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DA 3303 E hostanox P-EPQ 09.07 RZ

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Pigments & Additives Division<br />

Plastic Business<br />

Hostanox ®* P-<strong>EPQ</strong> ®<br />

Clarifier Effect in Polypropylene<br />

Exactly your chemistry.


Hostanox ® * P-<strong>EPQ</strong> ®<br />

Introduction<br />

Hostanox ® * P-<strong>EPQ</strong> ® is a highly<br />

effective processing and color<br />

stabilizer for thermoplastic polymers.<br />

It is particularly recommended for<br />

use in polyolefins, especially if tough<br />

requirements, such as high temperature<br />

or demanding shear conditions,<br />

severely attack polymer melts during<br />

processing.<br />

One unique effect of Hostanox P-<strong>EPQ</strong><br />

is its contribution to improved transparency<br />

of polyolefins. This additional<br />

benefit of the processing stabilizer is<br />

clearly pronounced in polypropylene<br />

homo- and copolymers and in LLDPE.<br />

2<br />

> Clarifier Effect in Polypropylene<br />

The classic nucleating agents, e.g.<br />

benzoates, phosphates or sorbitol<br />

derivatives, are typically intended to<br />

influence the spherulite size distribution<br />

and the morphology of semicrystalline<br />

polymers. Characteristic<br />

effects on the physical properties<br />

are, for example:<br />

> Increased crystallization<br />

temperature<br />

> Increased rate of crystallization<br />

> Increased degree of crystallinity<br />

> Reduced average size of the<br />

spherulites<br />

> Increased contact and/or seethrough<br />

clarity<br />

> Improved surface gloss<br />

> Enhanced dimensional stability<br />

of molded parts<br />

> Improved mechanical properties,<br />

such as tensile strength or flexural<br />

modulus<br />

Hostanox P-<strong>EPQ</strong><br />

Hostanox P-<strong>EPQ</strong> complements many<br />

applications of nucleating agents<br />

and may even compensate certain<br />

draw-backs. Such combinations offer<br />

additional benefits:<br />

> Improved color retention during<br />

melt processing<br />

> Minimized yellowing of formulations<br />

containing sorbitol derivatives<br />

> Full compatibility with nucleating<br />

agents<br />

Some examples on the aspects<br />

mentioned above are illustrated in<br />

the following two chapters. All tests<br />

were performed in third generation<br />

polypropylene random copolymers.


Nucleating Properties of<br />

Hostanox P-<strong>EPQ</strong><br />

Figure 1 illustrates the clarifying effect<br />

of Hostanox ® * P-<strong>EPQ</strong> ® measured<br />

on injection molded polypropylene<br />

plaques. After the addition of 0.1%<br />

Hostanox P-<strong>EPQ</strong>, the haze is reduced<br />

by 10 - 15 % compared to the control<br />

sample, whereas P-2 and P-4 have<br />

significantly weaker effects. This<br />

clarity improvement remains nearly<br />

unchanged during multiple extrusion<br />

at 270 °C. Typical clarifiers like NA-1<br />

can even lose their performance under<br />

severe stress conditions (e.g. peak<br />

temperatures, prolonged heat exposure<br />

of the melt), eventually yielding<br />

only marginally improved haze values<br />

in the finished plastic articles.<br />

The improved transparency achieved<br />

just by addition of Hostanox P-<strong>EPQ</strong><br />

correlates with an increase of the<br />

tensile strength (TS) and the crystallization<br />

onset temperature (COT).<br />

As shown in Figure 2, Hostanox P-<strong>EPQ</strong><br />

can improve the tensile strength by<br />

approx. 10 % compared to the reference<br />

(BS only), whereas the competitive<br />

stabilizers have less effect on this<br />

property. The processing stabilizer<br />

Hostanox P-<strong>EPQ</strong> can act to a certain<br />

extent as a nucleating agent. It can<br />

improve the clarity of polypropylene<br />

and enhance its mechanical properties.<br />

Haze (%) after ...<br />

50<br />

40<br />

30<br />

20<br />

10<br />

0<br />

BS only P-<strong>EPQ</strong> P-2<br />

P-4<br />

BS + NA-1<br />

Procedure: Multiple Extrusion at 270 °C.<br />

Specimens: 1 mm Injection Molded Plaques.<br />

Figure 1: Haze of Polypropylene Plaques<br />

1st Extrusion 3rd Extrusion 5th Extrusion<br />

Additives: BS: 0.05 % AO-2 + 0.1 % CaSt;<br />

0.1 % Processing Stabilizer each;<br />

0.25 % Nucleating Agent NA-1.<br />

Tensile Strength<br />

(N/mm<br />

30<br />

150<br />

2 ) TS COT<br />

COT (°C)<br />

20<br />

10<br />

0<br />

BS only P-<strong>EPQ</strong> P-2<br />

P-4 BS + NA-1<br />

Procedure: Mechanical Testing and DSC<br />

Performed after one Extrusion Pass<br />

at 270 °C.<br />

Specimens: 1 mm Injection Molded Plaques.<br />

Additives: BS: 0.05 % AO-2 + 0.1 % CaSt;<br />

0.1 % Processing Stabilizer each;<br />

0.25 % Nucleating Agent NA-1.<br />

Figure 2: Crystallization Onset Temperature (COT) and Tensile Strength (TS) of Polypropylene Random Copolymer<br />

