About this family
Every polymer on this page is built the same way: a carbon–carbon double bond opens and adds to the growing chain, leaving a saturated –CH2–CHX– backbone behind. The backbone is therefore identical in all of them. Everything that distinguishes polyethylene from PVC from PTFE is the substituent X, and the span that one variable covers is the widest in polymer science – from a material that melts at 130 °C and is sold by the tonne as film, to one that survives 327 °C and nothing sticks to.
The commodity plastics cluster here because the chemistry is cheap and tolerant: free-radical initiation, no rigorous exclusion of water, monomers that come straight off a cracker. That is also why the family is where most controlled-polymerisation methods were developed and tested, and why so many of the entries below are specialty monomers made to give a familiar backbone one unfamiliar property.
What sets the properties
Three things about the substituent set the properties. Size and stiffness govern Tg: hydrogen leaves the chain free to rotate and polyethylene sits at −110 °C, a methyl group raises polypropylene to −10 °C, and a phenyl ring raises polystyrene to 100 °C. Polarity adds interchain attraction on top – chlorine is not much larger than a methyl group, but poly(vinyl chloride) reaches 80 °C because the C–Cl dipoles pull neighbouring chains together. Hydrogen bonding does more again: poly(vinyl alcohol) reaches 85 °C and poly(N-vinylpyrrolidone) 175 °C dry.
Regularity decides whether the polymer can crystallise at all, and that is a question about stereochemistry rather than about the substituent. Any carbon carrying X is a stereocentre, so an ordinary radical polymerisation gives an atactic chain that cannot pack – which is why commercial polystyrene is a transparent glass with no melting point, while the isotactic form crystallises. Polypropylene is the commercial case that matters: atactic polypropylene is a tacky material of no structural use, and isotactic polypropylene, melting at 165 °C, is one of the most-produced plastics on earth. Nothing separates them but the arrangement of successive units.
Two entries here are made by a route the drawing does not reveal. Poly(vinyl alcohol) cannot be made from vinyl alcohol, which tautomerises to acetaldehyde faster than it could ever polymerise; it is made by polymerising vinyl acetate and then hydrolysing the ester, so the degree of hydrolysis is a formulation variable and commercial grades are really vinyl alcohol–vinyl acetate copolymers. Fluorinated members behave unusually for a different reason: fluorine is small enough not to disrupt the chain but forms a continuous sheath around it, which is why polytetrafluoroethylene melts at 327 °C, dissolves in nothing, and has the lowest surface energy of any bulk polymer.
All 208 in the library
Sorted by parent name, ignoring the leading "poly" and any locants – so poly(2-hydroxyethyl methacrylate) files under H. 189 of the 208 carry a note, and every one is searchable by drawn structure on the structure search page. 42 have a CAS registry number for the polymer; most specialty polymers have never been assigned one, and the number you find in a catalogue is usually the monomer's, which is why the field is blank rather than borrowed here.
A
Poly(4-acetoxystyrene)
The protected form in which poly(4-hydroxystyrene) is normally made: the free phenol interferes with radical and anionic polymerisation, so the acetate is polymerised and then hydrolysed off. It is a general lesson in the field - when a functional group fights the polymerisation, polymerise its ester and remove it afterwards.
Polyacetylene
The polymer that started conducting polymers, and the one nobody uses. A bare alternating single-double backbone, so the p orbitals overlap along the whole chain and doping raises the conductivity by orders of magnitude - the result that won the 2000 Nobel Prize in Chemistry. It is also insoluble, infusible and oxidises in air within minutes, which is why every conducting polymer since has been an attempt to keep the conjugation and add a side chain that makes the material processable.
Polyacrylamide
Poly(acrylamide-co-acrylic acid)
The polymer pumped underground in enhanced oil recovery, and the superabsorbent in soil conditioners. Hydrolysing some of polyacrylamide's amides to carboxylates puts charge on the chain, which expands the coil and multiplies the solution viscosity - the property that lets it push oil through rock. Too much hydrolysis and it precipitates with the calcium in brine, so the degree of hydrolysis is the design variable. Not drawn: the composition is the point, and one repeat cannot carry it.
