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Journal of Chemical and Pharmaceutical Research, 2014, 6(7):1467-1473

ISSN : 0975-7384
Research Article CODEN(USA) : JCPRC5

Modification and characterization of polypropylene

Chengwu Li

Material Science and Engineering College of Shenyang Ligong University, China

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ABSTRACT

For increasing the toughness of polypropylene and expanding its applications,the modification mechanism
polypropylene is discussed in this paper, and the inorganic particles (calcium carbonate)and organic plastic
materials (polyethylene St) are used to modify the polypropylene in this article.The characterization of the
polypropylene modified by calcium carbonate and St-modified shows much better toughness and mechanical
strength than the pure polypropylene.

Key words: Polypropylene(PP); Modification;Calcium Carbonate; Polyethylene (St) and Characterization

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INTRODUCTION

Polypropylene (PP) is an excellent plastic material with a high heat distortion temperature, excellent rigidity,
electrical insulation, excellent resistance to folding and ease of molding. Therefore widely used in fiber, daily
necessities, packaging films, industrial products, paints and other fields [1-3]. In the five common plastics,
polyethylene and PVC production after domestic consumption is ranked second only to polyethylene. But also the
existence of polypropylene notch sensitivity, poor toughness, mold shrinkage Japanese do not wear other
shortcomings.

With the rapid development of the plastics industry, the industry needs to adjust the product structure, open up new
areas of application, increasing the variety and new high-performance grades, strong research and development of
technologies and modified PP modified products is extremely important, this paper modified polypropylene
research.

POLYPROPYLENE MODIFICATION EXPERIMENTAL METHOD

1.1THE MAIN RAW MATERIAL OF EXPERIMENTS
Polypropylene (powder), polypropylene (Sl004, F401), ultrafine CaCO3, crystal nucleating agent (1MB); 5 ~ 7%
octene, ethylene-propylene copolymer of 70%，crosslinking agent A, the crosslinking agent B , a dispersing agent A,
monomer A, monomer B, the monomer c, antioxidant (1076), co-antioxidants (DSTP), liquid paraffin.

1.2THE MAIN EXPERIMENTAL EQUIPMENT

Twin-screw extruder,injection molding machine, computer-controlled electronic universal testing machine, plastic
impact testing instrument and polarizing microscope

1.2 EXTRUSION PROCESS

The first zone temperature: 170-175C; second zone temperature (C):175-180; third zone Temperature: 185-190C;
Fourth District Temperature: 195-200C; die temperature: 190-195C; feed rate (rpm): 500 to 600; screw speed (rpm):
200.

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1.3 INJECTION PROCESS
The first zone temperature (C):170-175; second zone temperature (C): 180-185; third zone temperature (C):190-200;
nozzle temperature (C) :200-210; injection time (s ) 5; dwell time + cooling time (s): 10.

1.4GRAFTED POLYPROPYLENE SUSPENSION GRAFT TECHNOLOGY

Powdered PP, grafting monomer, a dispersing agent A, co-reactant, a dispersion time of deionized water, heated to
90 ℃, the amount of BPO was added portionwise a solution of the reaction for 2 hours, filtered, washed and dried.

1.5 MECHANICAL TESTING

Tensile properties: with cMT5104 computer-controlled electronic universal testing machine according GBl048-79
test, the specimen gage length: 50mm; test speed: 50mIll, min (if not otherwise specified); test temperature: 23 ± 1C;
Bending Performance: with cMr5104 computer-controlled electronic universal testing machine according
GBl048-79 test, the specimen span: 60mm; provisions deflection: 3.994 Shan; test speed: 2mm, m Rainbow test
temperature: 23 ± 1C; Impact: Impact Tester with cHARH7xcJ4 by GBl048.79 test, test temperature: 23 ± 1C.

