M C A

TECHNOLOGIES GmbH
(Switzerland)

Advances in the chemistry and technologies of organic pigments and additives for plastics: From appearance to functionality
Dr. Bansi L. Kaul, CEO
MCA Technologies GmbH 4105 Biel-Benken, Switzerland kaul@mcatechnologies.com http://www.mcatechnologies.com

It is all about: "Chemistry-our life, our future

About us

M C A

TECHNOLOGIES GmbH
(Switzerland)

Co-sponsors and table-top exhibitors at this conference. Brochures of our products and services available at the table top exhibition. Conducting/Supporting R&D & business development in environmentally friendly technologies and products; Todays presentation is a demonstration of that. Bridging gaps between science and technology to make lab curiosities as commercial realities.

Plastic processing

M C A

TECHNOLOGIES GmbH
(Switzerland)

Besides the equipment, plastic processing requires not only the virgin polymer and anti-oxidations and processing aids but also: Colorants-Pigments & polymer soluble dyes Functional and effect additives such as fire retardants Anti-aging, light-stabilizers & UV absorbs For the ease of incorporation of many of these ingredients into the polymer during processing, masterbatch form offers an ideal choice and opportunity

Recent issues and opportunities for masterbatch industry

M C A

TECHNOLOGIES GmbH
(Switzerland)

Diarylide replacements Heavy-metal pigments replacements New Pigment Technologies (DPP Pigments) Halogen-free and cost-effective fire/flame retardants
Food contact, packaging and toys regulations &

requirements Recycling and cradle-to-grave concerns All-in-one masterbatches (for cost effectiveness and competitive edge) Regulations(REACH etc.) and consumer conscience

Thermal Decomposition of Benzidine/Diarylide Pigments in Plastics

M C A

TECHNOLOGIES GmbH
(Switzerland)

I.e. Pigment Yellows 17 & 83 I.e. Pigment Oranges 13 & 34

R1 H2N R2 R2

R1 NH2

Only the tip of the ice-berg: Many azo pigments can also undergo similar thermal decomposition in plastics, generating toxic aromatic amines. Hence, in the future the masterbatches, and not the pigments, will have to be tested for the aromatic amine content.

Replacements of Diarylide Yellows in Plastics (middle-class)

O O O O H N O N O H N N H O CH3 N N O O

M C A

TECHNOLOGIES GmbH
(Switzerland)

H O

Pigment Yellow 155 (green shade) (Cost- & value-effective of most replacements)
O H H N O N H N O H CH3 N N X N N H3C H O N O H H N O N H

Pigment Yellow 139 (red shade) (Not compatible with HALS)

Pigment Yellow 180 (middle shade)

Pyrazolone Azo-Toner (Metal-Salt) Pigments

R1 R5 N N O M R4 ++ N H N R2 R3

M C A

TECHNOLOGIES GmbH
(Switzerland)

Pigment Yellow 183 Pigment Yellow 191 The new Basf Yellow (?) (Masterbatch 2011)

For better heat stability

High-Performance Cadmium Yellows Replacements

R4 R3 H

M C A

TECHNOLOGIES GmbH
(Switzerland)

R2 R1

N N H3C

O N O H

H N O N H

Pigment Yellow 138, green shade High colour strength

Pigment Yellow 181, red shade Poor colour strength

Pigment Yellow 110, red shade Poor colour strength

Cadmium Orange/Red Replacements

HO H N O N H CH3 O H N N N N H O

M C A

TECHNOLOGIES GmbH
(Switzerland)

H N O N H

N Ni N

O O

Pigment Orange 64, yellow shade

Pigment Orange 68, red shade One of the most stable of all organic pigments in engineering polymers (ABS, polyamides/nylons )

Disazo Condensation Pigments

Cl O R5 N R3 R4 R6 R5 R4 R3 N N OH H N O R2 R1 HO H N O R4 R3 N N R6 R5 H O N N H O N H R2 R1 H N O CH3 H O H N N Cl N O R5 R3 R4

M C A

TECHNOLOGIES GmbH
(Switzerland)

Pigment Yellow 93 Pigment Yellow 95

Pigment Red 144 Pigment Red 166 Pigment Red 214 Pigment Red 242

Red Azo-condensation Pigments

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TECHNOLOGIES GmbH
(Switzerland)

R=CF3: Pigment Red 242 ( Scarlet) R=Cl: Pigment Red 214 (Blue Red)

