2021

UNIVERSIDADE DE LISBOA

FACULDADE DE CIÊNCIAS

DEPARTAMENTO DE QUÍMICA E BIOQUÍMICA

Phenol & Formaldehyde free Printing Ink Resins

Henrique Costa Machado

Mestrado em Química Tecnológica

Versão Públ ica

Dissertação orientada por:

Doutora Ana Cristino

Doutor Rui Galhano dos Santos Lopes

I

Phenol & Formaldehyde free Printing Ink Resins

ANTICIPATING CHANGE

The Jack Pine—Tom Thomson, 1916-1917 .

III

“Study nature, love nature, stay close to nature. It will never fail

you”— Frank Lloyd Wright

V

ACKNOWLEDGMENTS

This piece would not have been possible

without the ceaseless support of my teachers,

family, colleagues, and friends. Their

friendship, experience, and aid has pushed me

further towards the conclusion of this work,

which I dedicate to all of them.

To Respol, thank you for this opportunity,

al lowing me to have such educational

experience in science and l ife.

To Ph. Ana Crist ino, thank you for al l the

advice on how to manage work and personal

l ife. Thank you for bel ieving in me.

To Ph. Rui Galhano and Professor Bordado I

thank the opportunity and trust given to me.

To Diogo Gomes, I thank the never -ending

availabil i ty to discuss science, work and other

subjects related to resin chemistry, industry,

and economics.

To my colleagues, Catarina, Margarida, Inna ,

David, Ricardo , Susana, Alexandra, and

Carina, I thank and treasure all the knowledge

they entrusted me, friendship, kindness, and

concern.

To Professora Maria José Lourenço and al l

other Química Tecnológica teachers, thank

you for your passion. I f inally understand what

i t means to be a student of Química

Tecnológica .

To my family, I thank the ir care, endless

support and for always believing in me, even

when my will wavered.

To my friends, thank you for al lowing me to

share this experience with you, and for always

being by my side.

To all the above, thank you for teaching me

that l ife is hard and sinuous but nevertheless,

rewarding. Thank you for let t ing me learn

from you. I will forever cherish this

experience.

VII

ABSTRACT

As a natural resin, rosin has been used as an ink component for the properties i t

imparts the result ing ink. Modifications to natural rosin have been long studied and

later applied in ink making to yield better performing products .

One major modification is the incorporation of Resol , phenol-formaldehyde resin,

with rosin. Modifying rosin in such fashion allows i t to display improved solubil i ty

in vegetal and mineral drying oils, another major component in inks.

Nevertheless, there are several health and environmental hazards associated with

formaldehyde and alkyl phenols used in Resol production, thus i t is important to

search alternative solubil i ty inducing modifications to rosin resins permitt ing the

drop of Resol .

Samples from the production of Resol modified rosin resins were investigated to

better understand the behavior of Resol .

Later, comparable structures to that of Resol were theorized and produced either as

pre-polymers later added in resin making reactions or integrating the resin making

process i tself .

Although results answering directly to the goals of this work were not achieved, the

not so satisfactory outcomes do serve a purpose. They may guide the correct path for

future research in this f ield and raise questions which were not thought of before.

Briefly, ester l inkage should be reduced or concealed. Bulkier structures are

preferred as they raise softening point. Aliphatic groups are needed to raise

solubil i ty. Higher molecular weights might be required. Other polymers besides

polyester may also be uti l ized but raise questions about bio decomposit ion. The

evaluation systems of these new resins could be modernized as they will possibly

serve new functions.

KEYWORDS: Rosin; Offset Printing; Modified Rosin Resins; Rosin Polyesters;

Resol free.

IX

RESUMO ALARGADO

A tradição da resinagem em Portugal é longeva, estando inicialmente a sua atividade

fortemente l igada ao equipamento naval em madeira.

