Development of an one component PU foam system in
aerosol cans, with a free MDI monomer content of less
than 1% of the total chemical weight
Andreia Joana Paiva Carvalho Mota
Dissertação para obtenção do Grau de Mestre em
Engenharia Química
Júri
Presidente: Professor João Carlos Moura Bordado (DEQB)
Orientador: Professor João Carlos Moura Bordado (DEQB)
Mr. Aster De Schrijver (Altachem)
Vogal:
Professor António Boavida Correia Diogo (DEMAT)
Novembro de 2009
Acknowledgements
First of all, my special thanks goes to Mr Aster De Schrijver in giving me the possibility of
working in a enterprise like Altachem, permitting me to learn and to achieve experience in this
field, allowing therefore the opportunity
pportunity of an experience of months out of my country, out of my
own, where this change became more than an internship but a life experience, where I did grow
in my identity.
I also want to thanks Professor João Bordado, for have stablished the connection between me
and Mr. De Schrijver, making this work possible and for all the precious support and help, given
after i came back to Portugal and when i really started my thesis.
I would like to express a special gratitude to Dr. George
George Georgiev, for being always present, for
support and help, while and after my internship in Altachem. Above all, for teaching me, for his
patience and, at last, for been with a kind availability for all that i’ve needed.
To Sven De Vis, I’m very thankfull
thankfull for all that he did for me, for being also available and for the
support since i started working in AltaGreen’s project, giving me always work when i felt lost and
making my days more interesting in Altachem.
My next thanks follows to:
The Portuguese
se community in Gent, i’m very thankfull to:
Ana Dionísio for made me feel accompanied in my daydreams, having shared her
artistic interests and points of view, that were met with mine, and due to this and more, to
became a pretty good friend.
Ana Luísa for having been along with me, a ‘house warrior’, a partner inside and outside
our home, making really apply, (since the last three months), this last word ‘home’ to the old
build we lived and for been revealed a good friend.
Duarte Neiva for having been always
always a smile to me and a comforting word, for his
attitude, his concerns to make people feel good without loosing his own personality and for all
the support and help in Altachem.
Inês Fernandes for all the patience and attention gave to me, for all the support
s
and
help in Altachem and not only in there, but mainly in the enterprise. There were several times
that without her in laboratory, i would probably do a lot of mistakes.
João Rodrigues for being always available to help me in Altachem and for all the
th given
support.
I
Pedro Pereira, for all the kind availability and the efforts developed to adapt us in Gent
and in Altachem. There is also a grateful words for the help given to me and for his concerns
about my work when i was in Ecofast. He had a lot of patience and was a good colleague.
Sandra Silva for helping me as much as she could when we’ve coming to Gent, for
being always there teaching, concerning, for really adapt me in a new town, a new country. She
was a truly friend and she had an unusual availability without expecting nothing in return.
And the latest are the first, for Maria Luís and Vítor Cadilha, a special thanks for had
been always there for me during these six months but mostly for having made my last month in
Gent some kind of a dream, when i think that we really had known each other and where we’ve
built a strong and indestructible relationship. Maria has an attitude and special behaviour that i
admired and Vítor is a sensitive person with who i had an empathy. So i thank you both, for
more than this, being truly friends of mine.
For all my friends that supported me but specially to whom had visiting me in Gent, making the
distance shorter and for making me feel better and care, i’m gratefull. They are: Márcia Oliveira,
Miguel Sousa, Joana Pereira, Tiago Lopes, João Teixeira, Filipa Quinas, Ivan Sousa and
Samuel Granadeiro.
A kind thanks for Márcia Oliveira for having been present in Gent for two times and for the help
given for my thesis.
I would like to express my gratitude also to Magda Troeira for the rare availability and friendship
given to me, she gave me truly help for my thesis when i most needed and for Miguel Dinis, i’m
thankfull for the very useful help in chemistry and for his sympathy.
A special thanks to Nuno Silva for had given me strong support and for his confidence in me
when i came back to Portugal.
Finally, my strongest thanks goes to my family for all the concerns and support. For the
presence of my mother visiting me in Gent and being with me after four months, making the
distance only a detail; for my sister for all the work she has done, contributing to my safe and
good flights in July, to my dear cat in not forgetting me when i was out for a long time and to my
father in making me feel welcome everytime and for having received me with open arms.
Thank you
II
Resumo
O presente trabalho prende-se com a produção de espumas de poliuretanos com um
reduzido teor em diisocianatos monoméricos e seu uso como espumas de um componente. O
principal objectivo foi o seu desenvolvimento com uma percentagem inferior a 1% de MDI
monomérico, assim integrando-se numa perspectiva ecológica e respeitando os limites da
responsabilidade ambiental, que cada vez mais adopta um papel importante na sociedade
industrial.
Este projecto foi denominado de AltaGreen, evidenciando o propósito que se pretende
atingir, a diminuição da percentagem de monomérico difenilmetano diisocianato, MDI.
Começou por se estudar uma formulação-mãe de nome backbone, de onde derivou a primeira
estrutura química da espuma, tendo-se em seguida, desenvolvido mudanças nas quantidades
respectivas dos seus componentes.
