DE1235501B - Use of homopolymers or copolymers of 3-methyl-1-hexene for the production of threads or films - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

DOIf

German class: 29 b-3/65

Number: 1235 501

File number: E 21430IV c / 29 b

Filing date: July 26, 1961

Open date: March 2, 1967

It is known that polyolefins can be shaped into films and spun into threads. However, the polyolefins used hitherto, in particular for the production of threads, always have at least one disadvantage which limits their general usability. So the known polyethylenes for example, have only melting points of about 115 to 132 ° C and the known polypropylenes only melting points of about 170 to 175 ⁰ C. As a result, can not be used wherever you need high melting points, ie from these polyolefins spun yarns for example not for the production of tire cord.

Other known polyolefins, such as. B. 3-methyl-1-butene and 4-methyl-1-pentene, have high melting points of about 300 ° C and 245 ° C, respectively, however the disadvantage that they can only be processed at temperatures above the so-called threshold temperature lying, d. H. the temperature at which the polymers are thermally degraded. When spinning therefore, only threads are obtained from polymers of 3-methyl-1-butene and 4-methyl-1-pentene with uneven molecular weight that are easily broken.

The invention was therefore based on the object of finding a polyolefin which has the disadvantages of does not have known polyolefins, d. H. in particular has a high melting point and, without to be thermally degraded, spun and drawn into threads of excellent quality and can be processed into foils.

It has been found that of the enormous number of possible olefins, 3-methyl-1-hexene is different excellent for the production of polymers that have the required properties.

With regard to the large number of known olefins that have been used to date for the production of threads and films have been suggested, however, for one or other of the reasons listed for many purposes can not be used, as well as the properties of structurally very similar olefins, such as. B. des 3-methyl-1-butene and 4-methyl-1-pentene was not to be expected that of all things according to the present application used 3-methyl-l-hexene would provide polymers that are excellent for Production of foils and threads would be suitable. The 3-methyl-1-hexene is completely unexpected for the production of polymers with high melting points and at the same time excellent deformation properties, d. h., The polymers can be in In contrast to other, very similar polymers, it is easy to process into foils and spin them into threads.

Use of homo- or
Copolymers of 3-methyl-l-hexene for
Manufacture of threads or foils

Applicant:

Eastman Kodak Company,
Rochester, NY (V. St. A.)

Representative:

Dr.-Ing. W. Wolff and H. Bartels,

Patent attorneys, Stuttgart N, Langestr. 51

Named as inventor:
Newton Henry Shearer Jr.,
Kingsport, Tenn .;
Milton Armor Perry,
Longview, Tex. (V. St. A.)

Claimed priority:

V, St. ν. America 11 August 1960 (48 842)

The subject matter of the invention represents a significant enrichment of technology than before no olefin polymers have become known which have the same good properties as those in the invention have described polymers when used for the production of threads or films.

Surprisingly, it has further been found that / ₀ from crystalline polymers of 3-methyl-l-hexene spun yarns by about 800 to 1000 ° and can stretch oriented filaments 8-9 g / denier.

The invention therefore relates to the use of homopolymers or copolymers of 3-methyll-hexene with a molecular weight of 1,000 to 250,000, preferably 20,000 to 60,000, for production of threads or foils.

The softening points of the homopolymers are generally above 200 ° C and usually between about 210 to about 215 ⁰ C. The densities of at least 0.87 and between about 0.88 and 0.91.

For the production of copolymers with 3-methyl-1-hexene, α-olefins with in particular are suitable up to 10 carbon atoms, such as ethylene, propylene, pentene, hexene, decene, dodecene, 5-methyl-l-hexene, 1-hexene, 4-methyl-l-pentene, but also compounds

709 517/516

such as styrene, butadiene, allylcyclohexane, allylcyclopentane. Particularly advantageous processing properties have copolymers of 3-methyl-1-hexene with ethylene or propylene.

