University of Tripoli Faculty of Engineering Metallurgical Engineering and Materials Science Graduate Studies

Home work no. 1

Properties &structure of polymer MME 680

(spring- 2013)

A- Name and Structure of Polymer

1- Polydimethylsiloxane(Tg=-123 )

2- Polyethylene(Tg=-120 )

3- Poly-(cis-1,4-butadiene) (Tg=-90 )

4- Poly-(cis-1,4- methyl butadiene ) (Tg= -73 )

5- Natural rubber(Tg= -72 )

6 - Butyl rubber( Polyisobutylene) (Tg= -65 )

It has a structure similar to polyetyhylene, except that each second carbon atom in the polymer chain is bonded to two methyl (CH3) groups. It is derived from the monomer isobutylene thus:-

Figure:- Structure of isobutylene and polyisobutylene or butyl rubber.

7-polychloroprene (Tg= -50 )

8- Poly(vinylidene fluoride) (Tg= - 40 )

9- Poly-(cis-1,4- propylene) (Tg= - 15 )

10-poly(methyl acrylate) (Tg= 10 )

11- poly(vinyl acetate) (Tg= 29 )

12- poly(methyl pentene) (Tg= 30 )

13-Ethylcellulose(Tg= 43 )

14-Nylon-6(Tg= 50 )

15-cellulose nitrate(Tg= 53 )

16-Polyethylene terephthalate(Tg= 69 )

17-Cellulose diacetate(Tg= 80 )

18-Poly(vinyl alcohol) (Tg= 85 )

19-polyphenylenesulfide(PPS) (Tg= 85 )

20-Poly(vinyl chloride) (Tg= 87 )

21-Polystyrene(Tg= 100 )

22-poly(methyl methacrylate) (Tg= 110 )

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23-Polyacrylonitrile(Tg= 120 )

24-poly(tetrafluoroethylene) (Tg= 126 )

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25-polyetheretherketone(peek) (Tg= 143 )

26-Polycarbonate(Tg= 150 )

27-Polyvinyltrimethylsilane(Tg= 170 )

28-polysulfone(Tg= 190 )

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29-Polytrimethylsilyipropyne(Tg= 200 )

30-polyetherimide(Tg= 210 )

31-Poly-(2,6dimethylphenylene oxide" ppo")(Tg= 210 )

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PPO is made of phenylene rings linked together by ether linkages in the 1,4 or para- positions, with a methyl group attached to carbon atoms in the 2 and 6 positions.

32-Polyethersulfone (PES) (Tg= 230 )

33-Polyimide(Kapton) (Tg= 300 )

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34-Polyoxadiazole(POD) (Tg= 450 )

B- Comparative between TG for Polymers Introduction

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Before comparative between TG for a polymers most be know why some polymers have high Tg's, and some have low Tg's. The very simple answer is this :How easily the chains move . A polymer chain that can move around fairly easily will have a very low Tg, while one that doesn't move so well will have a high one. This makes sense. The more easily a polymer can move, the less heat it takes for the chains to commence wiggling and break out of the rigid glassy state and into the soft rubbery state There are several things that affect the mobility of a polymer chain included:1-Backbone Flexibility( The more flexible the backbone chain is, the better the polymer will move, and the lower its Tg will be). In many polymer the main chain consist entire of c-c- bond which make the chain flexible wile when the main chain is completely unsaturated (ie. Constructed of- c=c bonds ) no rotation is possible and very rigid chain obtained and in case of chain containing both saturated and unsaturated bond c-c-c=c-c-c- the rotation around the single bond is still possible and the chain is flexible but less than single bond ; so that when a polymer has a backbone with a single bond has lower Tg than once a polymer has double bond and when another polymer have a backbone with mixed bond Tg for this polymer is lowest than both polymers . Introduction of hetrocyclic and aromatic group in backbone of chain lead Tg. Other element such as (nitrogen oxygen ) are linked with Carbon in backbone chain the presence its increase the flexibility(ie ,reduced Tg ) but of then ormtic or heterocylic group are also present in backbone tend to dominate the structure giving the chain rigid character .

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 For polymer s does not contain carbon atom in the back bone chains (inorganic polymers) sometimes are flexible such as silicon rubber that are containing silicon rather than carbon -si-o and another are rigid such as poly phosphazene -p=N2- Side group such as Pendant Groups "Fish Hooks and Boat Anchors" And Pendant " Elbow Room". (Bulky side groups also increase Tg because of the reduction of rotational freedom around the main chain ) Pendant Groups Part I: Fish Hooks and Boat Anchors Pendant groups have a big effect on chain mobility. Even a small pendant group can act as a fish hook that will catch on any nearby molecule when the polymer chain tries to move like corkscrew. Pendant groups also catch on each other when chains try to slither past each other. One of the best pendant groups for getting a high Tg is the big bulky adamantyl group. An adamantyl group is derived from a compound called adamantane.

A big group like this does more than just act like a hook that catches on nearby molecules and keeps the polymer from moving. It's a downright boat anchor. Not only does it get caught on nearby polymer chains, its sheer mass is such a load for its polymer chain to move that it makes the polymer chain move much more slowly. To see how much this affects the Tg, just take a look at

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two poly(ether ketones), one with an adamantane pendant group and one without.