1.6 POLARIZING MICROSCOPE

Law melt tablet,tablet temperature 220 ± 5C, non-isothermal crystallization using natural cooling in air

1.7 X-RAY DIFFRACTION ANALYSIS

Japan Science Rigaku D / Max 2550/PCX ray diffraction, cu Ka radiation wavelength 0.154nm, excitation voltage
40kv, inspire current 300rnA

RESULTS AND DISCUSSION

2.1 SUPERFINE CALCIUM CARBONATE MODIFIED POLYPROPYLENE

1) Electron microscopy characterization
Figure 1 clearly see that there are obvious interface between the crystal ball, and calcium carbonate plus a superfine
polypropylene photos can be seen, fine calcium carbonate added to make polypropylene spherulite, which also
borders become more blurred, this is due to the presence of ultra-fine calcium carbonate, polypropylene
crystallization process, promote the heterogeneous nucleation of polypropylene, and make part of the sub-α into β
crystal ball crystal ball. It can be explained as follows: ① After ultrafine calcium carbonate surface treated with
polypropylene polymer chain prone to physical and chemical combination can improve the binding force between
the two phases when subjected to external shocks, ultra-fine calcium carbonate matrix will induce shear yielding
deformation, absorb more impact energy, but too fine calcium carbonate content high, polypropylene melt easily
reunion, when under attack, the formation of a large number of voids and cracks, causing a decline in the overall
performance composite materials; presence ② superfine calcium carbonate crystallization can be used as a
nucleating agent of polypropylene spherulites refinement, also resulted in the generation of crystal-induced B
toughness of the composite material is improved; ③ polarizing microscope photographs.

Fig.1 Polarized light micrograph of PP(left) and 10%CaCO3/90%PP(right)

Unmodified PP, the external force is likely to rupture phase interface; while the modified PP / CaCO3 blends, the
phase interface unclear, the surface treatment agent is formed between the substrate and a resilient filler material
buffer layer, which can effectively transfer and stress relaxation interface, better able to absorb and disperse impact
from outside, thereby improving the impact strength of the composite.

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2)Calcium carbonate modified polypropylene x-ray diffraction analysis

Tab. 1 XRD data of CaCO3/PP

0.5%TMB/PP 0.5%TMB/(10%CaCO3&90%PP)
Wc,x=53.46%; K=29.88%; S=30.34% Wc,x=55.90%; K=28.81%; S=17.74%
2-Theta/℃ d(nm) 2-Theta/℃ d(nm)
(110) 13.721 6.4484 (110) 13.694 6.4613
(300) 15.650 5.6577 (300) 15.681 5.6464
(040) 16.503 5.3671 (040) 16.467 5.3787
(130) 18.094 4.8987 (130) 18.094 4.8985
(301) 20.613 4.3053 (301) 20.678 4.2920

Table 1 x-ray diffraction results showed that the presence of ultrafine CaC03, reduced content of β-crystal, the
degree of order β crystals decreased, indicating that the ultrafine crystal CaC03 affect β induced crystallization
nucleating agent, and to facilitate increase in α crystals[4].

Data show: The CaCO3 is added to increase the crystallinity of PP, PP and increase the crystal size, the larger the
lattice parameters are increased, wherein the b axis is most increased significantly [5].

3)Influence on the mechanical properties of calcium carbonate modified polypropylene

As it shows in Table 2, when A is CaC03 beneficial to improve the tensile properties of polypropylene monomer is
covered, when B is cac03 monomer is coated to improve the bending properties of polypropylene favorable, and
when C is Cac03 monomer when coated polypropylene favorable impact performance improvement.
Tab. 2 Effect of monomer on the mechanical properties of PP

Tensile strength Tensile modulus Flexural strength Flexural modulus Izod impact strength
Items
(Mpa) (Gpa) (Mpa) (Gpa) (KJ/m2)
CaCO3 36.4 1.27 34.67 0.87 6.26
Monomer A 37.3 1.38 35.45 0.88 6.88
Monomer B 3.18 1.25 40.98 1.04 7.45
Monomer C 36.35 1.03 32.03 0.79 7.84

4) The impact of calcium carbonate filler content notched impact strength of PP

Experimental results show that the notch impact strength of PP increases to improve the first CaCO3 content
decreased and reached the maximum at about 5%. This is because the surface effect of nanoparticles, resulting in a
composite system when under attack, will produce more than the presence of micro-cracks in general filler absorb
more impact energy, thereby preventing further development of cracks and passivation, but if filler content is too big,
too close to the particles, micro-cracks are likely to develop into a macroscopic crack, making the notch impact
strength, shown in below Fig2.

