USE OF AN ETHYLENE POLYMER COMPOSITION FOR THE PRODUCTION OF FILM

Abstract: Use of compositions based on ethylen polymers for the production of film. The compositions comprise an essentially linear ethylene polymer which has a density not exceeding 935 kg/m³ and a molecular weight distribution not exceeding 18. The ethylene polymer contains a small number of short aliphatic branches from alpha-olefins having not more than 14 carbon atoms. The compositions comprise certain phosphorous com­ pounds, phosphites, phosphonites or phosohonic acid derivat­ ives, in an amount of at least 0.005 per cent by weight, based on the ethylene polymer. Films produced from the compositions have very satisfactory optical properties.

Description: USE OF AN ETHYLENE POLYMER COMPOSITION FOR THE PRODUCTION OF FILM The 'present invention relates to the use of compositions based cn ethylene polymers for the production of film. ore particularly the invention relates to the use of compositions based on an essentially linear ethylene polymer of low density and certain phosphorus compounds for this purpose. The use of phosphorus compounds as stabilizers in polyolefins is well-known. According to the US patent 4,187,212 a combination is used for stabilization of polyolefins, such as polyethylene and polypropylene, against thermooxidative deterioration. It is further known to use this kind of phosphorous compounds, triarylphosphites, in specific polyethylene materials produced with Phillips catalysts - a chromium -containing catalyst. This is for example described in the European patent application 0 000 025. According to this application, and closely related applications, e.g. European patent application 0 005 269, tris-(2,4-dialkylphenyl)-phosphite is used in Phillips-polyethylene to make the production of thin films possible. The base polymers, which are used, have densities varying between 935 and 960 kg/m3. Ethylene polymers, which are essentially linear, have low density amend fairly narrow molecular weight distribution, can be produced by specific methods, e.g. by gas-phase polymerization at low pressures. Films can be produced from these polymers without any greater problems and the polymers permit production of thin films without requirement on special additives. Films from these polymers do, however, not have satisfactory optical properties. A reduced gloss of the film is particularly -noticeable, compared with conventional polyethylene. According t the present invention, it has been found, that composiv-ons based on an essentially linear ethylene dyer of lo density and fairly narrow molecular weight distribution and certain phosphorous compounds, namely phosphites, phosphonites and phosphonic -acid derivatives, are very suitable for film production. Use op the mentioned phos @@@@@@s comp@@@@@ lead to an improvement in the optical pro- perties of the produced film, and particularly to an improve- ment of the gloss. The present invention thus relates to the use of an ethylene polymer composition for the production of film, which composition essentially comprises an ethylene polymer and at least 0.005 per cent by weight, based on the ethylene polymer, of a phosphite, phosphonite or phosphonic acid derivative, which will be defined in more detail in the following. The ethylene polymer in the composition is essentially straight and is a copolymer of ethylene and up to 20 per cent by weight, based on the ethylene polymer, of one or several alpha-olefins, having 3 to 14 carbon atoms. The ethylene polymer has a density of not more than 935 kg/m3 and a molecular weight distribution, Mw/mn, of not more than 18. the molecular weight, Mw, of the ethylene polymer should suitably be within the range 25000 to 500000. The phosphorous compounds in the compositions are seelected frdm the groups a) phosphites and phosphonites and b) phosphonic acid derivatives. The compounds in the group a) can be characterized by the general formula EMI2.1 wherein R1, R2 and R3, independent of each other, are alkyl, aryl, alkoxy or phenoxy groups, whereby the alkyl and alkoxy groups contain 1 to 30 carbon atoms. As mentioned R1 can be an aryl group and this includes