100<br />

50<br />

0<br />

3


Influence of NA-1 on the<br />

Stabilization of Polypropylene<br />

during Extrusion<br />

Data on the melt and color stability of<br />

polypropylene are shown in Figures 3<br />

and 4, illustrating the effect of the nucleating<br />

agent NA-1 on the performance<br />

of the stabilizers Hostanox ® *<br />

P-<strong>EPQ</strong> ® , P-2 and P-4 respectively. By<br />

using 0.1 % Hostanox P-<strong>EPQ</strong>, optimal<br />

melt stability is achieved for five repeated<br />

extrusions. Its effectiveness<br />

as melt stabilizer is almost maintained<br />

also in presence of NA-1.<br />

The corresponding results for the<br />

color stability shown in Figure 4<br />

support, furthermore, the preferred<br />

use of Hostanox P-<strong>EPQ</strong> also in<br />

nucleated polypropylene. It is evidently<br />

superior to the competitive<br />

phosphites P-2 and P-4.<br />

4<br />

MFR (g/10 Min.)<br />

at 230 °C, 5 kg<br />

20<br />

15<br />

10<br />

5<br />

0<br />

only BS+P-<strong>EPQ</strong> P-<strong>EPQ</strong> P-2<br />

P-4<br />

Procedure: Multiple Extrusion at 270 °C.<br />

Figure 3: Melt Stabilization of Polypropylene<br />

The distinct properties of nucleated<br />

polyolefins are significantly dependent<br />

on the chemical structure and the kind<br />

of nucleating agent applied. The typical<br />

heterogeneous nucleators, such as<br />

Hostanox 4030 or NA-3, are high<br />

melting, salt-like compounds which<br />

are primarily designed to improve<br />

crystallization kinetics and mechanical<br />

properties of a polymer. In contrast to<br />

this, dibenzylidene sorbitols like NA-1<br />

and NA-2 are preferably used as<br />

clarifiers, i.e. for reduction of haze.<br />

1 Pass 3 Passes 5 Passes<br />

Additives: BS: 0.05 % AO-2 + 0.1 % CaSt;<br />

0.1 % Processing Stabilizer each;<br />

0.25 % Nucleating Agent NA-1 each.<br />

Figure 5 shows the influence of<br />

processing stabilizers on the haze of<br />

polypropylene containing different<br />

nucleating agents.<br />

The formulations with NA-1 and NA-2<br />

in Figure 5 are examples for highly<br />

clarified polypropylene. In such cases,<br />

processing stabilizers contribute only<br />

marginally to further improvement of<br />

the optical properties. However, if<br />

heterogeneous nucleators are used<br />

(Hostanox 4030 and NA-3 in Figure 5),<br />

the generally higher haze values can<br />

be clearly reduced in combinations<br />

with Hostanox P-<strong>EPQ</strong>.


Yellowness Index<br />

(on Plaques)<br />

5<br />

4<br />

3<br />

2<br />

1<br />

0<br />

only BS+P-<strong>EPQ</strong> P-<strong>EPQ</strong> P-2<br />

P-4<br />

Procedure: Multiple Extrusion at 270 °C. Additives: BS: 0.05 % AO-2 + 0.1 % CaSt;<br />

