A LO G U E O D U C T C AT PR

P o ly e th y le ig h D e n s it y h

ne

t I Pe LI N

URS T WO C O LO T IO N O N E D IR E C

MeMbers of the MoL GroUP

PETROCHEMICALS

Introduction
on January 1st, 2004 the Petrochemical Division of MOL Group integrating Slovnaft, a.s. and TVK Plc. was established and started its operation, leaving the two companies legally independent. From July 1st, 2006 Slovnaft Petrochemicals, s.r.o the 100% subsidiary of Slovnaft, a.s. is the successor of Slovnaft, a.s., continuing with production and sales of petrochemical products. the strategic target of the group is to take the leading market position of its region due to the efficient operation of the Division. To achieve this target the production and sales activity of TVK Plc. and Slovnaft Petrochemicals, s.r.o were harmonized, increasing supply optimalization and improving product-portfolio. Thus, considerable synergy and efficiency-improvement can be reached. With the completion of process-optimalization the product-range of both TVK Plc. and Slovnaft Petrochemicals, s.r.o have been streamlined to provide the competitive edge for our customers on their markets. tIPeLIN is a registered trade mark for medium and high density polyethylene grades manufactured by TVK Plc. tVK unimodal medium and high density tIPeLIN grades (MDPE and HDPE) are produced by continuous suspension polymerization using low pressure catalytic process under licence of Phillips Petroleum Co. The density range of co-polymers produced with hexene-1 co-monomer grades is 0.9340.955 g/cm3. the new high density tIPeLIN types are produced by CX Process under licence of Mitsui. This slurry phase polymerization employing a super-high-activity catalyst and a two-reactor system. The density range of co-polymer grades produced with butene-1 co-monomer is 0.948-0.958 g/cm3.

T W O C O LO U R S

oNe DIRECTION

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

Polyethylene characteristics
Molecular and crystal structure, density

Polyethylene macromolecules and their co-polymers build chains consisting of thousands of -CH 2- units. Depending upon polymerisation, this chain develops different branches (Fig. 1). Owing to its molecular structure with branches of chain length, LDPE is referred to as branched polyethylene. In contrast with this, medium and high density grades have only short branches on their chains and are referred to as linear polyethylene. LDPE has long chain branches, which themselves are branched as well. These products are manufactured in a high pressure process (>1000 bar). Linear polyethylene is produced in a low pressure process (by Phillips grades about 40 bar and by Mitsui grades about 10 bar). Hexene-1 (Phillips grades) and butene-1 or propylene (Mitsui grades) co-monomer built in the chain of these polyethylene grades produces side chains. The number of side chains is proportional to the amount of co-monomer built in the chain. As a result of the built-in co-monomer, the density and the degree of crystallinity will decrease. Polyethylene density (0.910-0.970 g/cm 3) and molecular weight depend on polymerisation circumstances to some extent. Melt flow rate and density are characteristics indicative of the polyethylene grade. Higher density is associated with a higher crystallisation ratio and a lower number of branches.
Figure 1 hDPe MDPe LDPe

Polyethylene is a partially crystalline polymer. The relationship between crystallisation ratio and density of HDPE is shown in Fig. 2. The proportion of crystalline matter or the density decides the polyethylenes melting characteristic. The melting point rises with the increase in crystallinity and density. The melting point varies between the melting point of LDPE (ca. 110C) and that of HDPE (ca. 128C).
Figure 2
100 80

Crystallisation (%)

60 40 20 0 0.930 0.940 0.950 0.960 0.970 density (g/cm3)

Degree of crystallinity as a function of density

Molecular weight, melt flow rate, melt viscosity and flow characteristics Chain length, or the average molecular weight is one of the important characteristics indicative of the degree of linkage. Changes in the molecular weight will definitely change melt viscosity, highly effecting on the processing properties. A high molecular weight polymer has a high melt viscosity, that is, its flow characteristics are poorer. To measure flow properties, a parameter, melt flow rate is used according to ISO 1133. High melt flow rate means easy flowing and low molecular weight. Melt flow rate is defined by a one-point method, a test that can be performed quite easily under laboratory circumstances. It is important, however, that the molecular weights, melt flow rates and flow characteristics of identical polyethylene grades manufactured in different processes may differ even though they have the same melt flow rate.