The most heat stable and lightfast of all azocondensation pigments

BON-Azo Benzamidazolone Pigments

R2 R3 R1 N N OH H N O N H H N O

M C A

TECHNOLOGIES GmbH
(Switzerland)

Pigment Red 176 Pigment Red 185 Pigment Brown 25

Quinacridone/Perylene Pigments
11 10 9 8 O H N O 1 2 N H 3 4

M C A

TECHNOLOGIES GmbH
(Switzerland)

Quinacridone
2,9-Dimethyl: Pigment Red 122 (Magenta) 2,9-Dichloro: Pigment Red 202 (For nylons)

Perylene

Pigment Red 149

Dioxazine Violet

M C A

TECHNOLOGIES GmbH
(Switzerland)

Pigment Violet 23
One of the most cost effective and widely used organic pigment

Phthalocyanine Pigments

M C A

TECHNOLOGIES GmbH
(Switzerland)

N X N N

N Cu N N

Pigment Blue 15

Pigment Green 7

Universal workhorse pigments

Polymer Soluble Pigment Yellow 192 for Polyamides/Nylons

M C A

TECHNOLOGIES GmbH
(Switzerland)

Pigment Yellow 192

A polymer soluble dye with performance characteristics of a pigment in nylons; (like Pigment Yellow 147 in polyester )

DPP Pigments

M C A

TECHNOLOGIES GmbH
(Switzerland)

O HN NH O

Pigment Red 254

Pigment Red 264

Most successful of all recently introduced organic pigments suitable for polyolefins and PVC , styrenics, but not for engineering polymers . Generally not as stable as azo-condensation pigments in plastics

Green-Technologies of Pigments and additives

M C A

TECHNOLOGIES GmbH
(Switzerland)

Example: MCA solvent-free greentechnology of DPP pigments

State-of-the-art versus MCA Solvent-free DPP Pigment Technology

State-of-the-art synthesis

M C A

TECHNOLOGIES GmbH
(Switzerland)

MCAT synthesis

Reactants

Reactants
3-5 times solvent

MCA DPP Pigments Green Technology

Less energy demand Less chemicals demand Less safety risk
Less waste Higher productivity Better quality Products (nano-particles)

M C A

TECHNOLOGIES GmbH
(Switzerland)

Fire & Flame retardants

M C A

TECHNOLOGIES GmbH
(Switzerland)

Although not always a burning topic at the most masterbatch conferences, fire & flame retardants, with almost 2 million tons annual consumption are the largest volume but the least developed and therefore the most challenging of all polymer additives Fire Retardancy is not a choice but mostly a legal requirement And hence a major opportunity Considering the loadings required, compared to any other colorant or additive, dispersion technology here is a very critical factor, both for performance and economy

Burning issues of fire and flame retardants

M C A

TECHNOLOGIES GmbH
(Switzerland)

High loadings required Halogen + Peak heat release rate and smoke density Non-compatibility & reactivity

Promising of all future FRTechnologies:

M C A

TECHNOLOGIES GmbH
(Switzerland)

Fire-barrier technology
In the event of fire formation of a spongy charbarrier at the fire point by so-called self-immolation mechanism Extinguishing the fire and preventing its proliferation Lower loadings with low heat of glow & almost no smoke

Novel MCA PPM Triazines , to be presented, is now a recognized milestone of this technology

MCA PPM Triazine HF:

Novel, polymeric, halogen-free & chemically mostly inert universal nitrogen synergist
M C A

TECHNOLOGIES GmbH
(Switzerland)

Chemical Formula: C126H212N61O11 Exact Mass: 2755.8 Molecular Weight: 2757.4 Elemental Analysis: ; H, 7.75; ; O, 6.38

Universal synergist of FRs and co-synergists

Primary FR
Polyols

Effect
N-P-C-O char formation, acid scavenger

Phosphates & Phosphinates

MCA PPM Triazine HF

Minerals

N-Mineral-C-O Char formation

Low melting or liquids incl. NOR

Nanoclays /PTFE

Char + Antiplastification
Char: Carbon scavenger for less smoke and heat glow

Bromine based

MCA PPM Triazines: Suitability for polymers & resins

Polyolefins

M C A

TECHNOLOGIES GmbH
(Switzerland)

PU/Epoxides

MCA PPM Triazines

PC and its blends

PES/PA (particularly GF)

Why MCA PPM Triazines as nitrogen-synergists?