Inicialmente, apresenta-se um conteúdo geral do que são espumas de um componente, e
prossegue-se para uma comparação entre estas e as espumas produzidas em AltaGreen,
estabelecendo um paralelo e intrinsecamente uma ponte entre ambas.
Dado que este é um projecto recente, realizaram-se 31 formulações AltaGreen que
acabaram por não ser suficientes para estabelecer correlações entre variáveis de resposta e
variáveis de controlo. Além desse factor, também se depararam problemas relacionados com o
funcionamento do mixer do reactor que foram considerados fulcrais.
O que tornou este projecto tão estimulante foi equacionar as várias hipóteses de mudança
da backbone de forma a alcançar menos de 1% de MDI monomérico conjuntamente com a
obtenção e preservação de boas propriedades da espuma. Porém concluiu-se que estes dois
objectivos se tornam difíceis de conciliar simultaneamente.
Palavras-chave: espumas de poliuretano de um componente; MDI monomérico; backbone;
Altagreen.
III
Abstract
This study relates to the production of polyurethane foams based on polyols and
polyisocyanates with a low content of monomeric diisocyanates and its use as an one
component foam. The main objective was their development with less than 1% of free
monomeric MDI, thus taking part on an ecologic perspective where could also be respecting the
limits of the environmental responsibilities, which of them are having a growing role on the
industrial society.
The project started was called AltaGreen, created in order to achieve the decrease of the
percentage of free monomeric diphenylmethane diisocyanate, MDI. Therefore, a mother
formulation named backbone gave the first chemical structure of the foam that was followed by
changes on the respective amounts of its components.
First of all, general information about one component foams, with a comparison with
AltaGreen and forming a bridge between them, is present.
As it’s a recent project, have been made about thirty one formulations AltaGreen that were
not enough to enable the possibilities of making correlations between response and control
variables. Beyond this fact, it has been occurred another problems related with the mixer of the
reactor which were considered essential.
What has made this project so interesting was the challenge to achieve less than 1% free of
monomeric MDI together with the obtainment of acceptable properties of the foam.
Nevertheless the main conclusion of this work is that these two purposes are simultaneously
hard to arrange.
Key-words: one component polyurethane foams; monomeric MDI; backbone; AltaGreen.
IV
Index
Acknowledgements................................................................................................................. I
Resumo .................................................................................................................................. III
Abstract .................................................................................................................................. IV
Index ........................................................................................................................................ V
Index of Figures..................................................................................................................... VI
Index of Tables ..................................................................................................................... VII
Abbreviations ...................................................................................................................... VIII
1.
Introduction..................................................................................................................... 1
2.
One Component Foams ................................................................................................. 2
2.1.
Basic Polyurethanes Chemistry ................................................................................... 2
2.1.1
2.2.
Chemicals used ....................................................................................................... 3
OCF Formulations ........................................................................................................ 4
2.3.1
Materials and Methods ............................................................................................ 5
2.3.1.1
Reactants and Additives ......................................................................................... 6
2.3.1.2
Methods ................................................................................................................... 7
2.4
Basic Calculations ........................................................................................................ 8
2.5
Formulations ................................................................................................................ 9
2.6
Results ....................................................................................................................... 10
2.6.1
2.7
Quick Tests ............................................................................................................ 11
Discussion and Conclusion ........................................................................................ 12
3.
Annexes......................................................................................................................... 13
4.
AltaGreen ...................................................................................................................... 14
4.1
Calculations ............................................................................................................... 15
4.1.1
AltaGreen Calculations .......................................................................................... 16
4.1.2
Conclusions about Calculations ............................................................................ 17
4.2
Backbone .................................................................................................................. 18
4.3
Experimental Procedure ........................................................................................... 19
4.4
Formulations and Results ......................................................................................... 20
4.5
Discussion of Results ................................................................................................ 21
4.6
Conclusions ............................................................................................................... 22
5.
Conclusion .................................................................................................................... 23
6.
References .................................................................................................................... 24
Appendix 2 .............................................................................................................................. 25
2.1
Quick Test of AltaGreen Formulations ....................................................................... 25
2.2
Dimensional Stability Results of AltaGreen Formulations ......................................... 26
V
Index of Figures
VI
Index of Tables
VII
Abbreviations
VIII
1. Introduction
1
One Component Foams
1.1.
Basic Polyurethanes Chemistry
2
2.1.1
Chemicals used
3
1.2.
OCF Formulations
4
2.3.1 Materials and Methods
5
2.3.1.1
Reactants and Additives
6
2.3.1.2
Methods
7
2.4 Basic Calculations
8
2.5 Formulations
9
2.6 Results
10
2.6.1
Quick Tests
11
2.7 Discussion and Conclusion
12
2. Annexes
13
4. AltaGreen
14
4.1
Calculations
15
4.1.1
AltaGreen Calculations
16
4.1.2
Conclusions about Calculations
17
4.2
Backbone
18
4.3
Experimental Procedure
19
4.4
Formulations and Results
20
4.5
Discussion of Results
21
4.6
Conclusions
22
5. Conclusion
23
6. References
24
Appendix 2
2.1
Quick Test of AltaGreen Formulations
25
2.2
Dimensional Stability Results of AltaGreen Formulations
26