Density: 0.94-0.97 g/cm3 Melting point (DTA): 123-128 oC

Density: 0.93-0.94 g/cm3 Melting point (DTA): 117-123 oC

Density: 0.91-0.925 g/cm3 Melting point (DTA): 105-115 oC

The schematic diagrams demonstrate the structure and number of branches of various polyethylene grades.

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

 Molecular weight distribution Polyethylene consists of molecules of different chain lengths, giving different molecular weights. This is clearly shown by the diagram demonstrating the frequencies of various molecular weight. Molecular weight distribution influences both processing and end product properties. For example, a narrow molecular weight distribution is needed for the injection moulding of resins if the moulded parts are to be free from all distortion and internal stresses which might compromise their environmental stress cracking resistance (ESCR). At the same time, a high molecular weight polyethylene with a wider molecular weight distribution is more suitable for blowing processes to manufacture pipes and films. It should be remembered, however, that the low and medium molecular weight fractions account for easy processing and the rigidity of the product. The high molecular weight fraction gives good mechanical properties (impact strength, creep and warp resistance and ESCR).

the narrower the molecular weight distribution - The lower the processability - The lower the internal stresses - The higher the stretchability when moltenr
Figure 3
NarroW MoLecULar WeIGht DIstrIbUtIoN
11 10 9 8 7 6 5 4 3 2 1 0

broaD MoLecULar WeIGht DIstrIbUtIoN

11 10 9 8 7 6 5 4 3 2 1 0

Relative Frequency

102

Relative Frequency

103

104

105

106

107

102

103

104

105

106

107

Logarithmic molecular weight

Logarithmic molecular weight

The most important property of HDPE is its mechanical strength with easy processing capability, and this can be realized through bimodal high molecular weight HDPE. The low molecular weight component provides good processability, while the high molecular weight component gives excellent mechanical strength.
Figure 4 MoLecULar WeIGht DIstrIbUtIoN of bIMoDaL tyPe Good Processability Excellent Mechanical Strength

102

103

104

105

106

107

Molecular weight

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

other properties
shrinkage The shrinkage of finished products manufactured from HDPE takes place in the crystallisation phase. The extent of crystallisation depends on the processing parameters (temperature, pressure, throughput, thickness, cooling speed, etc.), but molecular structure (weight and weight distribution, fine structure) is a further factor having an effect on crystallisation. Shrinkage accounts 3-4% in pipe diameters. Shrinkage can be max. 5% in fittings made from pipe grades. Shrinkage can be exactly determined only after 24 hours following injection moulding, because re-crystallisation and the compensation of the generated internal stresses will result in further dimensional changes in the finished products. The extent of after shrinkage is time and temperature dependent. After shrinkage time, when shrinkage can reach 1% max., can be reduced by increased storage temperatures. Weather resistance HDPE grades have a good resistance to light in the visible spectrum. However, when storaged in the open air, they can get damaged by the combined effects of atmospheric oxygen and UV radiation. As a result, their durability and tensile strength lessen, and they may discolour. The useful life of polyethylene can be increased by two or four times with a UV stabiliser added to the blend. The great number of available UV stabilisers allows manufacturers to select the right grade to make a product most suitable for the weather conditions, end product and the environment of application. Special carbon blacks, the best UV stabilisers so far, can extend the useful lives of the products by 10-15 times when added in amounts of 2-3%. Pigments also can improve UV resistance, although, these additives may cause some undesirable side effects, as well.

application
The wide range of grades and the careful selection of characteristics of the individual grades allow various applications including blown film grades for heavy duty bags, industrial bags, shopping bags, garbage bags and packaging films for medicines and foods; blow moulding grades to manufacture household plastic products, bottles and cans for foods including oils, soft drink extracts and large capacity barrels for household or industrial chemicals, corrugated pipes; Pipe grades for gas, drinking water, industrial waste and sewage water lines and pipe fittings, corrugated and protective pipes, steel pipe coating; sheet extrusion grades for sheets and thermoformed sheets.