Poly(acrylic acid)
Polyacrylonitrile
Acrylonitrile styrene acrylate
ABS with the butadiene rubber replaced by an acrylate one, which removes every double bond from the rubber phase - and with it the ultraviolet and ozone attack that yellows and embrittles ABS outdoors. Same toughening mechanism, same processing, weatherable. It is what exterior automotive trim and garden furniture are made from. Not drawn: a grafted two-phase blend.
Acrylonitrile-butadiene-styrene
A three-monomer blend/graft: a butadiene rubber phase toughens a rigid SAN matrix. Widely used for impact-tough moldings (LEGO, housings).
Poly(acrylonitrile-co-methyl acrylate)
The polymer nearly all carbon fibre starts as. Pure polyacrylonitrile is too tightly hydrogen-bonded to spin well and cyclises uncontrollably on heating; a few percent of a comonomer opens the structure enough to dissolve and draw it, and moderates the exotherm during stabilisation so the fibre does not burn instead of cyclising. Not drawn: the comonomer fraction is the specification.
Poly(N-acryloylazepane)
The seven-membered cyclic tertiary acrylamide, the most hydrophobic of the acryloyl-ring series and the one with the lowest cloud point.
Poly(N-acryloylglycinamide)
One of the few synthetic polymers with an upper critical solution temperature in plain water: the two amides per repeat unit hydrogen-bond to each other below the transition and to water above it, so it dissolves on heating rather than precipitating. Ionic impurities destroy the effect, which is why the early literature on it disagreed.
Poly(N-acryloylpiperidine)
The all-carbon relative of poly(N-acryloylmorpholine). Removing the ring oxygen removes the hydration that keeps that polymer soluble, and this one phase-separates near 5 C.
Poly(N-acryloylpyrrolidine)
A cyclic tertiary acrylamide with an LCST near 56 C, at the top of the useful range for this family.
Poly(N-acryloylthiomorpholine)
The sulfur analogue of poly(N-acryloylmorpholine). Replacing the ring oxygen with sulfur removes most of the hydration that keeps the morpholine polymer soluble at every temperature.
Aliphatic polyketone
Carbon monoxide and ethylene alternating perfectly under a palladium catalyst - one of the few commercial polymers made from CO, which is otherwise a poison rather than a feedstock. The regular carbonyls give strong dipole interactions and a melting point near 220 C, with wear resistance and barrier properties better than nylon and no moisture sensitivity. Its ketones are also photoreactive, so it degrades in sunlight, which is either a defect or a design feature.
Poly(allyl alcohol)
The textbook case of degradative chain transfer: the radical abstracts an allylic hydrogen far more readily than it adds to the double bond, so the chain stops almost as soon as it starts and allyl monomers give only oligomers. Those oligomers are useful as polyols precisely because they are short and heavily functionalised, but the failure to propagate is why no allyl polymer is a commodity.
Poly(allyl glycidyl ether)
Carries an epoxide on every repeat unit, so a chain can be made first and functionalised afterwards by thiol-ene at the allyl group or ring-opening at the epoxide - two orthogonal handles that do not interfere. It is the usual comonomer for putting crosslink sites into a polyether elastomer.
Poly(allylamine)
A weak polycation with a primary amine on a short arm off the backbone, which makes it both charged and easy to react with. Its charge titrates with pH, unlike a quaternary ammonium, so layer-by-layer films built from it can be assembled and then disassembled by changing pH - the basis of a large fraction of the polyelectrolyte multilayer literature. Normally supplied and used as the hydrochloride.
