Polymer Degradationand Stability 45 (1994) 71-76

ELSEVIER

~) 1994 ElsevierScience Limited Printed in Northern Ireland. All rights reserved 0141-3910/94/$07.00

The recovery of photodegraded low density polyethylene from green houses and solars (S-LD-PE). III. Rheological properties of the melts of certain blends based on S-LD-PE
D o i n a Staicu & Horia Paven
Institute for Chemical Research, Research Center for Plastics Materials, SPL. lndependentei, NR. 202, 77208, Bucharest 6, Romania
(Received 3 December 1993; revised version received 3 February 1994; accepted 8 February 1994)

In order to reuse photodegraded low density polyethylene from green houses and solars, it has been physically modified with EPDR, bitumen atactic polypropylene. Thermodynamically compatible blends, selected by DSC and dielectric spectroscopy studies, were moulded into hydroinsulating sheets, which exhibit useful properties. The influence of the degree of miscibility of the components at the molecular level on the rheological properties of melts of certain blends based on S-LD-PE is presented.

INTRODUCTION

EXPERIMENTAL

In order to reuse photodegraded low density polyethylene (S-LD-PE) from green houses and solars, it was physically modified with ethylene propylene diene monomer rubber (EPDR), bitumen (B), or atactic polypropylene (APP), after grinding, separation, washing and drying.t-7 Since the useful properties of the polymeric blends depends on the degree of miscibility of the components at the molecular level, attempts must be directed towards obtaining thermodynamically compatible blends. These were selected by DSC 1 and dielectric spectroscopy studies,2 which were assessed on the basis of their transition temperatures. Thus the blends studied, based on S-LD-PE, were analysed through DSC 1 measurements to obtain their melting characteristics and through dielectric spectroscopy their o~-relaxation. Thermodynamically compatible blends were extruded into hydroinsulating sheets which had good utilization properties. 3"7 The influence of the degree of miscibility of the components on the melt flow properties of the blends based on S-LD-PE is presented.
71

Work performed in order t o obtain compatible blends has already been described. 1-7 The influence of the degree of miscibility on the melt flow properties of the blends based on S-LD-PE, was studied by determining the influence of the blend composition on the kinematic viscosity, v, activation energy of viscous flow, E, and the non-Newtonian index values, n, and the comparison of these results with those obtained from the compatibility study presented. 1,2 The rheological properties studied were calculated from melt flow indices8-t using the following formulae:
v = r/= 5 10 5 G p MFI(T, G) E=R T~T2 InMFI(T~' G) T2- T~ MFI(T2, G) (stokes) (1)

(kJ/mol)

(2)

~(/ n = In

MFI(G;, T) In MFI(G/, T)

(3)

72

Doina Staicu, Horia Paven

Table 1. The theological properties of raw and photodegraded low density polyethylene

where n is the non-Newtonean index, v is the kinematic viscosity (stokes),/9 is the melt density (g/cm3), MFI is the melt flow index (g/10 min), Gi,/ are the weights upon the plastomer piston (kg), r/ is the dynamic viscosity (poise), TL2 are the operating plastomer temperatures (K) and E is the activation energy of viscous flow (kJ/mol). The melt flow indices were measured on a ' P O L I R E O ' capillary plastometer at 4 length/ diameter ratio, TI.2=190C and 200C and Gi,/= 2, 5, 10 kg. The results were presented in ternary diagrams, plotting the dependence of rheological properties as a function of the blends composition where P represents the difference between the modified and non-modified polymer properties. The physical and mechanical properties of S-LD-PE show that during its useful life, a degradation process takes place involving chain breaking, cross-linking and oxidation. That is why all the S-LD-PE properties including the rheological properties, differ from those of the primary polyethylene. 3 The change in the rheological properties of S-LD-PE is mainly due to the chain breaking and cross-linking processes (Table 1). Therefore, the MFI values are lower than those of the primary LD-PE. The flow activation energies of the S-LD-PE melt are higher than those of the primary polymer melt. Consequently, the nonNewtonian character of the flow is much more pronounced (the non-Newtonian index, n, of S-LD-PE is much lower).
Binary blends with E P D R