The 3-methyl-1-hexene required for the production of the polymers used according to the invention can according to the usual known processes which are used for the production of -olefins will. A particularly suitable process consists in the preparation of 3-methyl-1-hexanal by Hydroformylation of 2-methyl-1-pentene and subsequent Reduction of the 3-methyl-1-hexanal obtained to 3-methyl-1-hexanol. The alcohol will then acetylated with acetic anhydride and pyrolyzed over glass at 500 ° C.

Production of those which can be used according to the invention
Polymers

The polymerization of 3-ethyl-l-heptene can be carried out continuously or batchwise, in solution or in slurry. Possibly chain transfer agents such as hydrogen can be present in the polymerization.

The polymerization takes place in the presence of the customary, known, solid, stereospecific polymerization catalysts, which consist of at least two components, namely a salt of one of the transition elements of IV. to VI. Subgroup of the periodic table of chemical elements and an activator therefor. As transition elements are called: titanium, zircon, vanadium, molybdenum, chromium. In the salts used, the metals in their maximum value or in a lower value level. Examples of suitable salts are titanium tetrachloride, titanium tetrabromide, titanium trichloride, titanium tribromide, zirconium tetrachloride, vanadium trichloride, Molybdenum pentachloride, chromium trichloride.

Suitable activators are, for example, metal alkyls, metal alkyl salts and metal hydrides of aluminum, Zinc or metals from main groups I and II of the periodic table, as well as metals alone, for example sodium, potassium, lithium, zinc, amyl sodium, butyl potassium, propyllithium, dibutyl zinc, Diamyl zinc, dipropyl zinc, ethyl magnesium bromide, sodium hydride, calcium hydride, lithium aluminum hydride, Triethyl aluminum, tributyl aluminum, ethyl aluminum dichloride, cyclohexyl aluminum dichloride, Cyclobutyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum sesquichloride, Ethyl aluminum sesquibromide, dimethyl aluminum bromide, propyl aluminum dichloride, dibutyl aluminum chloride, Diethyl aluminum chloride.

In order to increase the stereospecific effect of the catalyst, the catalyst can also consist of three Components exist, the third component z. B. from a salt of an alkali metal, magnesium oxide, an aromatic ether, a hydride of aluminum, potassium and lithium, an alcoholate of sodium, potassium, lithium, calcium, magnesium, barium, strontium, aluminum, titanium and zirconia. In addition, tertiary amines or tertiary amines can be used as third components Phosphoramides, for example together with alkyl aluminum salts, be used.

In general, it has proven advantageous to use a molar ratio of activator to metal salt of 0.1: 1 to 12: 1 to be used. If the catalyst consists of three components, there is a molar ratio of the metal salt to the third component of about 1: 0.1 to about 1: 2 is sufficient. The concentration the catalyst in the reaction medium can be very different. Concentrations are appropriate from 0.1 or less to 3% of the more used.

The polymerization can be carried out under pressure, e.g. B. at atmospheric pressure or pressures up to about 70 kg / cm ² , and at temperatures from 0 to 250 ⁰ C, preferably 40 to 90 ⁰ C.

The polymerization can be carried out in the presence of e.g. B. aliphatic alkalis or cycloalkanol, such as pentane, Hexane, heptane or cyclohexane, or aromatic compounds such as tetrahydronaphthalene or decahydronaphthalene, be performed. Aromatic hydrocarbons, such as benzene, toluene, xylene, or halogenated aromatic compounds such as chlorobenzene, chloronaphthalene or orthodichlorobenzene can be used. Other suitable solvents are, for example Ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene, mono- and dialkylnaphthalenes, Methylcyclohexane.

For the preparation of 3-methyl-1-hexene and the preparation described in the following examples No protection is claimed here for the polymers used according to the invention.

example 1
a) Production of 3-methyl-l-hexene

10 g of triethylaluminum, 30 ml of dry heptane, 0.5 g of nickel acetylacetonate and 1.2 g of 1-hexyne were mixed with one another in a drying chamber filled with nitrogen. This mixture was then placed in an autoclave while being purged with nitrogen. Then 600 ml of liquid propylene were added, whereupon the autoclave was heated to 200 ° C. for 12 hours with shaking. After cooling to room temperature and releasing the pressure, the reaction mixture was placed in a flask cooled with dry ice. The reaction mixture was distilled from this flask by means of a 60.9 cm long column filled with glass bodies. 230 g of 2-methyl-1-pentene with a boiling point of 61 to 62 ^° C. at a pressure of 743 mm were obtained. The refractive index n'S was 1.3920.