Da resina extraída do pinheiro vivo separa -se, através da desti lação, a terbentina e a

colofónia. Enquanto a terbentina encontra a sua aplicação como solvente orgânico e

diluente de t intas e vernizes, a colofónia é uti l izada como material de partida na

produção de resinas com destino à produção de t in tas de impressão ou outras

coberturas de superfícies embora o seu uso sem recurso a modificações conheça

também muitos outros domínios.

Modificada, a colofónia pode sê -la de forma simples ou complexa. Transformações

simples da colofónia , como a obtenção do seu aducto com anidrido maleico ou ácido

fumárico, ou a produção de esteres simples, que vis am principalmente a melhoria das

suas propriedades intrínsecas.

Também através das modificações já mencionadas, a colofónia pode ser uti l izada

como unidade estrutural principal para a produção de poliéster es de peso molecular

elevado. A performance f ísica e química destas resinas confere às t intas produzidas

propriedades que permitem alcançar rotinas de impressão de qualidade.

Em particular, as t intas para impressão offset requerem um comportamento altamente

viscoso por se destinarem a processos de al ta -rodagem, sendo o seu aspeto muitas

vezes semelhante a pastas. Esta propriedade, entre outras de igual relevo, é conferida

pela resina com a qual a t inta é produzida. Assim, a própria resina necessita de

apresentar característ icas adequadas a esta aplicação, sendo elas, principalmente, a

viscosidade e a solubi l idade em verniz. A colofónia é então modificada através da

formação de adutos e esterifi cação, mas ainda com recurso à introdução de Resol ,

resina de fenol e formaldeído, para que possa satisfazer os cri térios de solubil idade

e viscosidade em verniz.

Contudo, a uti l ização de fenóis e formaldeído acarreta atenção redobrada aquando do

processo de produção que os envolve, assim como no tratamento de resíduos

associados. Existe ainda uma preocupação crescente relacionada com as suas origens,

nomeadamente no caso do fenol, que provem de matérias de natureza fóssil .

Assim, desenvolver um produto de performance semelhante às resinas modificadas

com fenol-formaldeído é não só uma antecipação sensata de futuras necessidades ,

como um ato de responsabil idade ambiental .

Este trabalho, desenvolvido e suportado n o Grupo Respol, visa precisamente a

investigação e desenvolvimento de uma resina com origem na colofónia, que possua

um comportamento semelhante às suas equivalentes produzidas com recurso a fenol

e formaldeído.

Por ser um trabalho sustentado na ideia de antecipação de um futuro panorama e por

estar fortemente l igado à indústria, a informação de acesso publico relacionada

diretamente com esta temática é reduzida. Em adição, nenhum produtor à data da

X

realização deste trabalho oferece, na sua gama de produtos, resinas de colofónia sem

fenol e formaldeído com desempenho semelhante aos objetivos propostos. Numa

consulta aos dossiers de produto registados no âmbito do REACH , realizada no final

de 2020, não constam resinas derivadas de colofónia produzidas com recurso a novas

matérias-primas ou processos. Pode constatar-se que para além da não

comercialização, também não se prevê que tal venha a acontecer num futuro próximo,

uma vez que o registo deve anteceder a entrada de um produto no mercado.

Com acesso unicamente às técnicas , química e formulações já conhecidas desta

indústria , foram delimitadas as guias principais deste trabalho e desenhado um plano

de abordagem ao problema. Assim, este trabalho possui um carácter fortemente

marcado pela ausência de suporte de trabalhos anteriores que possam indicar de forma

mais clara um método a seguir e por isso possui uma natureza bastante relacionada

com a procura e averiguação da abordagem mais viável , permitindo depois uma

investigação aprofundada e mais ciente dos contornos do problema.

O presente trabalho teve início com a caracterização de algumas amostras industriais

de resina de colofónia produzida com recurso a fenol e formaldeído. Compreender o

comportamento do Resol na resina e como este afeta a viscosidade e solubil idade, de

modo a poder desenhar uma solução mais medit ada para o problema em mãos foi

considerado o objetivo principal . Desde estudo, conclui -se que o Resol para além de

criar pontes l ineares longas, com peso molecular considerável , entre moléculas de

ácidos resínicos, fá-lo ainda através de uma estrutura de natureza altamente solúvel

em óleo alifáticos, mais ainda que a própria colofónia. Em adição, a natureza da sua

l igação química é estável e a mobilidade de cadeia contribui para aumentar a

viscosidade.