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

CODING SYSTEM
Grades produced by Phillips technology: TIPELIN medium and high density polyethylene grades (MDPE and HDPE) are identified by a code system consisting of two letters and five digits. Supplementary digits identify coloured compounds. Grades produced by Mitsui technology: TIPELIN high density polyethylene grades are identified by a code system consisting of four digits and one letter.

the first letter is for the application of the polymer f = Film b = Blow moulding P = Pipe extrusion

the second letter indicates the melt flow rate (Mfr) range in g/10 min at 190 c and 2.16 kg s < 0.2 a = 0.2-0.5 b = 0.5-1.0

the first and second digits are identical with the second and the third decimals of the number indicating nominal density

the first digit indicates the melt flow rate (Mfr) range in g/10 min at 190 c and 2.16 kg 6 = 0.1-0.9 7 = 0.05-0.10 8 < 0.05

the second digit Internal code

the third digit Spare number

7000F
FS 383-03
the third digit is an internal plant code the fourth and fifth digits identify the additive system in the polymer the fourth digit Modified grade alphabets at the end of the grade name show main application of the grade b = Blow moulding f = Film M = Pipe extrusion s = Sheet extrusion

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

Grade/ Parameter

Melt Mass flow rate (Mfr)

Density 23 c (4)

tensile strength at yield MPa Iso 527-3 22/19 (5) 19/18 (5) 21/19 (5) 22/23 (5) 22/20 (5) 26/25 (6) 24/22 (6) 26 (4) 29 (4) 30 (4) 28 (4) 27 (4) 19 (4) 25 (4) 25 (4)

tensile strain at yield (4) % Iso 527-3 11 11 12 13 13 13

tensile strength at break MPa Iso 527-3 50/43 (5) 46/40 (5) 45/40 (5) 48/42 (5) 43/41 (5) 60/45 (6) 68/45 (6) 28 (4) 33 (4) 31 (4) 30 (4) 32 (4)

tensile elmendorf Dart Drop tear strain (f50) at break resistance % Iso 527-3 650/750 (5) 700/800 (5) 600/700 (5) 700/750 (5) 700/800 (5) 500/550 (6) 480/560 (6) 1250 (4) 1100 (4) 1200 (4) 1250 (4) 1200 (4) 1300 (4) 1100 (4) 1200 (4) cN Iso 6383-2 58/400 (5) 60/410 (5) 50/350 (5) 26/270 (5) 25/240 (5) 20/170 (6) 20/170 (6) g Iso 7765-1 method a 120 (5) 110 (5) 100 (5) 110 (5) 60 (5) 220 (6) 250 (6) -

flexural Modulus (4)

Notched Izod Impact (4) kJ/m2 Iso 180/1a 13 13 8 9 18 16 23 16

spencer Impact strength MPa astM D 3420 36 (5) 35 (5) 33 (5) 35 (5) 25 (5) 140 (6) 180 (6)
-

Vicat shore D softening hardness temperature (4)

(4)

escr f50 b method h astM D 1693 200 (7) 55 (7) 250 (8) 700 (8) > 1000 (8) > 2000 (7) > 1000 (8) > 2250 (8)

oIt 200 c

(4)

application

Units test methods fs 340-03

bLoWN fILM GraDes

g/10 min Iso 1133/b 14 (3) 0.28 (1) 15 (3) 0.18 (1) 0.68 (1) 0.06 (1) 0.3 (2) 9 (3) 0.04 (1) 0.2 (2) 7 (3) 0.2 (1) 19 (3) 0.35 (1) 0.3 (1) 1.3 (2) 28 (3) 0.3 (1) 1.3 (2) 32 (3) 0.064 (1) 0.39 (2) 10.5 (3) 0.95 (2) 0.3 (2) 0.5 (2)