Fig. 2 Effect of CaCO3/PP content vs izod impact strength

5) Ultrafine CaCO3 on the performance of the modified cross-linked polypropylene

It can be seen from Figure 3 and 4, a similar variation of the mechanical properties of ultrafine CaCO3 modified
crosslinked PP, PP modified with ultrafine CaCO3, with the tensile strength of ultra-fine CaCO3 content increases
the composite modulus of elasticity and the gap impact intensity firstly increased and then decreased, compared with
the ultra-fine CaCO3 modified PP, significantly lower strength and modulus, and toughness is significantly higher,
which is a long-chain alkyl structure crosslinkers B related.

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Notched impact strength of the composite increases as the caco, content first increased and then decreased and
reached the maximum at about 5%. This is because the surface effect of nanoparticles, resulting in a composite
system when under attack [5], will produce more than the presence of micro-cracks in general filler absorb more
impact energy, thereby preventing further development of cracks and passivation, but if filler content is too big, too
close to the particles, micro-cracks are likely to develop into a macroscopic crack, making the notch impact strength.

Fig.3 Effect of content CaCO3/PP on the tensile strength

Fig. 4 Effect of content CaCO3 on izod impact strength

According to the results, impact strength with gap filler, coated polymer ratio increases continuously improve High.
This is because after in situ emulsion polymerization, forming with elastic Core-shell particle structure of the
cladding layer due to the presence of the polymer, significantly reduced from the surface of CaCO3 The energy,
reduce agglomeration of nano CaCO3 during melt mixing[6],it can be uniformly dispersed in the PP: Long chain
polymer by entanglement with the matrix resin and the matrix resin CaCO3 improved compatibility, increasing
Strong interfacial adhesion of the filler and the matrix, thereby increasing the notched impact strength of the
composite system, if the filler, The coating polymer is relatively small, due to the large presence of the
homopolymer of the monomer coating, and the polyethylene photopolymer[7]. Propylene compatibility there are
some differences, when the material is under attack, leaving the gap is easy to form stress concentration Impact
strength.

Tab. 3 Effect of velovity on the CaCO3/PP

Velocity Tensile strength Flexural strength Flexural modulus Izod impact strength
(rpm) (Mpa) (Mpa) (Gpa) (KJ/m2)
CaCO3 29.3 32.06 1.28 16.26
Monomer A 30.1 33.54 1.33 16.28
Monomer B 29.98 33.73 1.26 15.65
Monomer C 29.94 34.82 1.31 15.34

6) Screw speed of impact modified polypropylene ultra-fine calcium carbonate

Table 3 shows that the screw speed has little effect on the mechanical properties of ultrafine CaCO3 hiding acidic
polypropylene, mainly because in the case already have a certain speed, then increase speed to enhance superfine
polypropylene matrix resin CaCO3 the dispersion is not.

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2.2 GRAFTED MODIFICATION OF PP
1)Reaction mechanism grafted polypropylene
A radical initiator in the reaction suspension grafted polypropylene, PP is formed first macromolecular radicals; the
radical B is prone to lead to bond breaking reaction of polypropylene degradation. After the addition of styrene,
since the stabilizing effect of the benzene ring conjugated, PP macro radicals styrene monomer and easily connected
to the first styrene-based macromere to form a stable free radical, this reaction in the whole system is the
predominant the reaction, then the reaction with the styrene-based monomer is the reaction of free radical molecules.
We know that for copolymerization monomer, which is the determining factor of two monomer reactivity ratiosthe
monomer reactivity ratio study judged by the following formula [8].

Where ri (i = 1, 2) for the reactivity ratio. Q. e in the formula Q is a measure of the effect of the monomer; e is a
value characterizing the polarity effect of conjugated monomers. The basic principle is that, if the Q value close to
the size of the two monomers, then the two monomers copolymerizable prone contrary, if the Q value of the size of
the two very different monomers, indicates that they are not prone to the copolymerization reaction.

Tab. 4 the Q and e value of monomers

Monomer Q e
MAH 0.86 3.69
St 1.00 -0.80

It can be seen from the above data in the table, and MAH-grafted styrene monomer Q value is very close, so when
the Added a suspension system grafted styrene macromer after formation of styryl radicals, MAH contents can vary
And the styrene-based macromer easily radical copolymerization reaction, so that it by grafting monomers more
benzene Ethylene grafted onto the polypropylene chain length so that they have a greatly increased rate of graft.