70 g of 2-methyl-1-pentene and 3 g of cobalt carbonyl were placed in an autoclave under nitrogen, whereupon a mixture of carbon monoxide and hydrogen was injected ^{into the autoclave up to a pressure of 141 kg / cm a.} The reaction mixture was then ^{heated to 140 °} C. until a constant pressure of 211 kg / cm ^a had been established. The autoclave was then ^{cooled to 25 °} C. and emptied. A solution of 6 ml of concentrated hydrochloric acid in 100 ml of water was added to the reaction mixture, and the mixture was refluxed for 2 hours. The water layer was separated and discarded. The residue consisted of crude 3-methyl-1-hexanal. This was placed in an autoclave and 8 g of Raney nickel washed with alcohol was added. The autoclave was then brought to a pressure of 141 kg / cm ² by forcing in hydrogen. At this pressure and a temperature of 125 ^° C., 4 ¹ l was reduced for _{2 hours.} The catalyst was then filtered off and the filtrate

1 235 5Ql

distilled. The 3-methyl-1-hexanol obtained underdistilled at a temperature of 163 to 167 ° C a pressure of 734.2 mm. It had a refractive index η ?? of 1.4233.

In a flask connected to a reflux condenser was placed 560 g of acetic anhydride, which was heated to reflux temperature. Then 580 g of 3-methyl-1-hexanol was added dropwise and the reaction mixture was refluxed for 3 hours. The acetic acid and the unreacted components were then distilled off from the reaction mixture. By distillation of the residue was 173 g of 3-methyl-1-hexyl acetate having a boiling point 178-181 ⁰ C at atmospheric pressure condition. The compound had a refractive index of rf§ of 1.4144.

474 g of 3-methyl-l-hexyl acetate were / fed at a rate of 2 g min through heated to 500 ⁰ C glass beads. The crude reaction product was washed with water, then with alkali and finally with water again. After drying over calcium chloride, it was distilled. There were 104 g of 3-methyl-l-hexene having a boiling point of 82 ⁰ C, refractive index nl ° = 1.3966, was obtained. The 3-methyl-1-hexene was dried over sodium hydride and then distilled off therefrom to obtain a dry product.

b) Preparation of the polymer

0.57 g of triethylaluminum, 1.57 g of vanadium trichloride, 40 ml of benzene and 30 g of 3-methyl-1-hexene were introduced into a 500 ml pressure bottle in a drying chamber in a nitrogen atmosphere. The pressure bottle was then capped, removed from the drying chamber and placed on a shaker. The pressure bottle was then heated ^{to 75 ° C. for 12 hours.} The polymer obtained was cooled with shaking and then washed several times with methanol in order to remove the catalyst. After drying in an air oven at 5O ⁰ C was poly (3-methyl-l-hexene) obtained in the form of a white powder. The yield was 25 g. The softening point of the polymer was 210 to 215 ° C. The intrinsic viscosity of the polymer was 1.05.

When the experiment is repeated with 0.57 g of triethylaluminum and 1.54 g of titanium tetrachloride as a catalyst were 20.5 g of poly (3-methyl-l-hexene) having an intrinsic viscosity of 2.14 and a softening point 215-220 ⁰ C. obtain.

In a further experiment, 100 g of 3-methyll-hexene were polymerized in an autoclave with a capacity of 285 ml using 2 g of a catalyst consisting of ethylaluminum sesquisalt and hexamethylphosphoric acid triamide and titanium trichloride in a molar ratio of 2: 1: 3. After a polymerization time of 4 hours at 85 ⁰ C was added 91.3 g of poly (3-methyl-l-hexene) obtained with an intrinsic viscosity of 4.82 and a softening point 212-214 ° C.

c) Use according to the invention for production
of foils and threads

In all cases, threads with excellent results could be obtained from the polymers obtained by customary processes Spinning properties and pressing films with excellent properties.