Poly(N-(3-aminopropyl)methacrylamide)
A primary-amine methacrylamide, handled as the hydrochloride. Because the linkage is an amide rather than an ester, the pendant amine cannot attack the backbone the way it does in poly(2-aminoethyl methacrylate).
Poly(4-aminostyrene)
An aromatic amine on every repeat, which makes the polymer a weak polybase, a ligand for metals, and a substrate for diazotisation - the classic route to attaching dyes and biomolecules to a polystyrene support. The free amine inhibits radical polymerisation, so it is normally reached by reducing the nitro polymer.
Atactic polypropylene
Methyl groups placed at random, so nothing crystallises and the material is a soft tacky amorphous solid with no melting point at all - originally the unwanted fraction from early catalysts, now made deliberately for adhesives, roofing bitumen and sealants. The clearest demonstration in commodity plastics that tacticity alone separates a structural material from a glue. Same repeat unit as every other polypropylene - the difference is a property of the sequence, not of the unit.
Polyazulene
Built from azulene, the non-alternant isomer of naphthalene with a five- and a seven-membered ring fused and a genuine dipole moment - unusual in a hydrocarbon. That built-in polarity gives the polymer a smaller band gap than its naphthalene analogue and makes it electrochemically active in both oxidation and reduction. Not drawn: the polymerisation is not regiospecific, so the linkage pattern is not fixed.
B
Poly(N-benzylacrylamide)
The methylene spacer restores normal amide hydrogen bonding that the N-phenyl compound loses, while keeping the aromatic ring for pi-stacking.
Poly(N-benzylmethacrylamide)
The benzyl spacer restores the amide N-H hydrogen bonding lost in the N-phenyl polymer, giving a high-Tg but still hydrogen-bonded material.
Bottlebrush by grafting-onto
The third route to a bottlebrush, and the one that trades certainty for freedom. Backbone and side chains are made separately, each under whatever conditions suit it, and joined afterwards through a reactive pair - usually an azide and an alkyne, because that coupling still works when the site is crowded. The freedom is real: the two blocks never have to tolerate each other's chemistry, which is the only way to combine, say, a polypeptide with an oligonucleotide. The cost is that the last side chains have to reach attachment points already surrounded by the ones that got there first, so grafting density falls short of one per repeat and is never quite known. Grafting-through guarantees density but needs a macromonomer; grafting-from gives long backbones but crowds the growing radicals; grafting-onto is the fallback when neither block can be made in the other's presence. Reviewed by Verduzco, Li, Pesek and Stein, Chem. Soc. Rev. 2015, 44, 2405, and by Mullner, Chem. Commun. 2022, 58, 5683.
Bottlebrush by RAFT grafting-through
Grafting-through without a metathesis catalyst. A macromonomer is made with an ordinary polymerisable end - usually a methacrylate - and then polymerised under reversible addition-fragmentation chain transfer control, which tolerates water, acids, amines and unprotected functional groups that would stop a ruthenium catalyst. The trade is conversion: a growing radical adds a whole polymer chain each time, so the reaction slows badly as it proceeds and backbones stay shorter than ROMP reaches. Where ROMP wins on backbone length and speed, RAFT wins on what the side chain is allowed to contain, which is why it is the usual choice for charged or biologically functional brushes.
Poly(4-bromostyrene)
Polystyrene carrying a handle. The aryl bromide is inert during polymerisation but reacts cleanly afterwards in palladium-catalysed couplings, so the polymer is a scaffold for attaching almost anything to a well-defined backbone. The heavy atom also gives strong X-ray contrast, useful for imaging domains in block copolymers.
Poly(1-butene)
A polyolefin whose selling point is creep resistance under sustained pressure at temperature, which is why it is used for hot water pipe. It has an awkward habit: crystallised from the melt it first forms a metastable tetragonal phase and then converts over about a week to the stable trigonal one, getting harder and denser as it goes, so parts have to be conditioned before they are to specification.
