6. mca technologies gmbh.pdf

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TECHNOLOGIES GmbH(Switzerland)

Advances in the chemistry and technologies of organic pigments and additives for plastics:

From appearance to functionality

Dr. Bansi L. Kaul, CEOMCA Technologies GmbH

4105 Biel-Benken, [email protected]

http://www.mcatechnologies.com

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

http://www.mcatechnologies.com

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About usCo-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; Today’s presentation is a demonstration of that.

Bridging gaps between science and technology to make lab curiosities as commercial realities.

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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

Plastic processing

For the ease of incorporation of many of these ingredients into the polymer during processing,

masterbatch form offers an ideal choice and opportunity

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Diarylide replacements Heavy-metal pigments replacements New Pigment Technologies (DPP Pigments)Halogen-free and cost-effective fire/flame retardants

Recent issues and opportunities for masterbatch industry

Food contact, packaging and toys regulations & requirementsRecycling and cradle-to-grave concernsAll-in-one masterbatches (for cost effectiveness and competitive edge)Regulations(REACH etc.) and consumer conscience

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Thermal Decomposition of Benzidine/Diarylide Pigments in

Plastics

NH2

R2

R1

NH2

R2

R1

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

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.

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Replacements of Diarylide Yellows in Plastics (middle-class)

HO

NH

NH

O

N

CH3

O N

N

H

HO

NH

NH

O

N

CH3

XON

N

H

Pigment Yellow 155 (green shade) (Cost- & value-effective of most replacements)

Pigment Yellow 180 (middle shade)

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

NN O

HO

N

NH O

ONN

H

CH3

HO

OO

OO

O

O

O

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Pyrazolone Azo-Toner (Metal-Salt) Pigments

M++

N

NR5

ON

NH

R2

R4

R1

R3

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

(Masterbatch 2011)

For better heat stability

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High-Performance Cadmium Yellows Replacements

R3

R4

R1

R2 ONN

H

HO

NH

NH

ON

CH3

Pigment Yellow 138, green shade

Pigment Yellow 110, red shade

Pigment Yellow 181, red shadeHigh colour strength

Poor colour strength

Poor colour strength

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Cadmium Orange/Red Replacements

N

N

O

O

N

H

H

OH

N

CH3N

NO

H

H

Pigment Orange 64, yellow shade

NH

NH N

NO

O

ONi

One of the most stable of all organic pigments in

engineering polymers (ABS, polyamides/nylons )

Pigment Orange 68, red shade

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Disazo Condensation Pigments

NN O

HO

N

NH O

ONN

H

CH3Cl

HO

N

N

R1

R2

R4

R3

HO

H

Cl

R5

R3R4

R5

N

OHN

R1

R2

N

N

OHH H

O O

N

R5

R3

R4

R6

NR3

R5 R4

R6

Pigment Yellow 93Pigment Yellow 95

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

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The most heat stable and lightfast of all azo-condensation pigments

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

Red Azo-condensation Pigments

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BON-Azo Benzamidazolone Pigments

OH

NH

NN

O

R2

R3

R1

N

NO

H

H

Pigment Red 176Pigment Red 185Pigment Brown 25

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12

348

9

1011 N

N

O

O

H

H

Quinacridone/Perylene Pigments

2,9-Dimethyl:Pigment Red 122 (Magenta)

2,9-Dichloro: Pigment Red 202 (For nylons)

Quinacridone Perylene

Pigment Red 149

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Dioxazine Violet

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

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NN

NN

N

N

N

N

CuX

Phthalocyanine Pigments

Pigment Green 7Pigment Blue 15

Universal workhorse pigments

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Polymer Soluble Pigment Yellow 192 for Polyamides/Nylons

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

Pigment Yellow 192

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DPP Pigments

NHHN

O

O

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

Pigment Red 254 Pigment Red 264

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Example: MCA� solvent-free green-

technology of DPP pigments

Green-Technologies of Pigments and additives

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

State-of-the-art synthesis

3-5 times solvent

MCAT synthesis

Reactants

Reactants

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MCA� DPP Pigments Green Technology