0.1 % Processing Stabilizer each;<br />

0.25 % Nucleating Agent NA-1.<br />

Figure 4: Color Stabilization of Polypropylene<br />

Haze (%)<br />

60<br />

50<br />

40<br />

30<br />

20<br />

10<br />

0<br />

1 Pass 3 Passes 5 Passes<br />

only BS 0.1 % P-<strong>EPQ</strong> 0.1 % P-2 0.1 % P-4<br />

NA-1 NA-2 Hostanox ® *-4030 ®<br />

Procedure: Haze measured after one<br />

Extrusion Passage.<br />

Specimens: 1 mm Injection Molded Plaques.<br />

Figure 5: Effect of Processing Stabilizers in Nucleated Polypropylene<br />

NA-3<br />

Additives: BS: 0.05 % AO-2 + 0.1 % CaSt;<br />

0.25 % Nucleating Agent each.<br />

5


Conclusion<br />

Hostanox ® * P-<strong>EPQ</strong> ® has to be considered<br />

as the additive of choice in<br />

applications of polypropylene where<br />

superior stabilization is required.<br />

Particularly in clarified or nucleated<br />

polypropylene, the use of Hostanox<br />

P-<strong>EPQ</strong> safeguards excellent melt and<br />

color stability during processing of<br />

the resin.<br />

6<br />

Experimental<br />

Third-generation polypropylene random<br />

copolymer was melt compounded<br />

with the respective additive formulations.<br />

The following base stabilization<br />

(BS) was used: 0.1 % calcium<br />

stearate plus 0.05 % AO-2. Processing<br />

stabilizers (PS) were applied at 0.1 %<br />

and nucleating agents (NA) at a level<br />

of 0.25 %.<br />

Preparation of the Samples<br />

Additives were dry blended with the<br />

polymer and pre-extruded at 210 °C.<br />

Multiple extrusions were carried out<br />

on a single screw laboratory extruder<br />

(compression ratio 1:3, L:D = 25, 50<br />

rpm). The strand was chilled in water<br />

and pelletized. These samples were<br />

used for MFR characterization, reprocessing<br />

and for injection molding<br />

into 100 x 100 x 1 mm3 plaques on<br />

an Arburg Allrounder 221-75-350 at<br />

245 °C.


Mode of Characterization<br />

Melt Flow Ratio (MFR) according<br />

to ASTM D-1238 (equivalent to ISO<br />

1133) using pelletized polymer.<br />

Yellowness Index (YI) according<br />

to ASTM D-1925 measuring light<br />

reflection on 1 mm plaques.<br />

Haze Value according to ASTM D-1003<br />

measuring light scattering through<br />

1 mm plaques.<br />

Tensile Strength (TS) according to DIN<br />

53455 applying a crosshead speed of<br />

10 cm/min. The specimens for tensile<br />

testing were punched out of 1 mm<br />

injection moulded plaques.<br />

Crystallization Onset Temperature<br />

(COT) measured on Mettler DSG.<br />

Temperature (COT) 20 thermoanalyzer.<br />

Starting temperature 200 °C, cooling<br />

rate -10 °C/min.<br />

Key to Abbreviations<br />

AO-2:<br />

Tetrakis-[methylene-3-(3',5'di-tert-butyl-4'-hydroxy-phenyl)propionate]-methane<br />

P-2:<br />

Tris(2,4-di-tert-butylphenyl)<br />

phosphite<br />

P-4:<br />

Tris(nonylphenyl) phosphite<br />

(TNPP)<br />

Heterogeneous Nucleators<br />

Hostanox ® * 4030:<br />

Aluminium-monohydroxy-di-<br />

(4-tert-butyl-benzoate)<br />

NA-3:<br />

Sodium-di-(4-tert-butyl-phenyl)<br />

phosphate<br />

Homogeneous Nucleators<br />

NA-1:<br />

1,3:2,4 Di-benzylidene sorbitol (DBS)<br />

NA-2:<br />

1,3:2,4 Di-(4-methyl-benzylidene)<br />

sorbitol<br />

7


Please note<br />

This information is based on our present state of knowledge and is intended to provide<br />

general notes on our products and their uses. It should not therefore be construed<br />

as guaranteeing specific properties of the products described or their suitability for<br />

a particular application. Any existing industrial property rights must be observed.<br />

The quality of our products is guaranteed under our General Conditions of Sale.<br />

® = Trademark of Clariant registered in numerous countries<br />

®* = Trademark registered in numerous countries and licensed to Clariant<br />

Edition: September 2007<br />

www.pa.clariant.com<br />

Clariant International Ltd.<br />

Pigments & Additives Division<br />

Marketing Plastic Business<br />

Rothausstrasse 61<br />

4132 Muttenz<br />

Switzerland<br />

Phone: +41- 61- 469-7466<br />

Fax: +41- 61- 469-7540<br />

Clariant Produkte (Deutschland) GmbH<br />

Pigments & Additives Division<br />

Marketing Plastic Business<br />

Ludwig-Hermann-Straße 100<br />

86368 Gersthofen<br />

Germany<br />

Phone: +49 -821-479-2693<br />

Fax: +49 -821-479-2968<br />

Clariant Production (France)<br />

Pigments & Additives Division<br />

Marketing Plastic Business<br />

Boîte Postale 149<br />

68331 Huningue Cedex<br />

France<br />

Phone: +33 -389-89-6000<br />

Fax: +33 -389-89-6197<br />

Exactly your chemistry.<br />

<strong>DA</strong> <strong>3303</strong> E_09/07

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