Um poliéster de colofónia é t ipicamente produzido com recurso a monómeros de

pequenas dimensões, como os ácidos resinicos, adutos de colofónia e poli óis como o

pentaeritr i tol . A porção fenólica é a única com extensão apreciável e por isso é a

entidade que permite criar algum distanciamento entre centros mais condensados

compostos pelos restantes monómeros. Com a remoção do Resol , este espaço que

permite à macromolécula respirar perde-se e obtém-se uma est rutura fortemente

intrincada que resulta na perda de viscosidade e na redução da superfície de contacto

com o solvente.

Reintroduzir estruturas deste t ipo na matriz da resina pode então permitir recuperar

total ou parcialmente o comportamento perdido com a remoção do Resol . É

importante então que estas estruturas sejam principalmente l ineares, ou com

backbone l inear, sejam maioritariamente alifáticas ou com exter ior al ifático, que

possam ou tenham origem em recursos renováveis e sejam de toxicidade reduzida ou

nula. Alguns polímeros pensados para responder a estas necessidades foram

sintetizados e introduzidos mais tarde na produção da resina de colofónia . Alguns

dos monómeros uti l izados nestes pré -polímeros foram ainda introduzidos como tal

em formulações de resina de modo a tentar obter algum tipo de estrutura l inear in

si tu e sem recurso a preparações adicionais.

Além da possível reintrodução de estruturas deste t ipo ponderou -se e testou-se a

uti l ização de algumas modificações simples na formulação da resina que incluem

XI

alterações de processo, introdução de polióis al tamente funcionais e modificação com

óleos vegetais de cadeia curta, entre outros.

É ainda importante referir que existe um a relação muito forte entre as propriedades

da viscosidade e solubil idade em resinas sem Resol . Modificações que aumentam a

solubil idade implicam sempre perdas de viscosidade e vice -versa, sendo por isso

ainda mais importante encontrar métodos que permitam escapar a esta dualidade.

Das modificações simples mencionadas, a adição de componentes em duas fases

produziu aumento significativo da viscosidade sem perca de solubil idade , quando

comparada com a mesma formulação com adição numa fase e solubil idade médi a.

Ficou evidente que a modificação ao processo permite alterar apenas umas das

propriedades, neste caso a viscosidade. No entanto, quando se tentou recorrer a este

método para aumentar a viscosidade de uma formulação de solubil idade alta, não se

verificou o seu incremento. É possível que este efeito apenas se confirme a partir de

um dado l imite inferior de componente éster, que regula fortemente o fator da

solubil idade. Outras modificações como a uti l ização de outros óleos vegetais e

polióis de alta funcionalidade não produziram efeitos apreciáveis.

Da uti l ização de poliésteres substi tutos de Resol , ou seus monómeros, na formulação

de resinas verificou-se que para valores de solubil idade próximos dos desejados, a

resposta viscosa é depreciável. No entanto, em ambos os casos confirmaram-se a

existências de espécies de baixo peso molecular em quantidades muito superiores às

t ípicas de resinas produzidas com recurso a fenol e formaldeído. A presença destas

espécies é responsável pelo aumento da pol idispersividade de pesos moleculares e

consequente redução da resposta viscosa. Contudo, como no caso destas formulações

se introduziram novas espécies químicas é plausível que o l imite inferior de M w para

obtenção de resposta viscosa possa ser simplesmente superior aos que se encontram

habitualmente em resinas fenólicas.

Palavras-chave: Colofónia; Impressão Offset; Resinas Modificadas de Colofónia;

Poliésteres de Colofónia; Sem Resol .