also ring systems comprising two or three ring structures, e.g. bisphenylylene-derivatives. Aryl and phenoxy groups can be alkyl substituted in 2-, 3-, - and/or 5-position. Alkyl substituents do then suitably have 1 to 15 carbon atoms, and preferably 1 to 9 carbon atoms. This formula comprises as well symmetric and asymmetric phos whites as compounds of the di-phosphonite type. Particularly preferred compounds in this group are tris alk-ylphenyl-phosphites, tris-(2,4-dialkylphenyl)-hosphlts no tetrakis(2,.4-dialkylphenyl)-I4,-bisphenylylene-diphospho- I=. n the trisalkylphenyl-phosphites the alkyl groups are preferably nonyl groups. The alkyl groups in the two other mentioned phosphites and phosphonites have 1 to 9 carbon atoms.Particularly preferred compounds in the present compositions are trisnonylphenylphosphite, tris-(2,4-di -tert.butylphenyl)-phosphite and tetrakis(2,4-di-tert.butyl phenyl)-4,4'-bisphenylylene-diphosphonite. The phosphonic acid derivatives in the group b) can be characterized by the general formula EMI3.1 wherein R is hydrogen, a straight or branched alkyl group with 1 to 30 carbon atoms, an aryl group or a substituted aryl group, R1 and R2 independent of each other are hydrogen, a metal, or has the same meaning as R and n is an integer between 1 and 10, preferably 1. As examples of suitable metal salts of the alkyl phosphonic acids can be mentioned the salt of zink, nickel, calcium, sodium, titanium and aluminium. The phosphonic acid derivatives are suitably phosphonic acid, mono-esters or metal salts, and particularly such ones, wherein R is a phenyl group, substituted with one hydroxy group and two lower alkyl groups, having 1 to 6 carbon atoms, preferably tertiary butyl groups, n is 1 and R1 is hydrogen, metal, or a straight or branched alkyl group, having up to 22 carbon atoms. As examples of suitable phosphonic acid derivatives can be mentioned 0-ethyl-(IA-hydroxy-3,5-di-tert.butylbenzyl)- -phosphonic acid, 0-(2-ethyl-hexyl)-(4-hydroxy-3,5-di-tert.- butyl-benzyl)-phosphonic acid, O-stearyl-(4-hydroxy-3,5-di -tert.butyl-benzyl)-phosphonic acid, 4-hydroxy-3,5-di-tert.butyl-benzyl-phosphonic acid and O-stearyl-stearyl-phosphonic acid. The phosphorous compounds are present in the compositions in amounts of at least 0.005 per cent by weight, based on the ethylene polymer, and the amount should suitably be within the range 0.005 to 1 per cent by weight, preferably within the rane 0.005 to -0.5 per cent by weight. 2he nost .rmener¯ed phosphorous compounds are the previously mentioned phospites and diphosponites. The ethylene polymers, which form the base material in the present compositions are essentially linear, have a low density and a fairly narrow molecular weight distribution. In this respect they are radically different from conventional, by radical-initiation high pressure polymerization, prepared polyethylene of corresponding density, which has a branched, complex molecular structure and a broad molecular weight distribution. Ethylene polymers to be used in the compositions of the invention can be prepared by co-ordination polymerization in the presence of metal-organic catalysts, e.g. by low pressure processes in slurry, solution or gas -phase, whereby the polymerization conditions and the catalysts are selected to give an essentially linear polymer. The catalysts can for example be based on chromium or titanium. Catalysts based on titanium are preferred. By linear polymer should be understood, that the branching, that occurs in the polymer, is dependent essentially only on the type and amount of comonomers. Preferably, ethylene polymers produced by a gas-phase process are used in the compositions, and particularly such polymers produced by the recently commercialized, so-called Unipol"-process. An example of this process is described in the Swedish patent 7603163-2. The process can be carried out in such a manner, that the polymerization of the monomers occurs in-a gas-phase in a fluidized bed of already formed granules of the polymer at a pressure of 5 to 25 kg/cm2 and a temperature of 75 to l250C. A catalyst based on titanium, magnesium and aluminium as active components, e.g. according