Polimerização.
Autor: Daniel Andrade | Publicado: 2014-10-09T01:16:00-07:00


Um pouco da história dos políeros



As macromoléculas vêm
sendo usadas há milênios pela Humanidade: o algodão, a lã, a seda etc.na
fabricação de tecidos; os cascos e chifres dos animais para fazer pentes,
botões etc.; o marfim das presas dos elefantes para fazer objetos de adorno,
teclas de piano etc.

Na metade do século
XIX, o marfim era usado também para fabricar bolas de bilhar. A popularização desse
jogo na Europa e nos Estados Unidos sofreu um abalo quando o preço do marfim
subiu vertiginosamente. Por isso uma fábrica norte-americana de bolas de bilhar
prometeu um bom prêmio a quem descobrisse um substituto para o marfim.



Em 1870, John Wesley
Hyatt submeteu uma mistura de nitrocelulose, cânfora e álcool a uma pressão
elevada e conseguiu um produto que foi denominado celulóide. Esse produto teve
sucesso, não só na produção das bolas de bilhar daquela época, mas também na
fabricação de dentaduras, colarinhos de camisas e, por fim, em filmes
fotográficos (substituído depois por acetato de celulose). Começou aí uma
corrida à procura de materiais sintéticos, que resultou, por exemplo, no
celofane (1892) e em plásticos da caseína (1897). Paralelamente iniciou-se também
uma busca de substitutos para as fibras naturais, visando principalmente à
produção de uma seda artificial. Em 1885, Chardonnet obteve uma primeira seda
artificial, à base de nitrocelulose (com o inconveniente de ser inflamável); em
1890, Despeissis conseguiu um primeiro tipo de raiom, a partir de algodão; em
1892, Ross e Beven produziram a viscose, também a partir do algodão.



Note então que todas
as tentativas partiam de polímeros naturais, de baixo custo (celulose de
algodão de segunda categoria, caseína do leite etc.), que eram modificados na
tentativa de se obterem produtos de melhor qualidade. Um grande passo foi dado
em 1907 por Leo Hendrik Baekeland, que produziu a baquelite a partir de moléculas
simples—o fenol e o formaldeído. O sucesso da baquelite foi imediato. Ela foi
usada no início do século XX na produção dos discos musicais de 78 rpm; depois,
em tomadas e interruptores elétricos, cabos de panelas etc. Até hoje, a baquelite
é usada na produção de chapas para revestimento de móveis. Atualmente, a tecnologia
de produção dos polímeros sintéticos está muito avançada. No entanto, devemos ter
sempre em mente as seguintes idéias gerais, que passamos a explicar a partir de
um dos exemplos mais simples, que é

o da produção do
polietileno. Antes, porém, vamos dar uma breve definição de polímeros.



Polímeros (do grego: poli,
“muitas”; meros, “partes”) são compostos de moléculas muito

grandes,
formados pela repetição de uma unidade molecular pequena, chamada monômero.

Por exemplo: n CH2 CH2 (... CH2 CH2 ...)n

&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;Etileno&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; &nbsp;Polietileno

&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Monômero&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; &nbsp;Polímero



Devido ao seu tamanho
avantajado, a molécula de um polímero é chamada de macromolécula. A reação que
produz o polímero é denominada reação de polimerização. Nessa reação, a
molécula inicial (monômero) vai, sucessivamente, se unindo a outras, dando o dímero,
o trímero, o tetrâmero e o polímero. Aparentemente, o processo poderia
prosseguir, sem parar, até produzir uma molécula de tamanho “infinito”. No
entanto, reações das extremidades da macromolécula com impurezas da própria matéria-prima
(inclusive com a água, presente na forma de umidade) acabam impedindo a
continuação

indefinida da reação.






Reação de Polimerização:

Polimerização(em
cadeia):



São aquelas que o monômeros
são adicionados sucessivamente até formar o polímero.

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Formação Rápida de Moléculas de Polímeros (1
segundo);

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Não existem subprodutos de reação;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Pesos moleculares elevados (-+ 105 );

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Reações características por 3 etapas:

<!--[if !supportLists]-->1-&nbsp;&nbsp;&nbsp; <!--[endif]-->Iniciação;

<!--[if !supportLists]-->2-&nbsp;&nbsp;&nbsp; <!--[endif]-->Propagação;

<!--[if !supportLists]-->3-&nbsp;&nbsp;&nbsp; <!--[endif]-->Terminação.