Example2
a) Preparation of the polymer

21.0 g of 3-methyl-1-butene and 68.6 g of 3-methyl-1-hexene as well as 0.4 g of triethylaluminum and 0.6 g of vanadium trichloride were placed in a pressure bottle. The autoclave was then heated to 7O ⁰ C and shaken it. After a polymerization time of 6 hours, ethanol was added to the reaction mixture. 41.7 g of copolymer could be isolated. The copolymer consisted of about 35 ° / ₀ of 3-methyl-l-butene and 65% 3-methyl-l-hexene units. The softening point of the polymer was 205 ^° C.

b) Use according to the invention for production
of threads and foils

A film pressed from the polymer by a known process was transparent and tough. Threads that were spun from the copolymer by conventional methods had strength of 4.8 g / denier.

Example3
a) Preparation of the polymer

20.4 g of styrene, 19.6 g of 3-methyl-1-hexene, 0.27 g of triethylaluminum and 0.73 g of vanadium trichloride were placed in a pressure bottle. The pressure flask contents were heated to 7O ⁰ C. After a polymerization time of 8 hours, ethanol was added to the reaction mixture, as a result of which 34.4 g of copolymer could be isolated. The copolymer consisted of about 50% 3-methyl-1-hexene units and 50% styrene units. The softening point of the copolymer was 198 ^° C.

b) Use according to the invention for production
of threads and foils

Clear, tough films could be pressed from the copolymer by known processes and threads with a strength of 6.2 g / denier could be spun by conventional processes. Both the films and the filaments were oriented by stretching at 100 ⁰ C.

Example 4
a) Production of a polymer

A mixture of 65 mole percent 3-methyl-l-hexene, and was added 5-methyl-l-hexene 35 mole percent of at 7O ⁰ C with a catalyst consisting of 0.43 g of triethylaluminum and 0.57 g of titanium trichloride, polymerized. When using 40 g of monomers, 36.3 g of a copolymer were obtained which consisted of 62.6% 3-methyl-1-hexene units and 37.4% 5-methyl-1-hexene units.

b) Use according to the invention for production
of threads

Highly elastomeric threads with excellent results could be produced from the copolymer using a known process Properties are woven.

Example 5
a) Preparation of the polymer

48 g of 3-methyl-1-hexene and 32 g of 1-hexene were polymerized in the presence of 1 g of a catalyst consisting of ethylaluminum sesquichloride, hexamethylphosphoric triamide and titanium trichloride in a molar ratio of 2: 1: 3. The polymerization was carried out at 7O ⁰ C with shaking. After a reaction time of 6 hours, the reaction mixture was diluted with isobutyl alcohol, whereupon the precipitated polymer was washed several times with hot isobutyl alcohol. The dry polymer was then extracted with diethyl ether to remove the amorphous constituents. The residue of the extraction was extracted with hot heptane at about 70 ⁰ C. The copolymer obtained was isolated from the heptane extract obtained. A total of 40.3 g of copolymer was obtained.

b) Use according to the invention for production
of threads and foils

The copolymer could easily be converted into thin, clear, shed tough foils. Furthermore, drawable threads with excellent properties decreased the melt spinning process, dry spinning process and wet spinning process. The received Threads could be drawn into threads with strengths of 3 to 5 g / denier.

Example 6

The procedure described in Example 5 was repeated except that the 1-hexene through Allylcyclohexane was replaced. The copolymer obtained was also easy to clarify, Potting tough foils and making elastic threads with high strength using the melt spinning process to process.

Equally favorable results were obtained when copolymers of 3-methyl-1-hexene and 4-methyl-1-pentene, allylcyclopentene or 1-pentene were used.

Claims (1)

Claim: Use of homopolymers or copolymers of 3-methyl-1-hexene with a molecular weight from 1000 to 250000 for the production of threads or foils.