to the European patent applications 0 004 645, 0 004 646 and 0 004 647, is injected continuously in the bed in an amount of 100 to 500 pp, based on the amount of added monomer. The polymerization reaction is carried out in the presence of hydrogen gas. The ethylene polymers in the compositions should be essentially linear, and the content of aliphatic branches, having a chain length of more than 12 carbon atoms, should be negligible. The greater part of the branches should in themselves be straight and not branched. The amount of snsHv aliphatic branches in the ethylene polymer should be between 1 and 60 per 1000 carbon atoms in the chain, and suitably between 5 and 30 per 1000 carbon atoms. The length of the branches should be between 1 and 12 carbon atoms, suitably between 1 and 8, and preferably between 1 and 4 carbon atoms. Ethylene polymers of this structure can be prepared by copolymerization of ethylene, and up to 20 per cent by weight, based on the polymer, of alpha-olefins, having 3 to 14 carbon atoms. One or several such comonomers can be employed. The density of the polymer material should not exceed 935 kg/mê, and is suitably within the range 910 to 935 kg/m . The amount of comonomer for a given density is adapted with respect to length of the comonomer, or comonomers, and greater amounts are required, when shorter comonomers are employed. The ethylene polymer suitably contains from 1 to 20 per cent by weight comonomer, and preferably from 3 to 10 per cent by weight, and the comonomers are alpha-olefins, having 3 to 14 carbon atoms. The comonomer, or comonomers, are suitably C3 to C10 alpha-olefins, and preferably C3 to C6 alpha-olefins. As examples of suitable comonomers can be mentioned propylene, l-butene, l-pentene, l-hexene, 4-methyl-pentene, l-octene. When the ethylene polymer is a copolymer, containing two or more monomers, besides ethylene, it is suitably a terpolymer of ethylene, propylene, or butene, and one higher olefin. The molecular weight distribution of the ethylene polymer should not be too broad, if the desired properties of the polymer are to be obtained. The molecular weight distribution can be established by gel chromatography, and is here given jays the ratio M /M . The ratio should not exceed 18, w n and it should be within the range 1 to 18. It is suitably within the range 1 to 10, and preferably within the range 1.5 to 6. The average molecular weight, Mw, should be roughly between 25000 and 500000, and is preferably between 50000 and 2500-D. Another measure of the molecular weight, used in ethylene polymer technology, is the melt index (MI2, vis cosity = ;OC, given as grants of material flowing from a s 2n^r--¯e^ ts equipment per 10 minutes). For ethylene polymers in the present compositions the melt index, MI2, according to ISO R 292, should be between 0.05 and 3, preferably between 0.2 and 2. The compositions are prepared by mixing the phosphorous compounds and the ethylene polymer by means of known mixing technique. The compounds can e.g. be mixed directly into the ethylene polymer in powder form, followed by extrusion, or they can be hot compounded into the ethylene polymer, followed by extrusion. Other additives, such as antioxidants, and processing aids of the metal-soap type, can, of course, also be incorporated in the compositions. Phenolic antioxidants can e.g. be incorporated in the composition, e.g. pentaerythrityl tetrakis g3-(3,5-di-tert.- butyl-4-hydroxyphenyl)-propionateJ, octadecyl-3-(3,5-di -tert.butyl-4-hydroxyphenyl)-propionate, and 2,6-di-tert.butyl-paracresol. These antioxidants are suitably used in amounts, exceeding- 0.01 per cent by weight, based on the ethylene polymer. It is particularly preferred, that the phosphorous compounds in the compositions are used in combination with metal salts of fatty acids, e.g. calcium, zink or potassium salts. The term fatty acids is here used for aliphatic monocarboxylic acids, having from about 6 carbon atoms to about 20 carbon atoms. Preferably, metal stearates are used. Combinations of phosphorous compounds and metal soaps give film, having excellent optical properties. The metal soaps are suitably used in