SynSolve Nano Building Blocks Polyurea with ... - PDA Europepda-europe.org/documents/3.KaiKlockemann.pdf · PDA Europe 2012 Annual Conference ... Nano Building Blocks Polyurea with

PDA Europe 2012 Annual Conference – Istanbul, 12-14 November © Kai Klockemann, Nitroil Polyurea GmbH

SynSolve® Nano Building Blocks

Polyurea with Antifouling

Antimicrobial Properties


- Polyurea offers a long service life expectancy

- Suffers from leaching / fugitive additives throughout the lifecycle, such as: - flame retardants - biocides - antimicrobial additives

- REACH and other continually accumulative restrictions (in Europe)

- Additivation with non-reactive products (leaching) or conglomerating molecular structures, affecting physicochemical performance and requiring high concentration


With this background the development started, initially with the three main application targets: - elastomers with modified surfaces for less friction, more hardness, … (without filler) - consistent, non-emitting flame retardancy properties in a purely amine-based polyurea - non-leaching antifouling coatings for marine and water industries besides antimicrobial coatings for hygiene applications


SynSolve: Synthesis-Solvolysis “Synthesis to solve coating problems” Sequential (closed-loop) production phases of - synthesis of a desired polymeric structure - solvolysis > 150°C - High temperatures prevent formation of stable urethane bonds, instead the released NCO-groups react with amine groups of reactive flame retardants, biocides like Irgarol® or Nitroil® Amine “N” or other amines to urea linkage. Irgarol® is a registered trade mark of BASF Corp.


- parallel reaction / covalent coupling of additives, such as flame retardants, biocides or other functional amines

-“Fall-out” of nano-particles with combined aminolysis leading to nano-reactive urea particles

- Basically a production of a polymer with subsequent destruction at temperatures >150°C

- Achieved nano-urea-particles remain reactive by their primary or secondary amine group as

- Incorporable, reactive urea particles of 2-25nm


Nano particles reduce consumption of additives like biocides or flame retardants by around 90%

Measured by Dynamic Laserlight Scattering, Hydrodynamic size of polyurea particles

Source: Fouling-Atlas.com


Elastomers with modified surfaces for less friction, more hardness, … (without filler)

measured by AFM – Atomic Force Microscopy

Conventional

polyurea

SynSolve®

polyurea


Antimicrobial coatings for hygiene applications


Non-leaching antifouling coatings for marine, off-shore infrastructure and water processing

Environmentally friendly


Biocidal antifouling

Organic (e. g. TBT,Diuron, BIT, PHMB, Zineb)

Inorganic (e. g. Copper oxides, Zinc)

Natural antifoulants

TBT-coating (triorganotin based)

Highly effective in reducing/controlling bio-fouling

Highly toxic to (all) marine organisms

also non-target organisms, enters food chain

High leaching rate

erosive, more than 4µg TBT per day

Prohibition of organotins in antifoulings (EC 2008)


- “Free of biocides” (by norm definition) - Non-erosive - Highly dense surface structure - High mechanical resistance


Environmentally friendly alternative

- Non - leachable

- Non - erosive

- No biocides / additives

- No VOC / solvents

- 100 % pure polyurea


Objective of a 100% solids coating with non-leaching

biocidal function for salt and fresh water, main

organisms to be defeated are:

- autotrophic organisms, such as Algae

- phylum Cnidaria, Hydrozoa incl. jellyfish and corals

- Cirripedia, such as barnacles / sessile encrusters

For livelihood all of these need the presence of a bio

film created by colonization of bacteria first in order

to develop further fouling to a carpet of vegetation

and finally breed to a self-sustaining bio system.


Macrofouling

Microfouling

Animal

Plant

Cirripedia / Sessile

encrusters

Autotrophic organisms

Unicellular organism

Barnacles

(in general, especially:)

Amoeba

Hydrozoa / Hydroids

Algae, such as

Marine Bacteria

Molluscs, Mussels

- Red Algae

Tube Worms

- Brown Algae

Plants, such as

Tunicates

- Green Algae

Diatoms (Algae)

Slimes / Bio film


- Permanent

fouling release

- Extremely

hydrophobic

- Corrosion

prevention

- Condensed

surface by

reacted nano

particles


We used DMA (Dynamic Mechanical Analysis) with

an automatic torsion pendulum (ATM 3, Myrenne

GmbH) to confirm the chemical derivation of

covalent coupling of e.g. biocides and performed

separate leaching tests, confirming these results.

