DE1230224B - Process for the production of completely crystalline copolymers of propylene and butene- (1) - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

CO8f

German: 39 c -25/01

Number: 1230224

File number: R 37449 IV d / 39 c

Filing date: March 13, 1964

Opening day: December 8, 1966

The invention relates to a method of manufacture completely crystalline copolymers of propylene and butene- (l) with increased molecular weight.

It is known to co-polymerize propylene and butene- (l) using the reaction product of trihexylaluminum with vanadium halides as the catalytic system (Chimica e Industria, 42, 1960, p. 468). The products thus obtained are amorphous, whatever the proportion of propylene and butene- (I) may be. It is also known to use mixtures of propylene and butene- (l), which contain up to 25 percent by weight of butene- (l), using di- or trichlorides of titanium or zirconium, which are formed by organometallic compounds of aluminum or a halide of these compounds are activated to copolymerize (USA.-: Patent 2,918,457). Polymer which must be removed to obtain the desired crystalline ^product: in the course of this polymerization, a considerable amount of amorphous forms. In addition, in such catalyst systems, the molecular weight of the polymer obtained is considerably reduced when the content of butene- (I) is increased. For example, the molecular weight decreases from 169,000 to 60,000 when the butene- (I) content is changed from 3 to 25%. The polymers with such a low molecular weight have limited application.

The invention now relates to a process for the production of completely crystalline copolymers of Propylene and butene (I), which is characterized in that a catalyst mixture is used for the polymerization used, that of a halide of a transition metal, an organometallic compound of aluminum, which may also contain halogen, and an ester, an amide or an ester amide the phosphoric acid, especially hexamethylphosphoramide, consists.

The catalyst systems used for this copolymerization are from the French patent 1,231,089 known for the production of crystalline polypropylene. These catalysts result in a crystalline polypropylene, but it has been found that its use in copolymerization of ethylene with propylene to form amorphous copolymers or mixtures of amorphous copolymers and crystalline homopolymers. It is therefore surprising that when using this Catalysts for the copolymerization of propylene and butene- (I) practically completely crystalline products can be obtained.

It has also been found that the process of manufacture completely
crystalline copolymers of propylene
and butene- (l)

Applicant:
Rhone-Poulenc SA, Paris

Representative:

Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Named as inventor:

Gibert Bo,

Philippe Perras, Lyon, Rhone;

Jean-Claude Quinat, Nantes-Loire atlantique

(France)

Claimed priority:

France of March 13, 1963 (927 838)

Copolymers produced according to the invention which contain 25 to 80% butene- (I), and in particular those containing 40 to 80% have excellent adhesive properties with respect to others Plastic materials, especially crystalline polypropylene, possess. These adhesive properties that the do not have amorphous polymers, make these copolymers valuable products for coatings and coverings for thermoplastic products and other substrates (paper) that are used for air and moisture want to make impermeable. In addition, this adhesiveness makes these products together their relatively low melting point, which is 125 ± 5 ° C, for the production of heat-sealable Valuable products made from a thermoplastic material made from for various reasons the elevated temperatures of the heat seal cannot withstand. So you can with the Manufacture of packaging bags and other similar products from polypropylene film common methods of heat sealing (heating rulers or baking) because of the permanent deformation (Shrinkage, wrinkling) that occurs along the weld line, a deformation that is due to the fact that the polymer must be heated to its melting temperature, which the

609 730/406

T 230

Impairment of the dimensional stability of the polypropylene film causes. In order to avoid these disadvantages, it was proposed to use the weld to make an intermediate layer of a thermally weldable thermoplastic resin, however, in order to achieve the adhesion of this intermediate layer to its support, it must be an electrical one Treatment (British Patent 913,476), possibly with the application of an undercoat on the carrier activated in this way (Belgian patent 613 561). When you on Films made of polyolefins a layer of the invention Applied copolymers produced, it is found that this layer without any preceding Treatment adheres firmly to its support and that the heat-sealing of the film without any Deformation at the weld seam is possible. The weld achieved in this way has a very good separation strength. In addition, the layer of copolymer that is inside the so produced changes Product, the quality of the gloss and the transparency of the polypropylene cover is in none Way that also maintains its smoothness.

These copolymers are completely in solvents, such as, for example, aliphatic and aromatic solvents or cycloaliphatic hydrocarbons, carbon disulfide and chlorinated solvents, like trichlorethylene, soluble. So you can find solutions with 2% in cyclohexane and solutions with 10% in Manufacture trichlorethylene.

For example

100 ecm of cyclohexane and 2 g of titanium trichloride are placed in an autoclave with a capacity of 500 ecm and 3.03 g of a mixture of 1.59 g of dichloroethyl aluminum and 1.44 g of hexamethylphosphoric acid amide. Purge with nitrogen and bring then 100 g of a mixture of propylene and butene- (I) in a certain molar ratio. One brings then place the autoclave in a thermostatic oven mounted on a vibrating device and its temperature is kept at 75 ° C. After 4 hours, the resulting from the polymerization is treated resulting mass with 500 ecm of methanol and filtered to separate the polymer. This lies in the form of blocks that can be converted into fine leaflets

ao cuts and by heating with 500 ecm of methanol treated under reflux for 24 hours. NaGh filtering and drying gives a white polymer, which is crushed to a powder by grinding. The characteristics of having monomers

as mixtures of propylene and butene- (l) in different The copolymers obtained by molar ratios are shown in the table below.

sample Propylene
Mole percent Butene (1)
Mole percent Specific
viscosity Insoluble
in acetone Optical
Melting point
° C 1 75 25th 0.720 92 148 to 149 2 70 30th 0.922 97.5 149 3 58 42 0.466 95.4 132 4th 45 55 0.674 93.5 125 5 35 65 0.791 98.2 125 6th 25th 75 0.922 98.5 125 7th 10 90 0.628 97.1 125

The viscosity of the products obtained is with 0.2% solutions in tetrahydronaphthalene 130 ° C is determined, and its optical melting point is determined with a polarizing microscope.