Less energy demand

Less chemicals demand

Less safety risk

Less waste

Higher productivity

Better quality Products (nano-particles)

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Fire & Flame retardants

• 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

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“Burning” issues of fire and flame retardants

High loadings required

Halogen + Peak heat release rate and smoke density

Non-compatibility & reactivity

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• In the event of fire formation of a spongy char-barrier 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

Promising of all future FR-Technologies:

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

Fire-barrier technology

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Chemical Formula: C126H212N61O11Exact Mass: 2755.8

Molecular Weight: 2757.4

Elemental Analysis: ; H, 7.75; ; O, 6.38

MCA� PPM Triazine HF: Novel, polymeric, halogen-free & chemically

mostly inert universal nitrogen synergist

MCA� PPM Triazine

HF

Phosphates & Phosphinates

N-P-C-O char formation,

acid scavenger

MineralsN-Mineral-C-O

Char formation

Char + Anti-plastification

Low melting or liquids incl. NOR

Bromine based

Nanoclays/PTFE Char: Carbon

scavenger for less smoke and

heat glow

Universal synergist of FRs and co-synergists

Polyols

Primary FR Effect

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MCA� PPM Triazines

Polyolefins

PES/PA(particularly

GF)

PC and its blends

PU/Epoxides

PPM Triazines: Suitability MCA� PPM Triazines: Suitability for polymers & resins

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PPM Triazines are particularly recommended where state-of-the-art 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 “Pre–intumescent” 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”

Why MCA� PPM Triazines as nitrogen-synergists?

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

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

Sample t1(S)

t2(s)

Dripping/Ignition of Cotton

Time to dripping

UL 94 Rating

PP 70 - Yes 6 (s) No Rating

PP+20% PPMT 765 (5% HF) 1 3 No No dripping V-0 (++)

Polypropylene 80% Polypropylene + 20% PPMT 765

Prof. Camino ĕt.ăl.: Politecnico di Torino Alessandria, Italy

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PPM Triazine 765 % 15 15 15 15 15

Flamestab NOR 116 % 1 1

Decabromodiphenylethane %

10 10

Antimony Trioxide 0 0

PTFE % 0.1 0.1

Total Burning time(t1+t2 s) > 260* 40(V-0)

12(V-0)

UL 94 (1.6mm/1.5 mm) N.C. V-2 V-0 ? V-2 V-0 ?

MCA� PPM Triazine 765 +Co-synergist in PP

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

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

Polyamide 6* 54.5 54.5 59.5 54.5

Additives 0.5 0.5 0.5 0.5

Glass fibers 25 25 25 25

Exolit OP 1230** 15 10 7.5 0

MCA� PPM Triazine HF 5 10 7.5 0

Melamine polyphosphate*** 0 0 0 20

Average burning time(s) 3 14 21 32

UL 94 (1.6 mm) V-0 V-0/V-1 V-1/V-2 n.c.

*(Ultramid B3S),** Clariant, ***Melapur 200 (BASF) Dr. Rudolf Pfaendner

Fraunhofer-Institut Darmstadt

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Patent applications :“Polytriazinyl compounds as flame retardants and light stabilizers”

European Patent application 2130854. Also in China, India, Taiwan, Japan

MCA� Proprietary volatile-organic-solvent-free technology*

Suspension polymerisation in the presence of catalysts

Examples: PVC made by suspension polymerisationPP made using Ziegler-Natta process

Patent granted in the USA (Patent No. 8,202,924)

*The “handprint” of the technology

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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 fireretardancy, 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.

Summary

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Future Outlook

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

6. mca technologies gmbh.pdf

Documents

mca ppm triazines

r2 r1

char formation

flame retardants

universal synergist

enable reduce

red shade

technologies gmbh