amounts of 0.1 to 1 per cent by weight, based on the ethylene polymer. A suitable weight ratio of phosphorous compounds and metal soap is from 1: ?5 to 25:1 preferably from 1:20 to 1:2. Film preferably biaxially oriented film, is produced from the above described ethylene polymer compositions in a conventional manner by casting or blowing, preferably by blowing. The blow ratio can hereby be within the range 1:1 to 5:1, and can suitably be up to 2:1. The thickness of the produced film can vary between 5 to 300 ym, and is preferably from 10 to 200 cm. The produced films have very favourable optical properties. The invention is further illustrated in the following examples which, however, are not intended to limit the same. Parts and per cent relates to parts by weight and per cent by weight, respectively, unless otherwise stated. Example 1 A base polymer was prepared from ethylene and about 7 per cent by weight of butene, according to the Unipol -process. The polymer material had the following properties: MI2 (according to ISO R 292) 1 MW/Mn 3-5 Density (according to ASTM-D 2839-69) kg/m3 919 Films were produced from compounds of this base polymer as such and from this and additives according to the invention. The base polymer and the additives were hot compounded in a twin screw mixer in laboratory scale at a temperature of about 2000C. 40 cm thick film was produced by blowing at 2350C at a blow ratio of 2:1. An extruder,-having a screw diameter of 30 mm and a 80 mm die, was used. Gloss, according to ASTM-2457, and haze in %, according to ASTM-D 1003, were measured on the produced films. The results are shown in the table below. The abbreviation TBPP is used for tris-(2,4-di-tert.butylphenyl)phosphite. Additive Amount % Gloss Haze 40 34 TBPP 0.1 99 16 TBPP 0.2 87 25 TBPP/Zn-stearate 0.1/0.3 100 16 TBPP/Zn-stearate 0.1/0.5 117 14 TSPP/Zn-stearate 0.03/0.5 110 15 Zn-stearate, comparison 0.3 70 28 Zn-stearate, comparison 0.5 75 25 Example 2 Compcunds and films we-re produced from the same base cer as in example 1 and according to the same technique. instead of phosphite, tetrakis(2,-di-tert.butylphenyl)-,4'- -bisphenylylene-diphosphonite was used. The latter is referred to as phosphonite below. Gloss and haze were measured on the produced films and the results are shown below. Additive Amount Z Gloss Haze 40 34 Phosphonite 0.1 93 21 Phosphonite 0.2 85 26 Phosphonite/Znstearate 0.1/0.5 97 17 Phosphonite/Znstearate 0.03/0.5 95 17 Example 3 Compositions according to the invention were prepared from the same base polymer as in example 1 and films were produced from the compositions. The base polymer and the additives were hot compounded in a Banbury-mixer in production scale at a temperature of 2200C. 40 fm thick film was produced by blowing at 235 C, blow ratio 2:1. An extruder, having a diameter of 70 mm and a 200 mm die, was used. The results from measurements of gloss and haze are shown in the table below. Additive Amount % Gloss Haze 60 30 TBPP q. 13 110 13 TBPP/Zn-stearate 0,03/0.5 108 14 Example 4 Compositions according to the invention were produced from the same base polymer as in example 1. The base polymer and the additives were hot compounded in a conti nuous mixer in production scale at a temperature of 220 C. Films were produced from the compositions in the same manner as described in example 3. Gloss and haze were measured on the produced films. Additive cunt a Gloss Haze 6o 30 100 O.GH 100 15 T"?P/Zn-stear:ate C .08/0.5 105 s-xample Another batch of base polymer was prepared fro ethyl- ene and about 7 per cent by weight of butene according to the Unipol-process. The polymer material had the following properties: MI2 (according to ISO R 292) 0.9 MW/Mn 3.5 Density (according to ASTM-D 2839-69) kg/m3 918 Film was produced from compounds of this polymer as such and from this and additives according to the invent ion. As comparison film was also produced from compound of the base polymer and a phenolic antioxidant. The base polymer and the additives were hot compounded in a twin screw mixer in laboratory scale at a temperature of about 2000C. 40 cm thick film was produced by blowing at a temperature of 235 0C at