MANUFACTURING OF BIODEGRADABLE POLYETHYLENE

1. MANUFACTURING OF BIODEGRADABLE POLYETHYLENE PRESENTED BY:- HASAN IJTABA KHAN MAFTUN 09-PE-12 FAISAL NADEEM 09-PE-07 KHAWAJA OWAIS KAMAL 09-PE-14 SYED HASSAN SAEED 09-PE-34 AHMED IMRAN QUREISHI 09-PE-03

2. BIODEGRADATION • Process by which organic substances are broken down by the environmental effects and by the living organisms. • Organic material can be degraded aerobically or anaerobically . • Biodegradable matter is generally organic material such as plant and animal matter and other substances originating from living organisms, or artificial materials that are similar enough to plant and animal matter to be put to use by microorganisms. • Biodegradable polymers are a kind of materials which degrades biologically. • The biodegradability of plastics is dependent on the chemical structure of the material and on the constituent of the final product, not just on the basic materials used in the production.

3. THE RANGE OF BIODEGRADABLE PLASTIC • Starch based products including thermoplastic starch, starch and synthetic aliphatic polyester blend, and starch and PVOH (polyvinyl alcohol) blends. • Naturally produced polyester including PVB (polyvinyl butadiene). • Renewable resource polyesters such as PLA (poly lactic acid). • Synthetic aliphatic polyesters including PCL (poly caprolactone). • Aliphatic-aromatic (AAC) co polyester. • Hydro-biodegradable polyester such as modified PET. • Water-soluble polymers such as polyvinyl alcohol and ethylene vinyl alcohol. • Photo-biodegradable plastics. • Controlled degradation additive master batches.

4. CLASSES OF BIODEGRADABLE PLASTICS • Compostable • Hydro-biodegradable • Photo-biodegradable • Bioerodable • Biodegradable

5. BACKGROUND OF STARCH-BASED POLYMERS • Our work relates to a biodegradable film prepared by chemical bonding of starch and polyethylene. • Polyethylene is polyolefin having the most widest general application, coupling agent such as maleic anhydride, methacrylic anhydride or maleimide which bonds with starch and polyethylene, and Lewis acid catalyst and to a process for preparing thereof.

6. BACKGROUND OF STARCH-BASED POLYMERS • Starch • Chemical formula of starch  (C6H10O5)n • Starch is a linear polymer (polysaccaride) made up of repeating glucose groups linked by glucosidic linkage in the 1-4 carbon position. • The length of the starch chain will vary with plant sources but in general the average length is between 500-20,000 glucose units. • There are actually two types of starch molecules: • Amylose • Amylopectin. • The only difference between the two is the arrangement of the molecules. • Amylose is essentially linear while amylopectin has many branches like a tree.

7. CHEMISTRY OF STARCH • Amylose • Amylose molecules consist of single mostly-unbranched chains with 500-20,000 α-(14)-D-glucose units dependent on source. • Hydrogen bonding between aligned chains causes retro gradation and releases some of the bound water.

8. CHEMISTRY OF STARCH • Amylopectin • Amylopectin is formed by non-random α-16 branching of the amylose-type α-(14)-D-glucose structure. • Each amylopectin molecule contains a million or so residues. • Each amylopectin molecule contains up to two million glucose residues in a compact structure with hydrodynamic radius 21-75 nm.

9. VARIETIES OF STARCH

10. VARIETIES OF STARCH • Corn Starch • Common cornstarch has 25% amylose. The two remaining cornstarches are high-amylose cornstarches; one has 50% to 55% amylose, while the second has 70% to 75%. Their size ranges between 5 microns and 20 microns • Maize Starch • Maize starch has irregularly shaped granules. High-amylose starches also have an irregular shape, but tend to be smooth. Some of these are even rod-shaped. High-amylose starches have a narrower size range: 5 to 15 microns, or even 10 to 15 microns, depending on the variety.