Examination of the X-ray diagram of these products shows a practically crystalline structure.

Example 2

1500 ecm of cyclohexane, 5 g of titanium trichloride and 22.71 g of a mixture of 11.91 g of dichloroethylaluminum and 10.80 g of hexamethylphosphoric acid amide are placed in an autoclave of 3600 ecm. The autoclave is flushed with nitrogen and a mixture of 210 g of propylene and 280 g of butene- (l) is then introduced. The mixture is then heated at 115 ^° C. for 6 hours, constant movement being ensured. The polymerization mass is then washed with 3000 ecm of methanol. The polymer, which is separated off by filtration, is cut into fine flakes, which are refluxed for 24 hours with 3000 ml of methanol containing 10% hydrochloric acid. After filtering, washing and drying, a white polymer is obtained, the specific viscosity of which, measured as in Example 1, is 0.200. The viscosity number is 0.94. X-ray testing and differential thermal analysis show that the polymer is completely crystalline.

A biaxially oriented polypropylene film is coated using a solution in trichlorethylene with 2 % of this copolymer. The amount of coating is 2.5 g / m ² . The welds of heat-sealed foil show a strength of 184 to 210 g / cm.

One prepares 2% solutions of samples 3 and 4 of the above table in cyclohexane, to which one 0.6 percent by weight of a stabilizer is added, which is made from a mixture of equal parts by weight of 4,4'-bis- (tert-butyl-6-m-cresol) -butylidene and lauryl thiodipropionate; the dissolution is accelerated by heating at 60 to 70 ° C under a nitrogen the atmosphere. In the solutions obtained in this way, biaxially stretched polypropylene films are immersed then dries for 5 minutes in a drying cabinet at 60 to 70 ° C. On each surface you have 1.5 to 3 g of the copolymers are applied per square meter of film. The foils have their initial appearance maintained. One finds by a peel test with an adhesive tape that the adhesiveness of the Copolymers on the polypropylene film is good and this adhesiveness after 24 hours of immersion in Water is maintained at 20 ° C. These foils also hold up to a 5 minute immersion in boiling Water out without any puckering or any other change in its appearance.

The heat sealing is carried out with the help of a welding device with a heating ruler, which at a

Temperature in the vicinity of 125 ⁰ C is kept. The welding tests are carried out with two surfaces which are coated in the same way or with a coated foil in connection with an uncoated foil. The strength of the weld is determined by dynamometric measurements of the separation strength, which are carried out on samples 15 mm wide. In the case of welds of two coated surfaces, this strength varies from 220 to 360 g (146 to 240 g / cm), depending on the amount of the deposited copolymer. In the case of welding a coated surface to an uncoated surface, this separation strength varies from 110 to 180 g (75 to 120 g / cm). In both cases, the products obtained show neither shrinkage nor deformation at the point of weld.

A comparison test of the heat sealing with the uncoated polypropylene f oh'e shows that that this film cannot be welded under the same conditions.

Samples of copolymers prepared as in Example 1 are heated, as described above, but dissolved in trichlorethylene.

These kept at 5O ⁰ C strip solutions are coated biaxially stretched polypropylene film and dried at 100 ⁰ C.

The peel test with the adhesive tape shows that the adhesion of the coating to the film is perfect is.

Various foils are heat-sealed with the coated surfaces facing each other, under the following conditions.

A film is folded in such a way that the coated surfaces are opposite, with the fold is perpendicular to the squeezing direction.

Samples are cut from this film in the direction of pressing out and starting from the fold with a width of 37.5 mm and a length of ίο a total of 500 mm.

Each folded sample is placed on a steel heating ruler held at 100 ° C. and subjected the pressure of a roll (covered with polytetrafluoroethylene) with a width of 27 mm and a Weight of 750 g, the six passages (three to and fro) in 1.5 seconds at 4 cm of the fold across feels the full width of the sample. After cooling for 5 to 15 minutes, the samples are subjected to a detachment test in a dynamometer according to L h ο m m e and A r g y. The pull speed is 20 mm / min. and you stop pulling after the bond has broken completely.

One also tests the water resistance of the seals by taking a series of samples throughout Immerse in boiling water for 30 minutes before performing the tensile test.

The results are compiled in the table below.

Coating solution Polymer % Butene- (1) concentration viscosity t ° C Coating Strength of seals after immersion % Propylene 42 % W / v cP 67 weight
(Dry matter) as such 58 50 1.93 80 67 g / m ^a 134 50 70 1.89 65 70 2.7 142 (R) *) 147 30th 80 1.46 45 67 3.5 120 (R) *) 80 20th 90 1.22 30th 69 2.0 58 (R) *) 100 10 100 1.43 30th 67 3.5 61 35 1.20 30th 3.8 19th 29 4.0 33

*) R = tear

It is found that the boiling water treatment does not affect the strength of the seal in any way reduced.

For contents of 40 to 70% of butene, the separation test does not lead to any detachment of the seals, however, tearing of the film itself, which affects the value of the seal with regard to the strength of the copolymer, that adheres to the polypropylene, still highlights.

Claims (1)

Patent claims: Process for the production of completely crystalline copolymers of propylene and butene- (l), characterized in that a catalyst mixture is used for the polymerization, that of a halide of a transition metal, an organometallic compound of Aluminum, which can also contain halogen, and an ester, an amide or an ester amide the phosphoric acid, especially hexamethylphosphoramide, consists. A priority document was displayed when the registration was announced. 609 730/406 11.66 © Bundesdruckerei Berlin