XII

INDEX

Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

1. Respol Group, Work Envi ronment and Framing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.1 Respol—History and Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.1.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.1.2 Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

1.2 Manufacturing Routines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

1.3 Organizational Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1.3.1 Research and development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1.4 Quality, Health, Safety, Security and Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

2. Theoretical Framing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.1 Ink making and Offset printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.1.1 The Offset Printing Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.1.2 Ink formulation and Offset Inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

2.1.3 Requirements for Offset Printing Inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

2.1.4 Varnish Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

2.1.4.a Reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2.1.4.b Compatibil i ty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2.2 Phenol-formaldehyde Modified Rosin Resins — From Pine to Ink . . . . . . . . . . . 12

2.2.1 Pine Resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

2.2.1.a Composit ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

2.2.1.b Rosin Modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

2.2.2 Synthesis and Chemistry of Phenol -formaldehyde Rosin Resins and

Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

2.2.2.a Methylol Phenol—Lederer-Manasse reaction .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

2.2.2.b Oligomerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2.2.2.c Chroman Ring formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2.2.2.d Diels-Alder Addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.2.2.e Esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.2.2.f Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

2.2.2.g Etherification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

2.2.3 Industrial Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

2.3 Hansen Solubil i ty Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

2.4 Alternative Solubil i ty Inducing Modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

XIII

3. The Problem—Approach and Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

3.1 Targets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

3.2 Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

4. Equipments and Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

4.1 Evaluating Rosin Polyesters—Standard Analytical Practices . . . . . . . . . . . . . . . . . . . 27

4.1.1 Softening Point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

4.1.2 Cloud Point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

4.1.3 Acid Value or Number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

4.1.4 Varnish Viscosity and Rheologic Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

4.1.4.a Rotational Tests with Controlled Shear Rat e, CSR .. . . . . . . . . . . . . . . . . . . 29

4.1.4.b Flow Curves: Stress vs rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

4.1.4.c Structure Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

4.1.4.d Curve Fit t ings: Power -Law and p-Ostwald . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

4.1.4.e Oscillatory Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

4.1.4.f Phase Shift , Storage Modulus and Loss Modulus . . . . . . . . . . . . . . . . . . . . . . . 31

4.1.4.g Sample preparation and Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

4.1.5 Gel-permeation size -exclusion chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

4.2 Associated Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

5. Methodologies, Outcomes and Evaluations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

5.1 Assessment of Phenol -formaldehyde Prompted Property Changes During

Industrial Manufacturing Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

5.2 Study of Catalysts in Esterification Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

5.3 Polyester making in glass beakers and pilot reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

5.3.1 Trials based on resin acids and i ts modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

5.3.1.a Trial 1-Rosin adduct and DEG .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

5.3.1.b Trial 2-Resin acids, Maleic anhydride, Cardanol and MPG .. . . . . . . . 44

5.3.2 Trials based on dimmer acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

5.3.2.a Trial 3-Radiacid and DEG .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

5.3.2.b Trial 4-Radiacid and MPG .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

5.3.2.a Trial 5-Radiacid and MPG replication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

5.3.2.b Trial 6-Radiacid, TMP, Maleic anhydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

5.3.3 Trials based on isophthalic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

5.3.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

5.4 Experiments at Pilot Scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

5.4.A Equivalent Functionali ty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

5.4.B Acid Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

XIV

5.4.2 Case Study 1—Introduction to resin making, process variations and

swop in raw materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

5.4.2.a Batch 01—Tester Batch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

5.4.2.b Batch 02—First Improved Batch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

5.4.2.c Batch 03—Introduction of RCB .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

5.4.2.d Batch 04—Introduction of process changes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

5.4.2.e Batch 05—Introduction of coconut oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

5.4.2.f Batch 06— Introduction of Boltorn P1000 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

5.4.2.g Batch 07—Boltorn H2004 introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

5.4.2.h Batch 08—First formulation with Radiacid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