kg/m3 Iso 1183-2 934 938 938 947 947 954 948 950 955 958 954 954 948 948 948

MPa Iso 178 900 800 1100 1100 1500 1350 1300 1450 1700 1550 1600 950 1300 1350

c Iso 306/a120 117 118 119 125 124 126 125 127 129 127 126 127 118 125 125

Iso 868 59 60 60 63 63 64 63 64 65 65 64 64 61 63 63

min eN 728 26 18 40 55 50 30 42 5 8 27 26 40 > 50 > 120 120

Heavy duty bags, industrial films, multilayer films, blend component for LDPE Bags, shopping bags, multilayer films, blend component for LDPE Bags, shopping bags, multilayer films, blend component for LDPE Extra thin packaging films, bags, shopping bags, garbage bags Blend component for LDPE primarily for shrink film, Split fibre for wowen bags, technical textiles, twines Ultra-thin film, merchandise bags, disposal waste bags Industrial liners, carrier bags, heavy duty bags Bottles and cans of max. 10 litre capacity for aggressive household chemicals and detergents Bottles and cans of max. 30 litre capacity for non-aggressive household chemicals, cosmetics and oils. for non pressure resistant pipes Thin walled small bottles for consumer goods (cosmetics, daily care) Bottles and containers for detergents and household chemicals, corrugated pipes Jerry can for aggressive industrial chemicals, sheet extrusion PE 80, black type gas and water pipes, steel pipe coating, injection moulded fittings, extruded sheets and profiles Pipe and sheet manufacturing, protective pipes sheet extrusion Pipe and sheet manufacturing. jerry can for aggressive industrial chemicals,

fa 381-10
UNIMoDaL

fs 383-03 fs 471-02 fb 472-02 7000f

bIMoDaL

8000f bs 501-17
UNIMoDaL

bLoW MoULDING GraDes

ba 550-13 6000b
bIMoDaL

6300b 7300b

PIPe aND sheet extrUsIoN GraDes

UNIMoDaL

Ps 380-30/302 (black) (9) 7700M

(9)

bIMoDaL

7100s

(9)

Notes: (1) MFR at 190 C and 2.16 kg (2) MFR at 190 C and 5 kg (3) MFR at 190 C and 21.6 kg (4) Values have been measured on standard pressed specimens (ISO 293) conditioned at room temperature (ISO 291) (5) The thickness of the film: 0.025 mm for the mechanical measurement (MD/TD: MD = machine direction, TD = trans direction) (6) The thickness of the film: 0.015 mm for the mechanical measurement (MD/TD: MD = machine direction, TD = trans direction) (7) Values have been measured in 100% Igepal CO-630 on standard pressed specimens (ISO 293) conditioned at room temperature (ISO 291) (8) Values have been measured in 10% Igepal CO-630 on standard pressed specimens (ISO 293) conditioned at room temperature (ISO 291) (9) It is recommended the pellets to be dried before use.

10

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

Processing conditions
of tIPeLIN MDPe and hDPe grades
film manufacturing Considering their characteristics, TIPELIN film grades are medium and high density polyethylenes with a typically wide molecular weight distribution. To manufacture these grades an HDPE production unit with a 0.7-1.2 mm die gap and melt temperatures of 200-220 C are recommended. To produce optimum mechanical properties a high blow up ratio (minimum 4:1) should be applied. Generally the frost line height is 5-8 times the die diameter. TIPELIN FS 340-03, FS 383-03, FA 381-10 and FB 472-02 may be processed on machines designed for LDPE as LDPE, LLDPE or other blends containing HDPE. Depending on the extruder design and processing conditions, the thickness range can be 0.007-0.200 mm. Pipes and sheet extrusion Pipes and sheets can be manufactured from a TIPELIN base compound in a profile extrusion process. TIPELIN pipe grade is specifically designed for pipes and fittings suitable for delivering both gases and liquids under pressure. For the extrusion of TIPELIN profiles, a screw of at least 20 D, shorter compression zone (1-3 D) and a 2-2.5 compression ration should be applied. The constant pitch of the screw should be equal with or less than the diameter. Recommended processing temperatures are 170-220 C for extrusion and max. 250 C for injection moulded fittings. According to the extensive testing of the long term performances, TIPELIN unimodal pressure pipe resin fulfill the requirements of PE 80 classification. blow moulding TIPELIN blow moulding grades are high density polyethylenes with typically low MFRs and a wide molecular weight distribution. TIPELIN blow moulding grades process well on extruders whose screw is not less 20 D, constant pitch is equivalent with or less than diameter, compression zone is shorter (1-2 D) and where compression ratio is 2.5-3. Recommended melt temperatures are 180-220 C.
storage and handling Pellets are packed in 25 kg PE-LD bags and transported on stretch-wrapped pallets at eligible load of polymer 1250 kg or 1375 kg. Heat treated pallets are available as well. Transportation in a road silo or rail silo is also available. For more detailed information please contact Slovnaft Petrochemicals and TVK sales representative. Since polyethylene is a combustible substance, the fire safety rules applicable for combustible materials in warehouses and store rooms should be observed. If polymer is stored in conditions of high humidity and fluctuating temperatures, then atmospheric moisture can condense inside the packing. If it happened, it is recommended the pellets to be dried before use. During the storage polyethylene should not be exposed to UV radiation. Producer does not take responsibility for any damages caused by adverse storage. reach statement Polymers are exempt of REACH registration. However their raw materials which mean monomers, catalysts and most additives have been pre-registered. TVK is committed to fully respect this new legislation and will only use REACH compliant raw materials. At this point in time TVK HDPE TIPELIN does not contain any substances specifically identified as SVHC at greater level than 0.1%. application for foods Most TIPELIN grades satisfy the regulations applied by the European countries (EEC). Because several European countries apply restrictive regulations for the allowed migration values of additives in packaging material in contact with food, it is recommended that customers contact TVK for some special information or product licenses for food industry. safety Under normal circumstances, polyethylene is not regarded as hazardous material when in contact with the skin or when inhaled. However, any contact with the molten polymer or the inhalation of the released gases should be avoided in processing. It is recommended to install exhaust units over processing machines and to secure good ventilation of the place. For further information see Material Safety Data Sheet. recycling Polyethylene resins are suitable for recycling using modern recycling methods. In-house production waste should be kept clean to facilitate direct recycling.
Disclaimer The information provided in this publication has been compiled to the best of our present knowledge. However, in view of the various applications of polyethylene resins and the equipment used, the processing conditions may differ. The recommendations and data herein are to be construed as informatory only and do not relieve users from carrying out their own tests and experiments prior to processing in order to check suitability for a specific use. It is the responsibility of those to whom we supply our products to ensure that any proprietary rights and existing laws and legislation are observed. Our products are under continuous development, therefore we reserve the right to change the information presented in this brochure at our own discretion. The REACH statement herein does not constitute legal advice. The REACH statement is provided for informational purpose only.