Property (unit) Raw 1. Melt flow index (g/10 min) T = 190Cwith 2.16 kg 5 kg 10 kg 2000C with 2.16 kg 5 kg 10 kg 2. Non-Newtonianindex T = 190Cwith 2.16 kg 5 kg 10 kg 2000C with 2.16 kg 5 kg 3. Kinematicviscosity (104 stokes) T = 190Cwith 2.16 kg 5 kg 10 kg 200C with 2.16 kg 4. The melt flow activation energy (kJ/mol), heating from 190Cto 200C 2.16 kg 5 kg 1.86 8.0 20.85 2.38 0.72 23.36 0-57 0.62 0.62 0.59 0.77

LD-PE Secondary 0.28 1.0 3.75 0.22 1.28

0.66 0.63 0.59 0.47 0.42

58.064 31.25 23.98 47.37

38.57 25.0 13.30 49.09

33.677 34.577

43.884 44.925

E P D R induces important changes in the rheological properties of the polymer melt as shown in Fig. 1. It is well known that the viscous flow activation energy and the melt viscosity characterize the energy consumption required for melt processing and the non-Newtonian index gives information about the melt stability for various processing conditions (i.e. ~,-shear rate, temperature).S-~ From Fig. l(a) it can be seen that every 5% of E P D R decreases the kinematic viscosity of the S-LD-PE by about 5-10stokes, the melt flow activation energy by about 7 kcal/mol (Fig. l(b)) and the non-Newtonian index by approximately 0-04 units (Fig. l(c)). This kind of change shows that this modifier reduces only the energy consumption required

for melt processing and does not increase the melt flow stability for various processing conditions. As previously demonstrated L2 the blends of S-LD-PE with E P D R are, to a great extent, thermodynamically compatible. However, the miscibility of the two components is not complete because the blend with the highest EPDR concentration (i.e. 15%) retains a small shoulder on its melting endotherm at T = 126C, the temperature of the second melting endotherm of the S-LD-PE. Thus partial miscibility of the E P D R and S-LD-PE macromolecules results in only a partial improvement in the flow properties of the melts of the blends.
Binary blends with A P P

Figure 1 also shows the influence of APP on the rheological properties of the S-LD-PE melt. Addition of 5% of the modifier reduces the kinematic viscosity of the S-LD-PE by about 10K J/tool and the non-Newtonian index by about 0.07 units. The decrease in the activation

The recovery of photodegraded, low density polyethylene

(a)

73

Percentageincrease (b) Percentage increase ([plM / lO0[p] S-LD-PE) ([pIM / lO0[pl S-LD-PE) 10 15 ~ 5 10 15
I I ~'~ 0 I 1 r/-~ _5 I

(c)

Percentage increase ([pIM/ 100[p]S-LD-PE)

5 10 15
r

-5

-10 ~ -15

~ -15 -20 -25 -30 -35 -

ii -20
-25

P -0"15 I

Fig. 1. Change in: (a) kinematic viscosity (stokes); (b) activation energy of viscous flow (kj/mol); (c) non-Newtonian index of S-LD-PE modified with EPDR, APP and bitumen.

energy of viscous flow cannot be considered a real improvement in the melt flow properties. It must be emphasized that this modifier reduces, more than E P D R , the energy consumption required for melt processing and the stability of the melt for various processing conditions. It was previously demonstrated 5 that the S-LD-PE blends with APP are not completely miscible. The melting endotherms of these blends still preserve a small shoulder at 126C, the temperature at which the S-LD-PE has its second melting endothermic maximum. Therefore, the quasi-total miscibility of S-LD-PE with APP, leads only to a decrease in the energy consumption required for melt processing.