Poly(N-(butoxymethyl)acrylamide)
A blocked self-crosslinking amide: on baking it liberates butanol and reverts to the N-methylol, which then condenses. Blocking it this way gives the storage stability that N-methylolacrylamide lacks.
Poly(butyl cyanoacrylate)
Surgical superglue. The two electron-withdrawing groups on the same carbon make the double bond so electrophilic that trace surface moisture initiates anionic polymerisation in seconds - no catalyst, no mixing. The butyl ester is the shortest chain whose degradation products tissue tolerates; the methyl version sets faster but the formaldehyde it releases as it degrades is too irritating for internal use.
Poly(tert-butyl vinyl ether)
The most hindered of the common vinyl ethers, and glassy near 90 C where the methyl version is a rubber below room temperature - the whole difference is how freely the pendant group can rotate. Acid cleaves the tert-butyl ether cleanly to poly(vinyl alcohol), so it also serves as a protected precursor that dissolves in hydrocarbons.
Poly(N-butylacrylamide)
Hydrophobic enough that the homopolymer is no longer water-soluble; it is used as the hydrophobic comonomer that pulls the LCST of acrylamide copolymers downwards.
Poly(N-butylmethacrylamide)
The C4 N-alkyl methacrylamide, at the point in the series where the polymer stops being water-soluble.
Poly(N-tert-butylmethacrylamide)
A hindered, hydrophobic methacrylamide with a high Tg, used as the rigid comonomer in hair fixatives and in thermoresponsive copolymers.
Poly(4-tert-butylstyrene)
C
Chlorinated polyethylene
Polyethylene chlorinated in suspension, which disrupts the crystal and converts a rigid plastic into a rubber - the degree of chlorination tunes it continuously between the two. Around a third chlorine gives an elastomer that resists oil, weather and flame, used as a jacket for wire and as the impact modifier that makes rigid PVC pipe tough. Not drawn: chlorination is random along the chain.
Poly(2-chloroethyl vinyl ether)
A vinyl ether carrying a displaceable chloride, so a cationic polymerisation gives a well-defined chain that can then be converted wholesale to esters, amines or azides. It is one of the few monomers that combines living cationic polymerisation with a reactive handle, which is why it appears wherever a precisely defined functional polyether is needed.
Poly(4-chlorostyrene)
Polystyrene with a chlorine para on the ring, which raises the glass transition by about 20 C and the refractive index with it. Its main use is as a model: it is nearly isomorphous with polystyrene but has a very different electron density, so a block copolymer of the two gives sharp X-ray contrast between domains that would otherwise be invisible.
Chlorosulfonated polyethylene
Chlorinated polyethylene carrying a few sulfonyl chloride groups, which is what lets it be cured - the chlorines alone give no useful crosslink. The result resists ozone, acid and weathering to a degree that made it the standard for pond liners, inflatable boats and roofing for decades, and it holds colour where a carbon-black-filled rubber cannot. Not drawn: both substitutions are random and sparse.
Poly(chlorotrifluoroethylene)
Comb polymer
What a bottlebrush is before it becomes one. Graft a backbone loosely, or with short side chains, and the grafts stay out of each other's way: the backbone keeps its normal flexibility and the molecule is still a coil, just a branched one. Raise the grafting density or lengthen the side chains and the grafts begin to overlap, the steric cost of a coiled backbone becomes unpayable, and the molecule straightens into the extended cylinder that earns the name bottlebrush. There is no sharp line between the two, which is why the same material is called a comb in one paper and a brush in the next, and why quoting a grafting density and a side-chain length says more than either word does.
Crosslinked polyethylene
The repeat unit is ethylene and stays ethylene - what changes is that a few carbons per thousand are joined to a neighbouring chain, by peroxide or by grafted silane that condenses in hot water. That is a relationship between chains, not a change to any one of them, so it cannot appear in a repeat unit; what it does appear in is the behaviour, since the network no longer melts and the pipe holds pressure at temperatures where polyethylene would creep.
