with one liter of a 50:50 mixture of water io slurry was filtered and the filter cake

and alcohol containing 0.5 g of potassium- 1 hour with one liter of a 50:50 mixture

slurried carbonate. After filtering, water and alcohol with a content of 0.5 g potassium

this washing repeated without potassium carbonate and slurried lium carbonate. After filtering

the polymer washed with the aqueous alcohol was washed again without potassium carbonate.

slurried in 50 ml of acetone. Get the moist poly and the washed with the aqueous alcohol

Polymer was slurried in 50 ml of acetone in vacuo at 80 ° C. for 2 hours. That

dries. . wet polymer was for 4 hours in a vacuum

A yield of 150 g of dry 80 ° C. was dried.

powdered polymer with an average A yield of 90 g dry,

Molecular weight in excess of about, 300,000, a 20 powdered polymer with an average

basic molar viscosity of about 3.9 and a molecular weight of over 150,000, a basic

Melt index of 1.6 obtained at 230 ° C. The physimolar viscosity of about 2.9 and a melting point

^; Typical properties of the polymer are obtained in the index at 230 ° C of 4. The physical

Table listed. Properties of the polymer are listed in the table

25 led.

^Beis P ^ieI7 example 9

In the one provided with a stirring device in one provided with a stirring device

0.7-1 stainless steel reactor according to Example 1 0.7-1 pressure stainless steel reactor were under

under an argon atmosphere, 0.54 g of an argon atmosphere, 0.5 g of 3 TiCl ₃ · AlCl ₃ and 6 ml

3TiCl ₃ -AlCl ₃ and 7.1ml of a one-molar solution of a one-molar solution of diethylaluminum

of diethylaluminum chloride in cyclohexane filled chloride in cyclohexane. The reactor was

fills. After adding 0.35 atmospheres of hydrogen and sealed, heated to 65.5 ° C and within

400 ml of liquid propylene were added to the reaction 5 g of gaseous ethylene for 5 minutes, wel-

partner polymerized for 1 hour according to Example 1, the 35 more fully polymerized in a further minute

The reactor was blown off and flushed with argon. Then sated. The reactor was heated to 82 ° C and

Were in the polypropylene in the reactor 50 ml of liquid 200 ml of liquid propylene (density 0.58 g / cm ³ ) under

Siges butene-1 (density: 0.67 g / cm ³ ) introduced, 10 Mi stirring supplied. The pressure corresponded to this

Nuts stirred at 38 ° C, the unreacted Bu- time that of the propylene monomer at the same time

ten-1 blown off and the polymer according to Example 1 40 weight. After 30 minutes at about 82 ° C, the

cleaned. The reactor was blown off, purged with argon and opened

A yield of 75 g of polymer was cooled to 51.5 ° C. Within 15 minutes,

an average molecular weight above about 400,000, which is gradually introduced into the polypropylene in the reactor 15 g

jj) an intrinsic molar viscosity of about 4.0 and gaseous ethylene introduced. At the end of

obtained a melt index at 230 ° C of 0.2. The addition of ethylene was less than 0.07 atmospheric pressure

physical properties of the polymer are in and the temperature 65.5 ° C. The ethylene residual pressure

listed in the table. was consumed in 5 minutes.

To obtain the polymer were then

Example 8 500 ml of methanol added to the reactor, the alcohol

50 holic slurry of polymer half a

Stirred in an hour provided with a stirrer, transferred to a 2-1 beaker, and 0.7-1 pressure stainless steel reactor were heated to boiling with stirring. The hot 0.28 g of 3 TiCl ₃ · AlCl ₃ slurry was filtered in an argon atmosphere, the filter cake was filled with 3.7 ml of a one molar solution of diethylaluminum for 1 hour with one liter of a 50:50 mixture of minium chloride in cyclohexane. The molar ratio of water and alcohol with a content of 0.5 g of aluminum to titanium was 2: 1. The reactor scraped lium carbonate. After filtering, the seal was closed, 0.35 atm hydrogen was applied, this washing was repeated without potassium carbonate and 400 ml of liquid was collected at 24 to 32 ° C. with stirring, and the propylene washed with the aqueous alcohol (density: 0.58 g / cm ³ ) supplied. The poly-polymers slurried in 50 ml of acetone. The polymerisation temperature was increased to about 65.5 ° C. within about 5 hours in a vacuum for up to 10 minutes. The 80 ° C dried.