11. VARIETIESOFSTARCH • Potato Starch • Potato starch has about 20% amylose. Potato starch granules are large with a smooth round oval shape. Of the starches commonly used for food, potato starch is the largest; its granules range in size from 15 to 75 microns. • Rice Starch • Common rice starch has an amylose: amylopectin ratio of about 20:80, while waxy rice starch has only about 2% amylose. Both varieties have small granule sizes ranging from 3 to 8 microns.

12. VARIETIES OF STARCH • Tapioca Starch • Tapioca starch has 15% to 18% amylose. Tapioca granules are smooth, irregular spheres with sizes ranging from 5 to 25 microns. • Wheat Starch • Wheat starch has an amylose content of around 25%. Its granules are relatively thick at 5 to 15 microns with a smooth, round shape ranging from 22 to 36 microns in diameter. • Soya bean Starch • Soya bean starch has irregular shaped granules. Common Soya bean starch has 7% amylose. Its granules range in size from 10 to 90 microns.

13. VARIETIESOFSTARCH

14. CATEGORIESOFSTARCHBASEDPOLYMERS • Thermoplastic starch products. • Starchsyntheticaliphaticpolyesterblend • StarchPBS/PBSApolyesterblends • StarchPVOHblends.

15. CATEGORIESOFSTARCHBASEDPOLYMERS • Thermoplastic Starch Products • Thermoplastic starch biodegradable plastics (TPS) have a starch (amylose) content greater than 70%. • It is based on vegetable starch, and with the use of specific plasticizing solvents, can produce thermoplastic materials with good performance properties and inherent biodegradability. • This can be overcome through blending, as the starch has free hydroxyl groups, which readily undergo a number of reactions such as acetylation, esterification and etherification.

16. CATEGORIESOFSTARCHBASEDPOLYMERS • Starch Synthetic Aliphatic Polyester Blends • Blends of biodegradable synthetic aliphatic polyesters and starch are often used to produce high quality sheets and films for packaging by flat-film extrusion using chill-roll casting or by blown film methods • Approximately 50% of the synthetic polyester (at approximately $4.00/kg) can be replaced with natural polymers such as starch (at approximately $1.50/kg), leading to a significant reduction in cost. • Furthermore, the polyesters can be modified by incorporating a functional group capable of reacting with natural starch polymers.

17. CATEGORIESOFSTARCHBASEDPOLYMERS • Starch and PBS/PBSA Polyester Blends • Polyesters that are blended with starch to improve material mechanical properties are Polybutylene succinate (PBS) or polybutylene succinate adipate (PBSA). • At higher starch content (>60%), such sheets can become brittle. • Plasticizers are often added to reduce the brittleness and improve flexibility. • Starch and PBS or PBSA blends are used to produce biodegradable plastic sheet, which can be thermoformed into products such as biscuit trays or film products.

18. CATEGORIESOFSTARCHBASEDPOLYMERS • Starch-PVOH Blends • Polyvinyl alcohol (PVOH) is blended with starch to produce readily biodegradable plastics.

19. MARKET SURVEY REPORT

20. MARKETANALYSISOFBIODEGRADABLEMATERIAL • The technology surrounding biopolymers and biodegradable packaging has been in the development stage for the last 15-20 years. • In the last five years have markets developed and much commercial growth been seen. • Only few companies are currently producing biodegradable packaging materials on a large enough scale to be commercially successful.

21. NUMBER OF COMPANIES WITH BIODEGRADABLE PLASTICS • Figure illustrates the trend, showing that the number of companies applying for patents increased through the 1990s and appears to have peaked in 2005.

22. BIODEGRADABLEMATERIAL’SMARKETOVERVIEW • Figure Identifying the top 30 companies listed as first assignee indicates which companies are most active in patenting new technologies and processes. • According to the Rapra report, 30 suppliers are currently active in the global biopolymer market, with BASF, DuPont and Mitsubishi Gas Chemicals dominating. • Novamont and Mitsubishi are also found among the patent leaders, suggesting that competition could heat up over the next few years.