The Tg of the polymer on the top is already decent at 119 oC, but the adamantyl group raises even higher, to 225 oC. Pendant Groups Part II: Elbow Room But big bulky pendant groups can lower the Tg, too. You see, the big pendant groups limit how closely the polymer chains can pack together. The further they are from each other, the more easily they can move around. This lowers the Tg, in the same way a plasticizer does. The fancy way to say that there is more room between the polymer chains is to say there is more free volume in the polymer. The more free volume, the lower the Tg generally. We can see this with a series of methacrylate polymers:

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You can see a big drop each time we make that pendant alkyl chain one carbon longer. We start out at 120 oC for poly(methyl methacrylate), but by the time we get to poly(butyl methacrylate) the Tg has dropped to only 20oC, pretty close to room temperature.

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Comparative

Polyvinyltrimethylsilane

Polytrimethylpropen

(a) Tg= -123

(b)Tg = 170

(c) Tg= 200

From the above structure of polymers we are clear to see the Tg for polytrimethylpropen is higher than polyvinyltrimethylsilane due to the effect of double bond in back bone and where the double bond decreased the flexibility of polymer as so as decreases Tg and make hard rigid polymer but a single bond in polyvinytrimethylsilane made a polymer less hardness and rigidity (i.e. some flexibility occur) and when compare this polymer with

polydimethlsiloxane ,it has lowest Tg duo to the replaced the carbon by( si-o) in main chain thats made flexible polymer and more chain movement.

polyethylene Tg= -120

Polystyrene(Tg= 100 )

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Butyl rubber Tg = -65

When the structure is simple and consisting of hydrogen bond around carbon in back bone made some crystallinety and Tg is low then when the methyl group bonded with Carbone such as butyl rubber and polyethylene the Tg increases from -120 in polyethylene to -65 in nature rubber by present of said group but whene replaced a hydrogen by vinyl group the Tg is change from negative charge to positive charge (ie. Is a highest tg than those ) because the ring of benzene made rigid hard polymer .

poly (cis ,1,4 butadiene) Tg = -90

poly (cis ,1,4 methyl butadiene) Tg =

-73

Natural rubber Tg = -72

Tg = -50

In above the all structure of polymer has a same back bone c=c double bond structure but have different Tg due to different crystallinety or aside group when compare the butadiene with methyl butadiene we see the methyl group prevent the movement of chain so that increases Tg but the natural rubber less

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Tg due to hydrogen bond but when replaced the hydrogen bond by Cl bonded. with carbon the CL reduced the flexibility chain as soon as increases Tg .

Polyvinylidene fluoride Tg = -40

Tg = 10

Polyvinyl acetate Tg = 29

Methyl pentene Tg = 30

Polyvinyl chloride Tg = 87

Polyvinyl alcohol Tg = 85

polyacrylonitrile Tg = 120

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the structure above all have the same back bone single (c-c )boned except polyacrylonitrile where have a single bond with branched has three bonded of carbon and N molecule these branched made hard rigid polymer and increase the tg of chain into from negative signal to highest positive degree from -40 into 120 and we can so the effect of molecule that are bonded with c-c is fluoride when bonded with c-c back bone is made flexible

different see

polymer and decrease tg but when replaced by cl the cl increase the rigidity of polymer and increase tg for polymer and OH molecule has about same effect and when backbone of chain is bonded with group such as acetate methyl cry late-methyl the distribution of group and oxygen joint with carbon effect of flexibility when the oxygen are joint in one side such as methyl acrylate is increased the flexibility of chain which reduce the tg of chain and when is capture between to carbon bond such as acetate increase tg by miner value but when replace oxygen by the methyl group the tg still is higher than those structure such as methyl pentene.

Polyphenylene sulfide Tg = 85

poly(2-6dimethylphenylene )Tg = 210

polyetheretherketone Tg = 134

We see from above Bulky backbone chain groups also increase Tg because of the reduction of rotational freedom main chain such as cycle benzene and the said group such ether increase Tg from above structure the in the Polyphenylene sulfide reduced tg and short length chain compared with ether

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and etherketone . and whene compare poly(2-6dimethylphenylene )with polyetheretherketone the Tg for poly(2-6dimethylphenylene ) is above the polyetheretherketone by 24 duo to the oxygen where made some flexibility .

Ethyl Cellulose Tg = 43

Cellulose nitrate Tg = 53

Cellulose diacetate Tg = 80

The bulky group present in cellulose increased Tg for chain see diacetate group in Cellulose diacetate where increased the comparability of structure and prevent the movement of chain but when replaced by small group such as nitrate the Tg is decreased but it is still greater than Ethyl because the present of nitrogen in side grope decreased the flexibility of movement of side group about chain as so as the Tg of cellulose is increased from left to right (ie Tg of Ethyl Cellulose Cellulose nitrate Ccellulose diacetate).

Tg = 190

Tg = 230

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Polysulfone backbone is just plain stiff but has some flexibility but when put the ether group in chain backbone the polymer's it will be more rigid and stiff as so as the Tg is high .

Tg = 50

polyoxadiazole Tg = 450

kapton Tg = 300

the position of nitrogen and oxygen molecule in chain it is effect in the Tg for a polymer because the bond between these molecules and carbon-carbon effect of flexibility of polymer thats we can be seen from above polymer where the nylon 6 has six carbon same polyoxadiazole but the Tg for nylon 6 is less duo to the rings of carbon distribution and the number of N and bonded it with carbon and oxygen the same effect for kapton . but the kapton is less Tg compared with polyoxadiazole duo to present oxygen that are distributed by away increased the flexibility of chain and reduced Tg buy some value but still higher duo to a complex ability of structure .

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