Clarified

Homopolymer for
Injection Moulding

John Kaarto
techX 2019

1 techX - Global Exchange of UNIPOL® PP Technology | April 2019 W. R. Grace & Co. | Confidential
 Clarified Homopolymer

Outline
▪ Purpose of Work
▪ Advantages of Clarified HPP versus Clarified RCP
▪ Applications
▪ Experimental Work
▪ Conclusions
▪ New Grade
▪ Potential Future Work

2 techX - Global Exchange of UNIPOL® PP Technology | April 2019 W. R. Grace & Co. | Confidential
 Clarified Homopolymer

Purpose of Work
▪ To develop a PP product meeting following performance targets:

▪ Homopolymer
▪ 20 MFR
▪ <20% Haze (1mm)
▪ For Injection Moulding
▪ Non-phthalate catalyst: CONSISTA® catalyst

3 techX - Global Exchange of UNIPOL® PP Technology | April 2019 W. R. Grace & Co. | Confidential
 Clarified Homopolymer

Why a clarified homopolymer (c-HPP)?

▪ Clarified homopolymer advantages over clarified random (c-RCP)
▪ Homopolymer has:
▪ Better heat resistance
▪ Better for microwaving
▪ Better stain resistance to food with tomatoes & oil
▪ Better stiffness
▪ Better topload; can be down-gauged (thinner walls)
▪ Higher Haze
▪ Difference vs c-RCP less at thinner thicknesses
▪ Difference can be reduced with higher concentration of NX8000
▪ No need for ethylene
▪ Site may not have ethylene; cannot make RCP
▪ Plant may not be configured for ethylene; cannot make RCP

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 Clarified Homopolymer

Applications
▪ Medical
▪ Syringes
▪ Pill Vials / Bottles
▪ Labware
▪ Food Storage

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 Clarified Homopolymer

Experimental Work
▪ Phase 1
▪ Starting Point: SHAC® 201 based homopolymer LH5831-20N
▪ 1900 ppm Millad® 3988i
▪ ISBM grade, 20 MFR, historically <20% haze
▪ Made pilot plant prototypes with newer generation catalyst: CONSISTA® C602
▪ Formulated with newer generation clarifier, Millad® NX8000.
▪ Ran tests at different XS levels
▪ Expected an improved product
▪ Phase 2
▪ Because Phase 1 expectations were not met
▪ Ran broader range of clarifier concentrations
▪ Moulded samples containing Millad® NX8000 at lower temperature
▪ Added more antacid in 2 pairs
▪ Purged extruder and IM machine between products containing Millad® 3988i
and NX8000
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 Clarified Homopolymer

Experimental Samples
Sample ID Catalyst Donor % XS Irganox® Irgafos® DHT-4A® Millad® Millad®
(Powder) 1010 168 (Kisuma) 3988i NX8000
(BASF) (BASF) (Milliken) (Milliken)
Viscotek® ppm ppm Ppm ppm ppm
PHASE 1
5D98 SHAC® 201 ADT5500 5.5 1000 1000 400 none none
Q670-1 C602 D9700 2.68 500 1000 180 1900
Q670-2 C602 D9700 2.68 500 1000 180 2000
Q670-3 C601 D9700 4.05 500 1000 180 2000
Q670-4 C601 D8700 1.64 500 1000 180 2000
PHASE 2
Q860-1 C602 D9700 2.67 500 750 180 1900
Q860-2 C602 D9700 2.67 500 750 180 2100
Q860-3 C602 D9700 2.67 500 750 360 2100
Q860-4 C602 D9700 2.67 500 750 180 2300
Q860-5 C602 D9700 1.5 500 750 180 none none
Q860-6 C602 D9700 2.67 500 750 180 2000
Q860-7 C602 D9700 2.67 500 750 180 2200
Q860-8 C602 D9700 2.67 500 750 360 2200
Q860-9 C602 D9700 2.67 500 750 180 2400