Newtonian index (Fig. l(c)) are lower. Thus, bitumen provides a decrease in the energy required for melt processing somewhat similar to that produced by APP but also results in a pronounced reduction in the melt stability for various processing conditions. It was previously demonstrated 1 that the bitumen and S-LD-PE macromolecules are not completely miscible. The DSC thermograms of these blends still preserve two small shoulders on the melting endotherms, at temperatures recorded for the second melting maximum of S-LD-PE. Thus the quasi-total miscibility of the S-LD-PE and bitumen macromolecules results in only a partial improvement in the melt flow properties.

Binary blends with bitumen Ternary S-LD-PE, E P D R , bitumen blends

The influence of bitumen on the rheological properties of S-LD-PE is also shown in Fig. 1. The melts of these blends of S-LD-PE and B show similar rheological behaviour to S-LD-PE blends with APP. The bitumen also induces a decrease in the three rheological studied properties. Compared with the influence of APP, the extent of decrease in the kinematic viscosity is similar (Fig. l(a)) while the viscous flow activation energy (Fig. l(b)) and the non-

The results of studies of the influence of bitumen on the rheological properties of binary blends of S-LD-PE and E P D R are shown in Fig. 2. The presence of bitumen also decreases the kinematic viscosity and the activation energy of viscous flow of these blends (Figs 2(a) and 2(b)), but it is very interesting that the non-Newtonian index increased (Fig. 2(c)) with higher quantities of modifier. Thus, compared with blends of S-LD-PE and

74

Doina Staicu, Horia Paven

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The recovery of photodegraded, low density polyethylene

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E P D R , the additional presence of bitumen in ternary blends results in lower energy for melt processing and a better stability for various processing conditions. Thus, increased miscibility at the molecular level between the S-LDoPE and E P D R molecules, due to the presence of bitumen, results in an important improvement in the rheological properties of the melts of these kinds of blends.

HYDROINSULATING SHEETS FROM COMPATIBLE BLENDS BASED ON S-LD-PE

The compatible blends of S-LD-PE with bitumen and E P D R or APP ~-6 were moulded into hydroinsulating sheets which proved to have good properties under site conditions. 7

CONCLUSIONS Ternary S-LD-PE, APP, bitumen blends

Thermodynamically compatible blends of S-LDPE with bitumen and E P D R or APP have improved melt flow properties. Thus the energy necessary for melt processing is lower and the stability of the melts for various processing conditions is much better.

The presence of bitumen in the blends of S-LD-PE with APP results in a strong decrease in the kinematic viscosity (Fig. 3(a)) of the activation energy of viscous flow (Fig. 3(b)), and a significant increase in the non-Newtonian index (Fig. 3(c)). It was previously demonstrated I that because the DSC thermograms show only one endothermic melting maximum and no additional shoulders at the values of temperature specific to the individual components (as happened with the binary blends) the ternary blends of S-LD-PE with APP and bitumen are thermodynamically compatible. Consequently, these blends have better rheological properties. Thus the energy required for melt processing is lower and the stability of the melts for various processing conditions is much better.

REFERENCES
1. Staicu, D., Polym. Deg. Stab. (in press). 2. Staicu, D., Revue Roumaine de Chimie, Romania (in press). 3. Staicu, D., Materiale Plastice, Romania (in press). 4. Staicu, D., (ICECHIM But.), Ro. Pat. 86376 (January 5, 1985); Chem. Abstr., 18 (1986) 154741. 5. Staicu, D., (ICECHIM Buc.), Ro. Pat. 97231 (February 13, 1987); Chem. Abstr., 113 (1990). 6. Staieu, D., (ICECHIM Buc.), Ro. Pat. 97232 (February 13, 1987); Chem. Abstr., 113 (1990). 7. Staieu, D., Hidrotehnica, 36 (1991) 160. 8. Jinescu, V. V., Physical and Thermodynamic Properties of the Plastics Materials. Ed. Tehnica, Bucuresti, 1972. 9. Tudose, R. Z., Macromolecular Compounds Rheology. Ed. Tehnica, Bucuresti, 1973. 10. Paul, D. R., Polym. Engng. Sci., 13 (1973) 307.