a blow ratio of 2:1. An extruder having a screw diameter of 30 mm and a 80 mm die was used. The results from measurements of gloss and haze are shown below. The additives mentioned in the table are as follows: TBPP=tris-(2,4-di-tert.butylphenyl)-phosphite, TNPP=trisnonylphenylphosphite, Phosphonic acid derivative A=O-ethyl -(4-hydroxy-3,5-di-tert.butylbenzyl)-phosphonic acid, Phenolic antioxidant A=pentaerythrityl tetrakisJ3-(3,5-di- -tert.butyl-4-hydroxy-phenyl)-propionat S . Additive Amount ,0 Gloss Haze 60 24 TBPP 0.1 95 15 TIQPP 0.1 87 21 TNPP 0.2 89 17 Phosphonic acid derivative A 0.1 118 14 Phenolic antioxidant A, comparison 0.05 60 24 Phenolic antioxidant A, comparison 0.1 62 24 As evident from the results conventional phenolic antioxidants did not have any effect on the optical properties of the produced films. Example 6 The same base polymer as in example 5 was used. 'ilm was produced from compounds of the base polymer as such and of this with incorporated additives according to the invention. The base polymer and the additives were hot compounded in a twin screw mixer in semi-production scale at a temperature of about 2000C. Films were produced as in example 5. Gloss and haze were measured on the produced films. The following additives were used: TBPP=tris-(2,4-di-tert.butylphenyl)-phosphite, Phosponic acid derivative B=nickel salt of O-ethyl-(4-hydroxy-3,5-di-tert .butylbenzyl)-phosphonic acid. Additive Amount % Gloss Haze - - 80 20 TBPP 0.1 109 13 Phosphonic acid derivative B 0.1 116 14

Claims: Claims 1. Use of an ethylene polymer based composition, which composition substantially comprises an essentially linear ethylene polymer having a density not higher than 935 kg/m3 and a molecular weight distribution not higher than 18, which polymer contains 1 to 60 short aliphatic branches per 1000 carbon atoms in the chain, and at least 0.005 per cent by weight, based on the ethylene polymer, of a phosphorous compound selected from the groups phosphites, phosphonites and phosphonic acid derivatives for the production of film. 2. Use according to claim 1, whereby the ethylene polymer in the composition is a copolymer of ethylene and up to 20 per cent by weight of one or several alpha-olefins having 3 to 14 carbon atoms. 3. Use according to claim 1 or 2, whereby the ethylene polymer in the composition has a molecular weight distribution within the range 1 to 10. 4. Use according to any of the preceding claims, whereby by the ethylene polymer in the composition has a molecular weight, Mw, of from 25000 to 500000. 5. Use according to claim 1, whereby the phosphorous compound in the composition is a phosphite or phosphonite having the general formula EMI11.1 wherein R1, R2 and R3 independent of each other are alkyl or alkoxy groups having 1 to 30 carbon atoms, aryl or phenoxy groups. 6. Use according to claim 5, whereby the phosphorous compound is a trisalkylphenylphosphite, a tris-(2,4-dialkylphenyl)-phosphite or a tetrakis(2,4-dialkylphenyl)-4,4'-bis phenylylene-diphosphonite, wherein the alkyl groups have 9, 1 to 9, and 1 to 9 carbon atoms respectively. 7. Use according to claim 1, whereby the phosphorous compound in the composition is a phosphonic acid derivative naming the general formula EMI12.1 wherein R is hydrogen, a straight of branched alkyl group having 1 to 30 carbon atoms, an aryl group or a substituted aryl group, R1 and R2 independent of each other are hydrogen, a metal or has the same meaning as R and n is an integer between 1 and 10. 8. Use according to claim 7, whereby the phosponic acid derivative has the general formula EMI12.2 wherein R1 is hydrogen, metal or a straight or branched alkyl group having up to 22 carbon atoms, and R3 are lower alkyl groups having 1 to 6 carbon atoms, preferably tertiary butyl groups. 9. Use according to any of the preceding claims, whereby the composition also contains a metal salt of a fatty acid in an amount of at least 0.1 per cent by weight, based on the ethylene polymer.

Inventors: BOSTROM, MAGNUS, FRIMAN, BO YNGVE, Boström, Magnus
Applicants: UNIFOS KEMI AB
Application year: 1982
Main classification: C08L23
IPC codes: C08L101, C08L23, C08L7, C08K5, C08L21