5.4.3 Case study 1—Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

5.4.4 Case Study 2—Attempts at l inear polymer making . . . . . . . . . . . . . . . . . . . . . . . . 58

5.4.4.a Batch 09-Formulation with Radiacid. Difunctional reactions

priori t ized . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

5.4.4.b Batch 10- Formulation with Radiacid. Adduct formation priori t ized

59

5.4.4.c Batch 11- Processual adjustment of batch 10 .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

5.4.4.a Batch 12- Processual adjustment of batch 11 .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

5.4.4.b Batch 13-Formulation with isophthalic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

5.4.4.c Batch 14- Formulation with isophthalic acid pre -polymer . . . . . . . . . . 62

5.4.4.d Batch 15-Formulation with radiacid and TMP .. . . . . . . . . . . . . . . . . . . . . . . . . . 63

5.4.4.e Batch 16-Second base formula revision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

5.4.4.f Batch 17-Adjustment of batch 16 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

5.4.4.g Batch 18-Middle ground between batch 17 and batch 15 . . . . . . . . . . . . 65

5.4.4.a Batch 19- Adjustment of batch 18 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

5.4.4.a Batch 20-Radiacid pre-polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

5.4.5 Case study 2—Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

6. Final Remarks and Future Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

7. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

8. Appendix A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

8.1 Summary Tables—Case Study 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

8.2 Summary Tables—Case Study 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79

9. Appendix B . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

9.1 Processes—Case Study 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

9.1.1 Batch 01—Tester Batch.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

9.1.2 Batch 02—First Improved Batch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

XV

9.1.3 Batch 03— Introduction of RCB .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

9.1.4 Batch 04— Introduction of process changes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

9.1.5 Batch 05— Introduction of coconut oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

9.1.6 Batch 06— Introduction of Boltorn P1000 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

9.1.7 Batch 07—Boltorn H2004 introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

9.1.8 Batch 08—First formulation with Radiacid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

9.2 Case Study 2 Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

9.2.1 Batch 09-Formulation with Radiacid. Difunctional reactions

priori t ized . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

9.2.2 Batch 10- Formulation with Radiacid. Adduct formation priori t ized 87

9.2.3 Batch 11- Processual adjustment of batch 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

9.2.4 Batch 12- Processual adjustment of batch 11 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

9.2.5 Batch 13-Formulation with isophthalic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

9.2.6 Batch 14- Formulation with isophthalic acid pre -polymer . . . . . . . . . . . . . . 89

9.2.7 Batch 15-Formulation with radiacid and TMP .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

9.2.8 Batch 16-Second base formula revision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

9.2.9 Batch 17-Adjustment of batch 16 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

9.2.10 Batch 18-Middle ground between batch 17 and batch 15 . . . . . . . . . . . . . 90

9.2.11 Batch 19- Adjustment of batch 18 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

9.2.12 Batch 20-Radiacid pre-polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

XVI

INDEX OF FIGURES

Figure 0 .1 -Rosin transportat ion con ta iners. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

Figure 1 .1 -Flow chart of res in production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Figure 1 .2 -Typica l scheme of a reac tor u t i l ized for ros in modif icat ions . . . . . . . . . . . . . . . . . . . . . . . . 7

Figure 2 .1 -Const i tuents of mineral varnish o il . Examples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Figure 2 .2 -Left-Raw p ine resin ; Righ t -Colophony. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

Figure 2 .3 - Major ab ietane type resin ac ids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

Figure 2 .4 - Addi t ion of formaldehyde to a para -alkyl phenol, forming a monomethylol

phenol uni t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

Figure 2 .5 - Addi t ion of formaldehyde to monomethylo l phenol un it , fo rming dimethy lol

phenol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

Figure 2 .6 - Condensat ion reac tion of a monomethylo l phenol with a d imethylo l phenol.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

Figure 2 .7 - Chromane- l ike structure. Resol br idge between two res in ac ids. . . . . . . . . . . . . . . . 16

Figure 2 .8 -Maleic adduct formation v ia Diels -Alder react ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

Figure 2 .9 - Ester if icat ion reac tion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

