Development of an one component PU foam system in

aerosol cans, with a free MDI monomer content of le ss

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 of an experience of

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

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. Ge

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 thank

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 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 a

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 s

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 th

support.

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

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

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 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 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.

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

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 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 s

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 th

I

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

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

stablished the connection between me

and Mr. De Schrijver, making this work possible and for all the precious support and help, given

orge Georgiev, for being always present, for

support and help, while and after my internship in Altachem. Above all, for teaching me, for his

full 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

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

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

lways 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

Inês Fernandes for all the patience and attention gave to me, for all the support and

help in Altachem and not only in there, but mainly in the enterprise. There were several times

João Rodrigues for being always available to help me in Altachem and for all the given

II

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

III

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.

IV

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.

V

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 Chemicals used ....................................................................................................... 3

2.2. 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

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

VI

Index of Figures

VII

Index of Tables

VIII

Abbreviations

1

1. Introduction

2

One Component Foams

1.1. Basic Polyurethanes Chemistry

3

2.1.1 Chemicals used

4

1.2. OCF Formulations

5

2.3.1 Materials and Methods

6

2.3.1.1 Reactants and Additives

7

2.3.1.2 Methods

8

2.4 Basic Calculations

9

2.5 Formulations

10

2.6 Results

11

2.6.1 Quick Tests

12

2.7 Discussion and Conclusion

13

2. Annexes

14

4. AltaGreen

15

4.1 Calculations

16

4.1.1 AltaGreen Calculations

17

4.1.2 Conclusions about Calculations

18

4.2 Backbone

19

4.3 Experimental Procedure

20

4.4 Formulations and Results

21

4.5 Discussion of Results

22

4.6 Conclusions

23

5. Conclusion

24

6. References

25

Appendix 2

2.1 Quick Test of AltaGreen Formulations

26

2.2 Dimensional Stability Results of AltaGreen Formulations