2) Grafted polypropylene melt flow rate

It can be seen from Table 5, the content of MAH increases, the melt flow rate is gradually reduced, and the addition
of St, particularly the melt flow rate decreases. These data illustrate: In the process of grafting of the suspension,
with the increase of the content of MAH, st can effectively inhibit the degradation of polypropylene was added to
improve the rate of grafting of polypropylene, so that the polypropylene melt flow rate is reduced .

Tab. 5 MI of grafted PP

PP-g-MAH PP-g-MAH PP-g-MAH PP-g-MAH-St

Item Neat PP
(2.5%) (5.0%) (7.50%) (2.5%+2.5%)
MI(g/10min) 10 8.7 7.3 6.8 4.9

3) Infrared spectra of grafted polypropylene

After extraction grafted polypropylene film by pressing 200C by infrared spectroscopy analysis of the samples.

Fig. 5 shows the MAH appeared characteristic peaks 1659cm-1 and 3145 cm-1 Department indicates MAH grafted
on a polypropylene molecular chain.

Fig. 5 FTRI spectra of PP-g-MAH

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4) Grafted polypropylene orthogonal
Select the b (34) orthogonal table 6; select the experiment filler / coating polymer ratio, and grafted polypropylene
content the filler content of the composite of three factors.

From the experimental results described in below table 6 it can be seen its optimum conditions: A>B>C. As can be
seen from the poor image of the factors Ring degree: A, B, C, i.e., the filler / coating polymer maximum ratio of
grafted polypropylene content on the impact Times, minimal impact composite filler content.
Tab. 6 The results of orthogonal experiment

PP-g-MAH, Encapsulating St, Izod impact strength

Items monomer C
wt% wt% (KJ/m2)
1 10:1 10 2.5 12.6
2 10:1 7.5 5.0 11.8
3 10:1 5.0 7.5 11.4
4 7.5:1 10 5.0 13.5
5 7.5:1 7.5 7.5 10.4
6 7.5:1 5.0 2.5 10.6
7 5:1 10 7.5 10.4
8 5:1 7.5 2.5 9.5
9 5:1 5.0 5.0 10.1
K1 35.8 36.1 32.4
K2 33.9 31.2 35.6
K3 30.1 32.3 32.4
k1 11.9 12 10.7
k2 11.5 10.6 11.5
k3 9.8 10.6 10.6
R 2.2 1.7 1.2

5) Grafted polypropylene impact on the notched impact strength

According to the results of orthogonal experiment, notched impact strength increases with the content of the grafted
polypropylene continuous improvement and the maximum at about 10%. This is because a polar group grafted
monomer to improve the polarity of the PP, and PP to improve the interaction between the elastic covering layer to
improve the notched impact strength of the composite system.

Fig.6 Effect of content MAH/PP on the tensile strength

As with a MAH content increases, more of PP macromolecules are protected, you can make PP moderately
crosslinked to form three-dimensional network structure is conducive to absorb external impact energy; makes
notched impact strength increased; mutually crosslinked PP increased interaction between the polymer chains, so
easily slip occurs between polymer chains, causing the polymer chains to increase the force, thereby increasing the
rigidity of the polymer chains to increase the pull-PP tensile properties, however, when the crosslinking agent to a
certain extent, with the increase in the three-dimensional spatial network structure, and the crosslinking agent is
easily prone to self-polymerization reaction, the resulting tensile and impact properties of PP declined .

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Fig. 7 The effect of the PP-g-MAH content vs izod impact strength

CONCLUSION

The results show that the modified polypropylene its notch sensitivity, poor toughness and shrinkage greatly
improved to meet the polypropylene in different fields of application. Meanwhile the study also received the
following modified optimization program:

1) Superfine CaCO3 modified PP, B. PP, PP always crosslinking, the mechanical properties showed a similar pattern.
With increasing levels of ultrafine CaCO3, the mechanical properties of the composites showed a downward trend
after the first rise, at about 10% can be obtained excellent overall performance composite materials.
2) The multi-cell suspension graft polypropylene has a melt flow rate decreased with increasing the content of the
grafting monomer, the graft ratio relative increasing.
3）After three factors and three levels of orthogonal experimental study in situ polymerization grafted polypropylene
showed that the optimum conditions were: polymer coated filler roar 10:1; grafted polypropylene content of 10%;
composite filler content of 5 %, and filler/polymer coated extent than the greatest impact, followed by grafted
polypropylene content on composite filler content with minimal impact.

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