Figure 2 .10 - Lef t-Glycerol rosin es ter ; Righ t -Pentaery thr i tol ros in es ter . . . . . . . . . . . . . . . . . . . . 18

Figure 2 .11 - Possib le st ructure o f a phenol -formaldehyde modif ied ros in res in . Not ice

the st i l l avai lable react ive terminal groups. Orange -Abiet ic acid ; Blue -Maleic adduct;

Green-Reso l por t ion ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Figure 2 .12-Transester if ica t ion mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

Figure 2 .13-Pi lot reac tors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

Figure 3 .1 - Summary of phenol -formaldehyde free rosin resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

Figure 3 .2 - Summary of phenol -formaldehyde contain ing rosin resins. . . . . . . . . . . . . . . . . . . . . . . . 24

Figure 4 .1 -Acid value equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

Figure 4 .2 -Viscosi ty as function of shear rate and shear stress. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

Figure 4 .3 -Flow curves of var ious f low behaviours. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

Figure 4 .4 -Power-Law model equat ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

Figure 4 .5 -Phase sh if t as function of storage and loss modulus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

Figure 4 .6 -Pi lot reac tor up close. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

Figure 5 .1- Typical GPC of Phenolic Modif ied Rosin Resins before add it ion of male ic

anhydride and af ter d ischarge. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

Figure 5 .2 - Acid va lue evolution during ester if icat ion of glycerol with resin ac ids at

250ºC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

Figure 5 .3 -Acid value evolution during ester if icat ion of glycerol with resin ac ids at

200ºC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

Figure 5 .4 - Reso l molecule based on nonylphenol and formaldehyde. R 1 =C 9 or C 4

a l iphat ic in case of nonylphenol o r buty lphenol, respect ive ly. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

Figure 5 .5 - Available molecu les with hydroxyl function and var ious functional i t ies. a)

Glycerol b) DEG, Diethylene g lyco l c) Hexadecan -1-ol d) TEG, Tr iethy lene g lyco l e)

TMP, Tr imethy lopropane f) Pentaery thr i tol g) MPG, Monop ropylene Glycol h) Cardanol ,

R=C 1 5 H3 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

Figure 5 .6 - Available molecu les with carboxylic funct ion and var ious functional i t ies. a)

Stear ic acid b) Succin ic acid c) Male ic anhydride d) I sophtha lic acid e) Radiac id, two

possib le var ia t ions of the dimmer acid. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

Figure 5 .7 -Glass p i lo t reactor typica l apparatus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

Figure 5 .8 - Possib le result of the es ter if ica t ion reac tion of maleic adduct with

hexadecan-1-ol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

Figure 5 .9 - GPC chromatogram of Trial 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

XVII

Figure 5 .10- GPC chromatogram of Tr ial 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

Figure 5 .11-GPC chromatogram of Tr ial 3 -Radiacid and DEG polyester . . . . . . . . . . . . . . . . . . . . . . 46

Figure 5 .12 -Pred ic ted s tructure of Radiacid 0950 and MPG polyester . . . . . . . . . . . . . . . . . . . . . . . . . 46

Figure 5 .13- GPC chromatogram from Tr ia l 4 and corresponding thermal degradation

test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

Figure 5 .14 - -Predic ted st ructure of Radiacid 0950 and TMP polyester . Unsaturat ion

introduced by male ic anhydride is presen t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

Figure 5 .15-Resu lt ing gel f rom the tr ial 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

Figure 5 .16 - Possib le st ructure o f i sophthal ic ac id and MPG polyester . . . . . . . . . . . . . . . . . . . . . . . 49

Figure 5 .17- GPC chromatogram from Tr ia l 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

Figure 5 .18-Molecular weigh t dis tr ibu tion comparison of the bes t t r ia ls wi th Resol

port ion of phenol containing resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

Figure 5 .19-Equiva lent functional i ty equat ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

Figure 5 .20-Acid rat io equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