Policondesação;

São aquelas em que ocorre
eliminação de algumas molueculas pequenas, geralmente água quando dois grupos
funcionais diferentes reagem entre si.

Exemplos de grupos
funcionais:

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Álcoois;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Fenóis;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Ésteres;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Aldeídos e Cetonas;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Ácidos carboxílicos;

Onde esses grupos
funcionais estão presentes também em
essências, perfumes, plásticos, fibras têxteis sintéticas, e no álcool como
combustível para automóveis.

Sendo as características mais comuns são:

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Reações em etapas;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Evolução gradativa do peso Molecular;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Consumo rápido dos manômetros.

As polimerizações acontecem de diversas formas e em muitos casos por
diferentes situações. Aqui abordaremos os aspectos químicos, não se preocupando
muito com aspectos operacionais, além de mostrar as reações de forma
simplificada.



A polimerização pode ocorrer por:



Adição:

<!--[if !supportLists]-->ü&nbsp; <!--[endif]-->Polimerização por radicais livres:



- iniciação:



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<![endif]--><!--[if !vml]--><!--[endif]-->I &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; &nbsp;2 Rr



Propagação:



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<![endif]--><!--[if !vml]--><!--[endif]-->Rr1&nbsp;&nbsp;&nbsp; + monômero&nbsp;&nbsp; &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Rr2;



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<![endif]--><!--[if !vml]--><!--[endif]-->Rr2&nbsp;&nbsp;&nbsp; + monômero&nbsp;&nbsp;  &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;Rr3+ monômero;



Terminação:



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&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
(Combinação)





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" fillcolor="#4f81bd [3204]" strokecolor="#243f60 [1604]" strokeweight="2pt"/><![endif]--><!--[if !vml]--><!--[endif]-->Rr&nbsp;&nbsp; + Rs&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Pr + Ps

&nbsp;&nbsp;&nbsp;&nbsp;
Desproporcionalização



Características que formam polímeros em blocos



Catalizadores:



Reagentes de Grinar:



<!--[if !supportLists]-->ü&nbsp; <!--[endif]-->Brometo de Metil -&nbsp; magnésio;

<!--[if !supportLists]-->ü&nbsp;
<!--[endif]-->Sódio Trifenil – metila.



Metais Alcalinos Livres.



<!--[if !supportLists]-->ü&nbsp;
<!--[endif]-->Sódio;

<!--[if !supportLists]-->ü&nbsp; <!--[endif]-->Potássio;

<!--[if !supportLists]-->ü&nbsp;
<!--[endif]-->Lítio.

Dissolvidos em amônia líquida ou em suspenção com
solventes orgânicos.



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<![endif]--><!--[if !vml]--><!--[endif]-->R: Li&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; {R-
&nbsp;Li+ }



Polimerização Iônica:



Aplica-se a monômeros insaturados cujos
substituintes são doadores de elétrons.

Características polimerização de baixas
temperaturas:



Catalizadores: FRIEDEM _ CRAFTS:

Halogenetos de AI; Ti; Sn



Co-catalizadores: água e álcool.



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<![endif]--><!--[if !vml]--><!--[endif]-->TiC4 + RH&nbsp; &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; [
Ti1 Cl4R] [-] + H [+]





Polimerização por coordenação ( Ziegler -&nbsp; Natta)



Polimerização com catalizadores de Ziegler -&nbsp; Natta que são complexos de cloreto de metais
de TiCl4 de transição e compostos de organometálicos (trietil de alumínio).

Forma moléculas de polímeros lineares e permitem
estereoquímicos de reação.



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<![endif]--><!--[if !vml]--><!--[endif]-->TiCl4 + AlR3 &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;Ti Cl3R + AlR2Cl




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<![endif]--><!--[if !vml]--><!--[endif]-->Ti Cl3R + AlR2Cl &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; TiCl3
+ R&nbsp;&nbsp; + AlR3



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<![endif]--><!--[if !vml]--><!--[endif]-->TiCl3 + R&nbsp;&nbsp; + AlR3
&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; &nbsp;TiCl2[R+ + AlR2Cl]



Inibidores e retardadores



<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Uma reação é retardada se a velocidade é mais
lenta;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Uma reação é inibida se ela começa depois de um
tempo sem&nbsp; reação.