23. GEOGRAPHICALDISTRIBUTIONOFPATENTACTIVITYFORUSEOFBIODEGRADABLEMATERIALSGEOGRAPHICALDISTRIBUTIONOFPATENTACTIVITYFORUSEOFBIODEGRADABLEMATERIALS • Following figure shows that nearly half of the filings examined were published in the United States (USPTO). • The other half is divided among World patents (WIPO), European patents, Japanese and British patents.

24. ACTIVESUPPLIERSOFBIODEGRADABLEMATERIAL • Proctor and Gamble Limited. • BASF Germany. • DuPont. • Mitsubishi Gas Chemicals. • Nova Mont. • Nature Works. • Rodenburg Biopolymers. • Biotech. • Mitsubishi. • Merck Chemicals.

25. LOCALMARKETSURVEY • We have conducted local market survey and have reached to the conclusion that the biodegradable material is not available in the market. • We also have contacted the following companies and the results are the same as mentioned above. • Bin Rasheed • Umair Petrochemicals • MERCK Chemicals • P & G Pakistan • BASF Pak Ltd.

26. LOCALMARKETSURVEY • DENSO HALL SADDAR KARACHI • LIAQUATABAD KARACHI

27. DISPOSAL ENVIRONMENTS

28. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • Composting facilities or soil burial • Anaerobicdigestion • Wastewatertreatmentfacilities • Plasticsreprocessingfacilities • Landfill • Marine and freshwater environments • General open environment as litter.

29. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • COMPOSTING FACILITIES AND SOIL BURIAL • Composting and soil burial is the preferred disposal environment for most biodegradable plastics. • The degradation mechanism of biodegradable plastics in a composting environment is primarily hydrolysis combined with aerobic and anaerobic microbial activity. • Typically for full degradation, composting occurs over a 10 to 12 week period. • The degradation products of aerobic composting are compost and CO2.

30. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • ANAEROBIC DIGESTION • Anaerobic digestion is also gaining support as an alternative to landfills. • Methane production may be faster, more efficient and more predictable in this system and a useful end-product, compost, is also produced.

31. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • WASTE WATER TREATMENT PLANTS • Activated sewage sludge will convert approximately 60% of a biodegradable polymer to carbon dioxide. • The remaining 40% will enter the sludge stream where, under anaerobic digestion, it will be converted to methane. • Any biodegradable polymer that meets the compostability criteria will degrade even faster in a sewage environment.

32. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • REPROCESSING FACILITIES It is to be expected that if biodegradable plastics began to occupy a significant market share of the plastics market in the world that some material would end up in plastics reprocessing facilities. This could have significant effects on the sorting procedures required and the quality of recycled end products.

33. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • LANDFILLS • When conventional low- density polyethylene film was under bioactive soil for almost 40 years, the surface of the film shows signs of biodegradation with the molecular weight dropping by half the original. • The inner part of the sample was almost unchanged with the molecular weight being retained.

34. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • LANDFILLS • Environmentally degradable polymers could increase the capacity of landfill sites by breaking down in a relatively short time and freeing other materials for degradation, such as food scraps in plastic bags. • Typical landfill gas contains 50% methane and 45% CO2, with the balance composed of water and trace compounds.

35. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • MARINE AND FRESHWATER ENVIRONMENTS The rate of biodegradation in marine environments is affected by the water temperature. • In cold waters, the plastic material may still be in a form that could endanger marine life for an extended period of time. It is found that plastic is fully degraded in 20-30 days in a compost environment . • Thus seasonal and climatic effects on biodegradation rates need to be considered in relevant applications.

36. MAJORDISPOSALENVIRONMENTSFORBIODEGRADABLEPLASTICS • LITTER Plastic litter causes aesthetic problems as well as danger to wildlife resulting from entanglement and ingestion of plastic packaging materials and lightweight bags. Wildlife losses are an issue for the conservation of biodiversity, and losses due to litter have caused public concern.