The pressure at this point corresponded to that of the pro-It was a yield of 110 g of dry, pylene monomer in equilibrium. After a powdery polymer with an average Mo hour at 65.5 ° C, the reactor was blown off, molecular weight of about 580,000 to 680,000, one purged with argon and cooled to 43.5 ° C. Intrinsic molar viscosity of about 4.9 and a half of 2 minutes were obtained in the polypropylene in the melt index at 230 ° C of 0.9. The phy reactor gradually introduced 5 g of liquid hexene (l) (density: physical properties of the polymer are in the 1.38 g / cm ³ ). Listed after completing the table.

Tabel

10

Comonomer content ') 9rhmpi7- Heptane Crystal Notched bar Gurley tensile strenght IVlUUUl
at 1% Be
load-10- ³ example
No. O CIl 11 IClZ.-
index at
23O ⁰ C unsolvable
liches liner
Enamel embrittling
temperature Steepness
mg / 0.0508 at the
Stretch limit 17 o / o ethylene o / o ² ) point ³ ) O _C 4) cm ⁵ ) kg / cm ^{2 6} ) 178 1 0 4.3 92 168 + 4 6400 358.6 176 la 0 1.7 96.3 171 +50 6000 358.6 170 Ib 11% ethylene 3.4 96 17Y +55 7000 323.4 177 2 10% ethylene 0.2 90 167 -8th 5800 323.4 165 3 9% ethylene 0.7 93.4 169 2 5900 337.3 182 4th 5% ethylene 2.7 93 166 +5 7400 379.5 173 5 6% ethylene 5 91.5 168 + 18 7000 365.5 163 6th + 2% butene- ¹ ) 1.6 89 167 +5 7000 344.5 8% butene- ¹ ) 181 7th 5% ethylene 0.2 93 163 + 15 7900 337.3 174 8th 17% ethylene 4th 89 167 + 32 6000 365.5 130 9 0.9 88 167 -20 5500 323.4

^x ) Determined by infrared analysis.

² ) Determined by extraction with boiling heptane.

³ ) Determined under the microscope under crossed Nikols.

⁴ ) Determined in accordance with ASTM D 746-57 T, but with sheets 3.81 cm long, 0.635 cm wide and 0 cut from panels pressed at 204.4 ° C and cooled in the press at a rate of 3.89 ° C per minute 19 cm thick test pieces were clamped in the Scot test device with the broad side parallel to the baton and provided with a sharp razor blade with a 0.038 cm deep notch on the 0.19 cm thick side.

⁵ ) Determined in the Gurley stiffness tester.

⁶ ) Determined in accordance with ASTM D 638-60 T, however, 10.16 cm long, 0.635 cm cut from a plate pressed at 204.4 ° C, cooled at a rate of 3.89 ° C / min and measuring 15.24 cm wide and 0.0508 cm thick strips were clamped in the Instron tester with a jaw spacing of 2.54 cm and pulled apart at a speed of 50.8 cm / min. The modulus under a load of 1% was determined at a jaw distance of 5.08 cm with a pulling speed of 0.508 cm / min.

Example 10

The procedure of Example 5 was repeated, but now for the entire 60 minutes during which the propylene is polymerized at 65.5 ° C, continuously gaseous ethylene with a speed of about 0.008 per minute in

the reactor was introduced. The reactor was then blown off and, as in Example 5, ethylene was added. ■:. ■■ ;; '■■■

About 100 g of dry powdery polymer with a molecular weight above about 200,000 obtained which contained approximately 5.5% ethylene. The impact embrittlement temperature of the polymer was below 5 ° C.

Claims (1)

Claim: Thermoplastic molding compound, consisting of a) Polypropylene or a copolymer of at least 96 percent by weight propylene and up to 4 percent by weight ethylene and / or a C ₄ - to C ₈ -α-olefin and b) a polymer of the formulas PC or BPC or a mixture of such polymers, where B and C are each independently a polyethylene chain, a poly (C ₄ to C ₈ α-olefin) chain or a chain of a copolymer mixture represent two or more such ^{α-olefins 1S} and P is the chain of a polymer according to the definition given under a) and where the chains B and C together make up 1 to 40 percent by weight, based on the total mass, and the molecular weight (number average), determined by measuring the intrinsic viscosity of the polymers in the composition is at least 50,000. 25th