Inibidores:



<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Apresenta grande eficiência &nbsp;na captura de radicais livres;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Os radicais reagem mais rapidamente com os
inibidores que com os monômeros;

<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->São utilizados frequentemente para estocagem de monômeros,
Ex.: Fenóis, quinonas, aminas.



Retardadores:



<!--[if !supportLists]-->·&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;
<!--[endif]-->Apresenta menos reatividade com os radicais livres
competindo com o monômeros. Ex.: Nitro compostos, halogêneos.











PROCESSO DE POLIMERIZAÇÃO:



Compostos insaturados podem ser polimerizados em:



<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Massa (bulk ppolymerization);

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Solução

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Emulsão;

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Suspenção;

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->“slurry” (lama).



A escolha do método depende principalmente das
propriedades químicas dos monômeros, do equipamento necessário e da aplicação
do polímero.



&nbsp;Polimerização em massa:



O método mais antigo utilizado na preparação de polímeros
partindo de compostos insaturados. Este processo obtém polímeros puros pois
suas fontes de contaminação são poucas, sendo seus principais pontos:



<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Solvente -&nbsp; próprio do monômero;

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Iniciação – iniciador químico (peroxido);

&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; -- térmico;

&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; -- Radiação.

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Reação fortemente exotérmica (grande desvantagem)

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Aumento da viscosidade dificultando a transferência de calor;

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Variação do P.M. (Região superaquecida);

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Permite obtenção de peças moldadas a partir do monômero, sem pressão
com OTIMAS QUALIDADES OTICAS.

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Fabricação industrial de chapas de Polimetacrilato de metila.



Polimerização em solução:



&nbsp;Além do iniciador
e do monômero usa-se um solvente.



Como vantagens pode-se falar da facilidade de transferência
de calor, homogeneidade da temperatura e obtenção do polímero dissolvido – (
aplicação em revestimento pela remoção de solvente).



Como desvantagens fica&nbsp; apontado o retardamento de reação pelo
solvente e a dificuldade na remoção do solvente.



Muito aplicado em policondensação e tendo pouca
aplicação em poliadição, como exemplo temos o Polibutadieno.



Quando o polímero formado é insolúvel no meio
reacional temos tem-se uma polimerização em LAMA ( “slurry”) ou uma
polimerização com precipitação.



Como exemplos destes dois têm:



<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Acrílica nitrila;

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->ABS.



Polimerização em emulsão



Os monômeros se acham emulsificados em, um NÃO –
SOLVENTE, geralmente agua contendo iniciadores solúveis em água, persulfato de
potássio e emulsificantes (sabão). Com tamanho das partículas entre 0,001 - 1µ.
Onde os radicais livres se formam na fase da água e depois migrando para a&nbsp; fase orgânica.



As vantagens são:



<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Fácil controle da temperatura, pois apresenta baixa viscosidade;

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Homogeneidade de P.M. (Peso Molecular)

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Rápida e alta conversão.







As desvantagens:



<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->A dificuldade da remoção do emulsificante, sendo isso uma restrição na
aplicação.

Sendo bastate aplicado na indústria no ramo de PVC
e SBR.





Polimerização em suspenção



Através de forte agitação de um monômero + água
pode haver a formação de gotículas com tamanho que variam de 1-50µ ou ate 1000µ
(1mm) dependendo da densidade do monômero em relação a água.

São usados agentes de suspenção (estabilizadores)
para evitar a coalescência das gotículas viscosas de monômeros-polímeros em
suspenção.



Apresentando com vantagens as mesmas de uma
polimerização em emulsão e não tendo as mesmas desvantagens desta ultima,
torna-se baste empregada na indústria que trata de Poliestireno e SAN. E tendo
como agente de suspenção:



<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->TCP – Fosfato tricalsico;

<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Poli-ácool vinílico;


<!--[if !supportLists]-->Ø&nbsp; <!--[endif]-->Outros.