Cyclic olefin copolymer
Norbornene units copolymerised into polyethylene without opening their rings, so the bulky bicyclics sit in the backbone and stop it crystallising entirely. The result is a glassy, water-clear polyolefin with almost no water absorption and excellent transparency into the ultraviolet - which is why it has displaced glass for prefilled syringes and microfluidic chips. Not drawn: the norbornene fraction sets the glass transition and is the specification.
Poly(cyclohexyl vinyl ether)
Vinyl ethers cannot be polymerised by radicals but go readily by cation, and they alternate perfectly with fluoroolefins - which is the basis of the FEVE resins used on architectural aluminium. The cyclohexyl ring provides hardness and the fluoroolefin the weathering, giving coatings warranted for thirty years of sunlight.
Poly(N-cyclohexylacrylamide)
A rigid, hydrophobic acrylamide; the ring raises Tg substantially over the linear N-alkyl members of the series.
Poly(N-cyclohexylmethacrylamide)
A rigid, hydrophobic methacrylamide. The combination of a cyclohexyl group and an amide N-H puts its glass transition well above that of the corresponding acrylamide.
Poly(N-cyclopropylacrylamide)
The cyclopropyl ring is close in volume to an isopropyl group but far more rigid, and the polymer's LCST sits near 45 C - well above that of poly(N-isopropylacrylamide).
D
Poly(1-decene)
Oligomers of this are the polyalphaolefins that make up most fully synthetic motor oil - a hydrocarbon of uniform, branched structure with none of the waxy linear chains or reactive aromatics that a distilled mineral oil carries. The result pours at -50 C and oxidises far more slowly, which is the whole reason synthetic oil exists.
Poly(2,5-dialkoxy-p-phenylene vinylene)
The symmetric dialkoxy PPV, drawn with methoxy groups as the simplest member. Two electron-donating ethers raise the highest occupied level and narrow the gap, shifting emission to the red and making the polymer far easier to oxidise - which is both why it emits where it does and why these materials degrade in air unless encapsulated.
Poly(diallyldimethylammonium chloride)
The strong polycation of water treatment, and a rare case of a diene that cyclises as it polymerises. Each monomer has two allyl groups; the radical adds to one and then closes onto the other before propagating, so the backbone is a chain of five-membered pyrrolidinium rings rather than a crosslinked gel. The quaternary nitrogen is permanently charged, so like the sulfonates its charge does not titrate. Drawn as the cation; the chloride counter-ion is not shown.
Poly(dibutyl fumarate)
A 1,2-disubstituted monomer, which normally means it will not homopolymerise at all - the transition state is too crowded. Fumarate esters are the exception: they polymerise slowly to give a chain so stiff and extended that it behaves as a semi-rigid rod in solution, and unusually the propagating radical is stable enough to see by spectroscopy.
Poly(N,N-dibutylacrylamide)
A tertiary acrylamide too hydrophobic to dissolve in water at any temperature; it is used as the hydrophobic block in amphiphilic acrylamide copolymers.
Poly(diethyl fumarate)
The shorter ester of the same family, and stiffer still - substituents on every backbone carbon leave the chain almost no rotational freedom, so the glass transition sits above 130 C. The trans geometry is what allows it to polymerise where the cis maleate barely can, which is one of the cleanest demonstrations that monomer geometry rather than electronics can decide whether a polymer forms.
Poly(N,N-diethylmethacrylamide)
The methacrylamide counterpart of poly(N,N-diethylacrylamide), whose LCST sits near 32 C. Adding the alpha-methyl stiffens the backbone rather than making it more hydrophobic, which is why the methacrylamides of this family generally cloud at higher temperatures than their acrylamides.
Poly(N,N-dimethylacrylamide)
Poly(N-(3-(dimethylamino)propyl)acrylamide)
A cationic acrylamide. Unlike the aminoalkyl esters, the amide linkage does not hydrolyse in use, which is why these monomers dominate water-treatment flocculants.