M C A

TECHNOLOGIES GmbH
(Switzerland)

PPM Triazines are particularly recommended where state-of-theart nitrogen synergists, based on melamine and/or its derivatives have limitations due to any or many of the following reasons:
Sublimation and mould deposits Blooming (particularly incompatibility in polyolefins) Reactivity: Self-condensation and tridimensional (dendrimer) reactivity towards the monomers (urethanes, epoxides); and even polymers (such as polyesters by amidation; polyamides by cross-amidation and with primary FRs (APP) by Preintumescent reaction ((in processing); Heat stability Water solubility Hydrolytic & thermal stability/corrosivity (i.e. Melamine polyphosphate: being rather a weak acid-base salt, can undergo gradual dissociation in the presence of water in the polar polymer itself). Value-in-use: Cheap is not always cheap

MCA PPM Triazine HF-Ammonium polyphosphate combination: PPMT 765 (IS=intumescent system)
M

Polypropylene

(Switzerland) 80% Polypropylene + 765 A 20% PPMT

TECHNOLOGIES GmbH

Almost no burningV-0 & no smoke+, low heat release+

Sample PP PP+20% PPMT 765 (5% HF) t1
(S)

t2
(s) -

Dripping/Ignition of Cotton Yes No

Time to dripping 6 (s)

UL 94 Rating

70

No Rating

No dripping

V-0 (++)

Prof. Camino t.l.: Politecnico di Torino Alessandria, Italy

MCA PPM Triazine 765 + Co-synergist in PP

PPM Triazine 765 % Flamestab NOR 116 % Decabromodiphenyl ethane % Antimony Trioxide PTFE % Total Burning time(t1+t2 s) > 260* UL 94 (1.6mm/1.5 mm) N.C. 40 (V-0) V-2 0.1 15 15 1 15 1

M C A

TECHNOLOGIES GmbH
(Switzerland)

15

15

10 0

10 0 0.1

12 (V-0) V-0 ? V-2

V-0 ?

* t2 not recorded due to total burnout in t1; N.C.: no classification

MCA PPM Triazine HF & a phosphinate combination in glass-filled PA 6

Polyamide 6* Additives Glass fibers Exolit OP 1230** MCA PPM Triazine HF Melamine polyphosphate*** Average burning time(s) UL 94 (1.6 mm) 54.5 0.5 25 15 5 0 3 V-0 54.5 0.5 25 10 10 0 14 V-0/V-1

M C A

TECHNOLOGIES GmbH
(Switzerland)

59.5 0.5 25 7.5 7.5 0 21 V-1/V-2

54.5 0.5 25 0 0 20 32 n.c.

*(Ultramid B3S),** Clariant, ***Melapur 200 (BASF)

Dr. Rudolf Pfaendner Fraunhofer-Institut Darmstadt

MCA Proprietary volatile-organicsolvent-free technology*

M C A

TECHNOLOGIES GmbH
(Switzerland)

Suspension polymerisation in the presence of catalysts

Examples: PVC made by suspension polymerisation PP made using Ziegler-Natta process Patent applications : Polytriazinyl compounds as flame retardants and light stabilizers European Patent application 2130854. Also in China, India, Taiwan, Japan

Patent granted in the USA (Patent No. 8,202,924) *The handprint of the technology

Summary

M C A

TECHNOLOGIES GmbH
(Switzerland)

MCA PPM Triazines: Universal synergist of most fire/flame retardants, and in many polymers. MCA PPM Triazines should enable reduce the total loadings of many FR-systems, and therefore, the total cost of fire retardancy & processing, and thereby improve the quality of the plastic items and reduce the ultimate waste for environmental impact MCA PPM Triazines should enable achieve halogen-free fire retardancy, at a reasonable cost if and wherever required or desired MCA PPM Triazines should enable reduce the peaak heat release rate (pHRR) & smoke density for better fire safety, particularly if combined with brominated or even halogen-free (phosphorous based) flame retardants associated with this problem. Such properties are perhaps more important than even the flame for fire fighting, and for rescue and escape. Ease of incineration at the disposal stage is an environmental plus.

Future Outlook

M C A

TECHNOLOGIES GmbH
(Switzerland)

Novel masterbatching technologies that are gentle both towards the carrier as well as the colorants and additives Novel pigments, fully meeting the definition of a pigment i.e. total insolubility and inertness under the polymer processing conditions Polymer soluble colorants with the characteristics of pigments (Pigment Yellow 147 , Pigment Yellow 192) Better efficacy (low loadings) and environmentally friendly (from cradle to grave) fire retardants Multi-functional additives

Thank You