Figure 5 .21-Left-Boltorn H2004; Right -Boltorn P1000. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

Figure 5 .22-Left-Usual f inal appearance of a resin; Righ t -Resin wi th ge l . . . . . . . . . . . . . . . . . . . . 57

Figure 5 .23-Molecular weigh t evo lut ion dur ing reac tion of M24209H batch. GPC

analysis. Numbers correspond to sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

Figure 5 .24- Molecular weigh t evo lut ion dur ing reac tion of M24210H batch. GPC

analysis. Numbers correspond to sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

Figure 5 .25 - Molecular weigh t evo lut ion dur ing reac tion of M24211H batch. GPC

analysis. Numbers correspond to sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

Figure 5 .26- Molecular weigh t evo lut ion dur ing reac tion of M24212I batch. GPC

analysis. Numbers correspond to sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

Figure 5 .27- Molecular weigh t evo lut ion dur ing reac tion of M24213I batch. GPC

analysis. Numbers correspond to sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

Figure 5 .28 - Molecular weigh t evo lut ion dur ing reac tion of M24214I batch. GPC

analysis. Numbers correspond to sample# in Table 8 . 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

Figure 5 .29- Molecular weigh t evo lut ion dur ing reac tion of M24215I batch. GPC

analysis. Numbers correspond to sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

Figure 5 .30 - S ingle sample of M24217J batch. GPC analysis. Numbers correspond to

sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

Figure 5 .31 - Molecular weigh t evo lut ion dur ing reac tion of M24218J ba tch. GPC

analysis. Numbers correspond to sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

Figure 5 .32 - Molecular weigh t evo lut ion dur ing reac tion of M24219J ba tch. GPC

analysis. Numbers correspond to sample# in Table 8 . 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

Figure 5 .33- Molecular weigh t evo lut ion dur ing reac tion of M24220J ba tch. GPC

analysis. Numbers correspond to sample# in Table 8 .7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

Figure 5 .34-Some of the meta l p i lo t t r ia ls samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

Figure 6 .1 -Poss ible subst i tu t ion to Reso l . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70

Figure 6 .2-Sample v ials for GPC analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

XVIII

INDEX OF TABLES

Table 2 .1 - Composi t ion of mineral d rying o il s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Table 2 .2 - Summary of propert ies of di fferen t types of ros in . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

Table 2 .3 - Abie tane type resin acid content o f var ious spec imens and ta l l o i l . Adapted

from [21][22] and completed wi th some interna l information made avai lable by Respol.

Levopimaric and pa lustr ic acids are coupled together s ince GC-f id i s no t able to

dis t ingu ish between both acids. FOR 85 and FOR 90 are grades of tal l o i l d is t i l la tes. . . . . . 14

Table 2 .4-Summary of p r imary manufacture s tages, in their usual processing order , and

corresponding temperature ranges. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

Table 2 .5 - Hansen parameters for l iquids a t 25 ºC. Adapted from [35] . . . . . . . . . . . . . . . . . . . . . . . . 20

Table 2 .6 - Contr ibu tions for the Hansen so lubi l i ty parameters of structural groups.

Adapted from [35] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

Table 3 .1 - Collect ion of Technica l Char t Data f rom Target Phenolic Rosin Resins . . . . . . 25

Table 4 .1 - Summary of most ut i l ized test ing methods and their s ignif icance. . . . . . . . . . . . . . . 27

Table 4 .2 - Summary of rheologic behaviour , tes t methods and co llec ted data. -Summary

of rheolog ic behaviour , test methods and col lected data. Adapted from [39] . . . . . . . . . . . . . . . . . . 29

Table 4 .3-Flow behaviour accord ing to p -Ostwald value. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

Table 4 .4-Summary of f low behaviour accord ing to phase sh if t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

Table 4 .5-Retent ion vo lume ranges and their associa ted chemica l en ti t ies. . . . . . . . . . . . . . . . . . . 32