Poly(N,N-dimethylmethacrylamide)
A water-soluble tertiary methacrylamide with no LCST; the methacrylate backbone makes it stiffer and more hydrolysis-resistant than poly(N,N-dimethylacrylamide).
Poly(diphenylacetylene)
Two phenyls per backbone carbon, which crowds the chain into a stiff twisted conformation and makes it one of the most thermally stable substituted polyacetylenes - stable above 400 C, where the parent degrades in air within minutes. The same crowding gives an unusually high free volume, so films of it are studied as gas separation membranes.
Poly(N,N-dipropylacrylamide)
A disubstituted acrylamide with no N-H at all, so it cannot hydrogen-bond to itself. Its LCST near 20 C comes purely from the hydrophobicity of the two propyl groups.
Poly(divinylbenzene)
Two vinyl groups on one ring, so it crosslinks rather than forming chains - the crosslinker in every ion-exchange resin and polymer support bead. The percentage of it in a styrene bead sets the swelling and therefore the accessibility of the interior: 1 to 2 percent gives a gel that swells and lets reagents in, 8 percent gives a rigid bead that does not. Not drawn: a network has no repeat unit.
Poly(N-dodecylacrylamide)
The C12 associating acrylamide. A few mole percent in a polyacrylamide backbone raises solution viscosity by orders of magnitude through hydrophobic association.
Polydopamine
Stir dopamine in mildly alkaline water and it deposits an adherent film on essentially any solid - metal, oxide, fluoropolymer - which is the trick borrowed from mussel adhesive proteins, where catechol and amine together do the sticking. Its internal structure is still argued over: covalent indole chains, stacked non-covalent aggregates, or both, which is exactly why no structure is drawn here.
E
Poly(ethyl cyanoacrylate)
The ester in almost every consumer superglue, chosen as the compromise between the methyl version's speed and its irritancy. Its other use is forensic: warmed in a chamber, the vapour polymerises preferentially on the residues of a latent fingerprint, developing it as a white ridge pattern on surfaces where powder will not work.
Poly(ethyl vinyl ether)
Poly(N-ethyl-N-methylacrylamide)
An unsymmetrical tertiary acrylamide with an LCST between those of the dimethyl and diethyl polymers - the cleanest way to place a cloud point at an arbitrary temperature without copolymerising.
Poly(N-ethylacrylamide)
One methylene short of the thermoresponsive window; it stays soluble in water where poly(N-isopropylacrylamide) phase-separates at 32 C.
Polyethylene
The melting point given here is for high-density PE; branching drops it, and ordinary LDPE melts nearer 110 °C. The glass transition is the disputed one — assignments range from about −125 °C (Odian's Table 1-3) to −20 °C depending on which relaxation is called Tg.
Poly(ethylene-alt-chlorotrifluoroethylene)
ETFE with one fluorine swapped for chlorine, which is bulkier and more polarisable. That single substitution lowers the melting point by about forty degrees and improves adhesion and barrier properties, so it is used as a lining and a powder coating where ETFE would be needlessly hard to process.
Poly(ethylene-alt-tetrafluoroethylene)
Tetrafluoroethylene and ethylene alternate almost perfectly, which is the point: the CH2 groups break up the fluorine sheath enough to give a melt that can be extruded and a film with real tear strength, while keeping most of the chemical resistance. It is what the pillows of stadium roofs are made from - highly transparent to ultraviolet, self-cleaning, and about one percent the weight of the glass it replaces.
Poly(ethylene-co-vinyl alcohol)
The oxygen barrier layer inside almost every long-life food package. Poly(vinyl alcohol) has a superb barrier but dissolves in water; adding ethylene units makes it insoluble and processable while keeping most of the barrier, so the ethylene fraction is a direct trade of barrier against moisture tolerance. It is always buried between polyolefin layers, because humidity destroys its performance. Not drawn: the ratio is the specification.