To prove the biocidal effect, control samples of

common antifouling materials were prepared:

- Hempel Mille Ultimate®

- Nautic® F18

- International® VC 17m

- Copper (by Deutsches Kupferinstitut)


Mathis LabCoater unit (type LTE), elastomer film casting

Exposure tray for field testing with standard, biocidal

and control specimen


Rotational cylinder, The dynamic ship hull test

(d = 95mm, d / 1000*t / 60m/s) to be 5 kn (9,7 km/h) at 540 rpm

and 20kn (38,8 km/h) at 2170 rpm.

Dynamic test


UV resistance testing (Hönle UV technology, light

UVAPOT 2000 RF1 EPS SH, distance 30cm) for 6

days in a hot humid climate at 55°C with

60-80% humidity.

After testing Before testing




Sediment Exposition, static


Open Sea Exposition, static


CuZn23A3Co 4 mo – Int. self. pol. 2 yrs – Hempel Ult. 3 yrs – SynSolve Basis Amine “N” PUA 3 yrs – Marine S. Silicon 1 yr


Biofouling sites

Ships hulls,

Water-cooling

systems,

Water Reservoirs,

Sewage pipes &

treatment

facilities,

…


Biofouling sites

… water pipes,

sewage pipes…


Biofouling sites

Sea infrastructure,

Offshore structures,

Drilling rigs,

Port and pier

facilities,

Buoys,

Desalination units,

…


…Hygiene Coatings, Food Processing…


H2Nn-1

NH2RR O[ ]

PCL Compounds

yx] ][[ NH2

O

OR

O

OH2NRR

PBD Compounds

H2N

NH2R R]][[][x y z

n-1

O[ ]

OCN

CH2

NCO

CH2 N NC

O

H H HH

O

C NN

]][[][x y z

NCO

CH2

OCN

CH2

HH

O

C NN

HH

O

C NN

yx] ][[

O

OR

O

OCH2

OCN

CH2

NCO HH

O

C NN

HH

O

C NN

PTHF Compounds

Hydrophobic polyurea...


- New patented production process for nano-urea - for aliphatic and aromatic formulations - new educts for antifouling and antimicrobial pure polyurea coatings - proven to be non-leaching / non fugitive (by Torsion Pendulum and leaching tests) - Highly efficient as SynSolve only requires ~10% of conventional additivation due to surface exposure - REACH exempted (polymer) - reservations towards “nano” unsubstantiated as chemically reacted into polymer matrix - ongoing work in further fields (self-cleaning, fire retardancy, prepolymer components)


Thanks to:

Ms. Dipl. Chem. Uta Knoll, Technical University of

Applied Science, Wildau

Dr. H. D. Hunger, Performance Chemicals, Hamburg,

for the cooperation throughout the development project

Dipl. Ing. M. Bader, INPUT – Institute for Polyurethane

Technology, Hamburg, for physical testing of prepared

samples.


Institute for PolyUrethane Technology


Kai Klockemann Nitroil Polyurea GmbH

Liebigstrasse 2-20

D-22113 Hamburg, Germany

Tel. +49 - 40 - 325656-0

Fax +49 - 40 - 325656-16

[email protected]

Nitroil Polyurea:

• Raw-Materials • Formulation • System Blending

• Application Technology • Project Consulting

Nitroil and SynSolve are registered trademark ® of

Nitroil - Performance Chemicals - Hamburg

Certified by BVQI according to

DIN EN ISO 9001

DIN EN ISO 14001

Documents

SynSolve Nano Building Blocks Polyurea with ... - PDA Europepda-europe.org/documents/3.KaiKlockemann.pdf · PDA Europe 2012 Annual Conference ... Nano Building Blocks Polyurea with