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 Clarified Homopolymer

Experimental Results
Sample Catalyst % XS DHT-4A Millad Millad Pellet Moulding Haze Flex-Mod
ID (Powder) 3988i NX8000 MFR Melt (%) 1%sec
Temp 23°C
Viscotek ppm ppm ppm dg/min °C 1.0 mm MPa
PHASE 1
5D98 SHAC® 201 5.5 4 260 59 1280
Q670-1 C602 2.68 180 1900 25 256 19 1998
Q670-2 C602 2.68 180 2000 25 260 26 1811
Q670-3 C601 4.05 180 2000 26 260 23 1637
Q670-4 C601 1.64 180 2000 25 260 28 1918
PHASE 2
Q860-1 C602 2.67 180 1900 24 260 21 na
Q860-2 C602 2.67 180 2100 25 260 18 na
Q860-3 C602 2.67 360 2100 24 260 17 na
Q860-4 C602 2.67 180 2300 25 260 16 na
Q860-5 C602 1.5 180 none none 14 190-200 65 na
Q860-6 C602 2.67 180 2000 24 190-200 26 na
Q860-7 C602 2.67 180 2200 24 190-200 22 na
Q860-8 C602 2.67 360 2200 24 190-200 24 na
Q860-9 C602 2.67 180 2400 25 190-200 19 na

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 Clarified Homopolymer

Experimental Results – Key Observations

▪ Adding a higher amount of antacid did not give lower haze; therefore
180 ppm of DHT4A is sufficient to protect the clarifier.
▪ Need => 2100 ppm of Millad® 3988i to achieve <20% haze (1mm)
▪ Need => 2400 ppm of Millad® NX8000 to achieve <20% haze (1mm)
▪ A lower amount of Millad® 3988i (free flowing DMDBS) can be used
which can be a cost savings
▪ The composition containing Millad® 3988i achieves highest stiffness,
almost 2000 MPa with a normal level of XS (2.7%). Better than 1.6%XS
and 2000 ppm of NX8000. Almost like HCPP.
▪ The composition containing % XS Millad® Millad® Haze (%) DSC Tc
(Powder) 3988i NX8000 (°C)
Millad® 3988i has higher Tc. Viscotek® ppm ppm 1.0 mm °C
5.5 0 0 59 113
2.68 1900 0 19 132
2.68 0 2000 26 117
4.05 0 2000 23 115
1.64 0 2000 28 116
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 Clarified Homopolymer

Experimental Results – Plot Haze versus

Concentration of NX8000 or 3988i
Clarified Homopolymer
70

60
HAZE (%) on 1 mm plaque

50

40

30 NX8000
3988i
20

10

0
0 500 1000 1500 2000 2500 3000
ppm of CLARIFIER

Clarified HPP has haze significantly lower than non-clarified HPP. Millad® 3988i
systematically lower in haze versus NX8000 in this concentration range.

10 techX - Global Exchange of UNIPOL® PP Technology | April 2019 W. R. Grace & Co. | Confidential
 Clarified Homopolymer

CONCLUSIONS
▪ In homopolymer the Millad® 3988i seems more effective than the
NX8000 at concentrations in the 2000-2500 ppm range.
▪ To achieve <20% haze consistently we recommend 2300 ppm of Millad®
3988i.
▪ If 2300 ppm is added with +/- 10% feeding accuracy the haze is still
<20% at 2100 ppm; therefore 2300 ppm is a robust target.
▪ In brochure see UNIPOL® PP grade LH7086-20N.P
▪ If Millad® NX8000 is preferred we would recommend using >2400 ppm
and suggest 2600 ppm as target.
▪ If a lower haze value is needed then adding e.g. 4000 ppm of NX8000 is
an option if making a clarified RCP is not possible.
▪ Haze performance of advanced nucleators in HPP may be evaluated in
the future.

11 techX - Global Exchange of UNIPOL® PP Technology | April 2019 W. R. Grace & Co. | Confidential
 THANK-YOU !
Questions?

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 GRACE®, CONSISTA® and SHAC® are trademarks, registered in the United States and/or other countries, of W. R. Grace & Co.-Conn. MILLAD® is a
trademark, registered in the United States and/or other countries, of Milliken. UNIPOL® is a trademark of The Dow Chemical Company or an affiliated
company of Dow. W.R. Grace & Co.-Conn. and/or its affiliates are licensed to use the UNIPOL® trademark in the area of polypropylene. VISCOTEK® is
a trademark, registered in the United States and/or other countries, of Malvern Instruments, Inc. IRGANOX® and IRGAFOS® are trademarks, registered
in the United States and/or other countries, of BASF SE. DHT-4A is a trademark, registered in the United States and/or other countries, of KYOWA
Chemical Industry Co., Ltd. This presentation is an independent publication and is not affiliated with, nor has it been authorized, sponsored, or otherwise
approved by the aforesaid companies. This trademark list has been compiled using available published information as of the publication date of this
brochure and may not accurately reflect current trademark ownership or status. © Copyright 2019 W. R. Grace & Co.-Conn. All rights reserved.

13 techX - Global Exchange of UNIPOL® PP Technology | April 2019 W. R. Grace & Co. | Confidential