Ethylene-methacrylic acid ionomer
A polyethylene with a few percent of acid groups, partly neutralised with sodium or zinc. The metal carboxylates cluster into ionic aggregates that act as reversible crosslinks - they stiffen the solid and give it extraordinary cut resistance and elastic recovery, then come apart in the melt so it still processes as a thermoplastic. It is the cover of a golf ball and the seal layer of a food package. Not drawn: acid content and degree of neutralisation are the specification.
Ethylene-propylene rubber
A saturated-backbone rubber with excellent weather and ozone resistance; EPDM adds a small amount of a diene to allow sulfur vulcanization.
Ethylene-vinyl acetate
Vinyl acetate content softens polyethylene into a flexible, rubbery material used in foams, hot-melt adhesives, and film.
Poly(N-ethylmethacrylamide)
A water-soluble methacrylamide close to the boundary of thermoresponsive behaviour; copolymers with the isopropyl monomer tune the LCST across body temperature.
Eumelanin
The pigment of skin, hair and the substantia nigra, and a broadband absorber across the whole ultraviolet and visible range - a property no ordinary chromophore has. The absorption is now attributed to chemical disorder: many slightly different oligomers whose bands overlap into a continuum. Undrawn because that disorder is the structure.
Expanded polystyrene
Polystyrene beads impregnated with pentane, then steamed so the gas expands them and fuses them into a closed-cell foam that is about 98 percent air. Its properties are geometric rather than chemical: thermal conductivity close to still air, compressive strength from the cell walls, and a recycling problem that comes entirely from transporting a material that is mostly nothing. Chemically it is polystyrene, so a structure search finds both; what differs is the foam, not the molecule.
F
Fluoroelastomer
The elastomer used where everything else fails: fuels, hot oils, aggressive chemicals, and continuous service near 200 C. Enough fluorine to be inert, enough comonomer disorder to stay amorphous and rubbery rather than crystallising into a plastic. Its weakness is specific and well known - hot amines and steam attack the vinylidene fluoride units. Not drawn: a random copolymer whose fluorine content is the grade.
H
Poly(1-hexene)
A poly(alpha-olefin) with a butyl branch on every second carbon, which prevents crystallisation entirely - so unlike polyethylene or polypropylene it is an amorphous, tacky material at room temperature. Low-molar-mass versions are the synthetic base oils that have displaced mineral oil in engine lubricants, where a uniform branched hydrocarbon behaves far better with temperature than a distilled fraction.
High-density polyethylene
Polyethylene made with almost no branching, so the chains pack into a crystal that fills about seventy percent of the solid - hence the density, the stiffness and the opacity. The absence of branches is the whole difference from LDPE and it comes entirely from the catalyst, not the monomer. Milk bottles, pipe and chopping boards. Its repeat unit IS polyethylene's, so a structure search finds this alongside the other grades; the branching is what differs and no repeat unit can show it.
High-impact polystyrene
Polystyrene with rubber particles dispersed through it, formed in place by polymerising styrene in dissolved polybutadiene until the phases invert. A crack meeting a rubber particle crazes around it instead of running straight, which multiplies the energy absorbed - the same toughening mechanism as ABS, without the acrylonitrile. It is opaque for the same reason it is tough. Not drawn: a two-phase blend with grafted interfaces.
Poly(N-(2-hydroxyethyl)methacrylamide)
The amide analogue of poly(2-hydroxyethyl methacrylate). Replacing the ester with an amide removes the hydrolysis pathway that slowly releases ethylene glycol from pHEMA hydrogels.
Poly(N-(hydroxymethyl)methacrylamide)
The methacrylamide version of the self-crosslinking methylol monomer; the stiffer backbone raises the temperature at which the cured film softens.
Poly(N-hydroxymethylacrylamide)
The self-crosslinking acrylamide of the coatings industry: on baking, the N-methylol groups condense with each other and with amide N-H to form methylene and ether bridges, releasing formaldehyde and water.