12

ProDUct cataLoGUe hIGh DeNsIty PoLyethyLeNe

sales offices:
Germany TVK Inter-Chemol GmbH Fellnerstrasse 7-9. D-60322 Frankfurt am Main phone: +49 69 154 04 12 +49 69 154 04 31 fax: +49 69 154 04 41 e-mail: gaboragoston@tvkic.de andrasvarnai@tvkic.de Poland TVK Polska Sp. z o.o. ul. Wa wozowa 23/12 PL 02-796 Warszawa Poland phone: +48 22 545 70 70 fax: +48 22 545 70 60 e-mail: tvkpolska@tvkpolska.pl www.tvkpolska.pl Slovak Republic Slovnaft Petrochemicals, s.r.o. Vlie hrdlo 4846 824 12 Bratislava Slovak Republic phone: +421 2 58 59 7469 fax: +421 2 58 59 7381 e-mail: info@slovnaft.sk www.slovnaft.sk Romania SC. MOL Romania P.P. SRL Str. Danielopolu 4-6 ET2 Sector 1 Cod 014 134 Bucuresti, Romania phone: +40 21 204 85 00 +40 21 204 85 02 fax: +40 21 232 10 59 e-mail: ematei@molromania.ro petchem@molromania.ro Ukraine TVK Ukraine 04128 Kiev ul. Tupoleva, 19, office 303 phone: +380 44 374 00 80 fax: +380 44 374 00 90 e-mail: gnatalia@tvkukraine.eu

France TVK France 182 Avenue Charles de Gaulle F-92200 Neuilly sur Seine phone: +33 14 745 63 60 fax: +33 14 745 45 10 e-mail: tvk.france@orange.fr

Italy TVK Italia Srl. Via P. Teuli 1 I-20136 Milano phone: +39 02 58 30 55 23 fax: +39 02 58 30 34 92 e-mail: tvkitaly@energy.it

Austria MOL-Austria Handels GmbH Gartenbaupromenade 2/6 A-1010 Wien phone: +43 1 515 991 120 +43 1 515 991 121 fax: +43 1 513 37 55 1120 +43 1 513 37 55 1121 e-mail: JHauk@MOL.hu

Hungary TVK Nyrt. H-3581 Tiszajvros P.O.B. 20 phone: +36 49 52 13 55 fax: +36 49 52 24 10 e-mail: polymersales@tvk.hu www.tvk.hu

Other European Countries H-3581 Tiszajvros P.O.B. 20. phone: +36 49 521 162 fax: +36 49 522 410 e-mail: bpetra@tvk.hu

certificates
Slovnaft Petrochemicals TVK

PETROCHEMICALS

Published in April 2010