Table 5 .1-Summary of measured propert ies of industr ia l co llected samples f rom phenol

conta ining res ins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

Table 5 .2 - Summary of tr ia l s based on resin ac ids and i t s modif ica t ions. . . . . . . . . . . . . . . . . . . . . 43

Table 5 .3 - Summary of tr ia l s based on dimmers acids. Eq . functional i ty of Radiacid i s

obtained via i t s ac id va lue, 192 mgKOH/g. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

Table 5 .4 - -Summary of tr ial concerned with the use o f i sophthal ic acid . . . . . . . . . . . . . . . . . . . . 49

Table 5 .5-Summary of minera l con trol oi ls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

Table 5 .6- Summary of discharge propert ies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

Table 5 .7-Bol torn P1000 and H2004 propert ies summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

Table 5 .8-Summary of d ischarge propert ies of last recovered sample in case of ge ls . . . . . 58

Table 8 .1-Summary of weighted raw mater ia ls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

Table 8 .2-Summary of Equivalent Functional i t ies and corresponding ac id rat ios . . . . . . . . . . 77

Table 8 .3- Summary of measured propert ies for case study 1 batches. . . . . . . . . . . . . . . . . . . . . . . . . . 78

Table 8 .4-Summary of weighted raw mater ia ls and i t s corresponding percentages. . . . . . . . . 79

Table 8 .5-Cont inuation of Table 8 .4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79

Table 8 .6-Summary of Equivalent Functional i t ies and corresponding ac id rat io . . . . . . . . . . . . 80

Table 8 .7-Summary of measured propert ies for case study 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

1

GLOSSARY

AR—Acid ratio; relation between the total amount of hydroxyl and carboxyl

functions of a resin formulation

AV—Acid value; necessary amount of KOH needed to neutralize a resin sample;

mgKOH/g

CP-Cloud point; relat ive measurement of solubil i ty in varnish or test oil

Da—Dalton

DEG— Diethylene Glycol

GPC—Gel Permeation Chromatography

inc.—Incompatible; when resin sample is not totally soluble in i ts test oil

IPA—Isophthalic Acid

M c r-Crit ical molecular weight value from which viscosity is greatly M w dependent

MPG—Monopropylene Glycol

Mw-Mass-average molecular weight

na— Not available

P, Poise—1 P =0.1 Pa s - 1

p.Ost—p-Ostwald value

PTFE—Polytetrafluoroethylene

pTSA— para-toluenesulfonic acid

RCB—Rosin column bottom; By-product of tall oil dist i l lation. Highly viscous

l iquid.

REACH— Registration, Evaluation, Authorization and Restriction of Chemicals ;

SI—Structure Index; Measure of gel state

SP—Softening point;

Tack—Indicative and adimentional value that fundamentally suggests f i lm stickiness

TEG—Triethylene Glycol

Test Oil—Varnish oil for test procedures

THF—Tetrahydrofuran

TMP—Trimethylopropane

TOR—Tall oil rosin

3

PREFACE

The capacity of predicting what is around the

corner and manage a suitable response

beforehand, instead of simply reacting , grants

great momentum to those who possess i t .

With growing concerns about the

environmental state of our planet and because

great ideas must, in some way or another, be

economically supported to thrive, this work

focuses on anticipating a scenario were phenol

and formaldehyde use in ink resins is

abandoned.

Investigating early on how to achieve phenol

and formaldehyde free rosin resins, capable of

performing the same or better as the actual

phenol containing ones is not only an

environmental improvement but an economic

one as well , thus why dedicating t ime to this

issue is already relevant and necessary.

This document starts off with a brief

introduction to Respol history, activity, and

organization. An introduction about rosin, i t s

chemistry and applications in ink

manufacturing follows. A note on the approach

taken and suitable considerations are

presented next, followed by a description of

methods and routines. Outcomes are presented

after, together with their discussion,

concluding with f inal remarks.

This work was developed amidst the covid -19

pandemic. Therefore, i t was adapted to suit the

difficult ies created which in turn made i t more

interesting.