37. PROCEDURE OF MANUFACTURING STARCH BASED POLYETHYLENE

38. BIODEGRADABLEPOLYETHYLENECOMPOSITIONCHEMICALLYBONDEDWITHSTARCHBIODEGRADABLEPOLYETHYLENECOMPOSITIONCHEMICALLYBONDEDWITHSTARCH

39. BIODEGRADABLEPOLYETHYLENECOMPOSITIONCHEMICALLYBONDEDWITHSTARCHBIODEGRADABLEPOLYETHYLENECOMPOSITIONCHEMICALLYBONDEDWITHSTARCH • In this composition the polyethylene is selected from the group consisting of low density polyethylene LDPE. The LDPE which we have selected for our biodegradable starch based film is PETLIN-MALAYSIA of extrusion grade. • The radical initiator may be di-cumyl peroxide. • The Autoxidizing agent is one or more selected from the group consisting of manganese oleate, manganese stearate, ferrous oleate (II). Since we were unable to find autoxidizing agent due to its unavailability in the market, so as per our advisor recommendation we have not used autoxidizing agent in our formulation. • The Lewis acid catalyst is one from the group consisting of stearic acid and acetic acid . We have used stearic acid as a catalyst in our formulation. • The plasticizer is one selected from group consisting of oleamide, Viton poly (hexaflouropropylene)-copoly (vinylidene fluoride) or Erucamide Cis-13-1-docosenoamide. In our formulation we have not used plasticizer due to its unavailability in the local market.

40. PROPOSEDRATIOOFPOLYETHYLENEANDSTARCH

41. COMPATIBILTY OF LDPE WITH DIFFERENT TYPES OF STARCHES

42. PROJECT DESCRIPTION • Initially we have been suggested to make a starch based biodegradable polyethylene blown film through single screw extruder. • Afterwards the management of PLASTICS TECHNOLOGY CENTRE proposed us to manufacture a strip of starch based biodegradable polyethylene by using a profile die on BRABENDER PLASTICORDER.

43. FORMULATION FOR BRABENDER

44. MIXING • Mixing of the above two proposed formulation is carried out in a HANSCHEL MIXER for about 15 minutes. • Before putting the material in the mixer for mixing, the mixer should completely and thoroughly be cleaned with a clean cloth so as to avoid contamination of the two proposed batches.

45. PROCESSING AT BRABENDER • After mixing, the compound has been taken to the BRABENDER PLASTICORDER. • Profile die is used and the extrudate is manually cut with the help of a cutter to have it in a shape of a strip. • Initially the BRABENDER is operated to remove the last traces of the material left in the barrel in the last processing operation. • Once all the old material’s been removed, virgin LDPE has been added through the hopper to achieve the required temperature. • Since we were processing starch with LDPE for the first time in our carrier, we were stock feeding the machine so that the material should not block the nozzle of the machine. • Fans in the processing hall were kept closed to achieve the desired temperatures on the machine.

46. PROCESSING AT BRABENDER • Firstly we processed 80/20 ratio formulation so as to check the behavior of the machine with the starch incorporated batch. • After the production of 80/20 ratio batch, we processed pure LDPE so as to clean the barrel of the extruder for next formulation. • For 60/40 ratio formulation, the temperatures at the machine are slightly increased as the content of starch is greater as compared with the previous composition. Once the desired temperature range has been achieved, the strips of the proposed formulation have been produced. • Water bath has been used immediately after the die so as to cool the formed product.

47. PROCESSING PARAMETERS AT BRABENDER

48. TESTING

49. INTERNATIONAL ORGANISATIONS FOR STANDARDS AND TEST METHODS • American Society For Testing And Materials (ASTM) • European Standardization Committee (CEN) • International Standards Organisation (ISO) • Institute for Standards Research (ISR) • German Institute for Standardization (DIN) • Organic Reclamation and Composting Association (ORCA) (Belgium)

50. DIFFERENCEBETWEEN STANDARDS FOR BIODEGRADATION