Poly(N-(2-hydroxypropyl)methacrylamide)
The backbone of the HPMA copolymer drug conjugates - the first synthetic polymer-drug conjugates taken into clinical trials. It is water-soluble, non-immunogenic and, unlike the polyesters, not degraded in circulation.
Poly(4-hydroxystyrene)
The backbone of deep-UV photoresists, and the reason modern chips can be patterned at all. The phenol is acidic enough to dissolve in aqueous base, so a protected version - typically the tert-butoxycarbonyl ester - is insoluble until acid generated by the exposing light strips the protecting group, at which point the exposed regions wash away. One photon generates a catalyst that deprotects many units, which is the chemical amplification that made 248 nm lithography sensitive enough to be practical.
I
Poly(indenofluorene)
A partially ladder-type backbone: bridging carbons tie neighbouring phenylenes together so they cannot twist out of plane. Planarising the chain narrows the emission line and raises the fluorescence yield, which is the whole reason to go to the trouble - a twisted polyphenylene emits broadly and inefficiently. Not drawn: I could not fix the parent hydrocarbon's formula independently of my own sketch, so the usual arithmetic check would have proved nothing.
Inverse-vulcanised sulfur polymer
Better than 80 percent elemental sulfur by mass, made by dissolving a vinyl crosslinker directly into molten sulfur above 159 C where the S8 ring opens to a diradical chain. It uses a waste product of petroleum refining that accumulates in open blocks by the million tonnes, and the resulting material binds mercury from water and works as a cathode in lithium-sulfur cells. Undrawn because the sulfur rank between crosslinks is a distribution, not a number.
Poly(isobutyl vinyl ether)
The branched isomer of the butyl ether, some 30 C higher in glass transition for the same atoms - the branch resisting the rotation the straight chain allows. It was also one of the first polymers shown to be made stereoregular by cationic polymerisation at low temperature, which made it a historically important test case for tacticity control.
Polyisobutylene
Amorphous at rest, so only Tg applies in ordinary use; the 44 C melting point in Odian's Table 1-3 is for the strain-crystallised form, which is why a stretched butyl rubber behaves differently from a relaxed one.
Poly(N-isopropyl-N-methylacrylamide)
Methylating the nitrogen of poly(N-isopropylacrylamide) removes the amide N-H entirely. The polymer still has an LCST, which is the standard evidence that the transition does not require inter-chain hydrogen bonding.
Poly(N-isopropylacrylamide)
Best known for its LCST (~32 °C in water), a solution cloud point, not the same property as Tg.
Poly(N-isopropylmethacrylamide)
The alpha-methyl raises the LCST to about 44 C, roughly twelve degrees above poly(N-isopropylacrylamide) - the cleanest illustration that backbone hydrophilicity, not just the side group, sets the transition.
Isotactic polypropylene
Every methyl group on the same side of the chain, which lets the polymer wind into a helix and crystallise - the form that made polypropylene a commodity rather than a curiosity, and the discovery that earned Natta a Nobel Prize. Melting near 165 C with high stiffness. The repeat unit is identical to any other polypropylene; what differs is the arrangement of successive units, which no single repeat unit can show. Searching this structure returns all four polypropylene entries together.
Poly(itaconic acid)
Two carboxylic acids per repeat instead of one, and a monomer made by fermenting sugar rather than from oil - itaconic acid is on every list of priority bio-based platform chemicals. The double acid gives a higher charge density than poly(acrylic acid) and makes it a strong scale inhibitor and dispersant. It polymerises sluggishly because the 1,1-disubstituted alkene is sterically hindered, which is the main reason it has not displaced acrylic acid.
L
Linear low-density polyethylene
Density lowered on purpose rather than by accident: a few percent of butene, hexene or octene puts short branches of controlled length at controlled intervals, with none of the long branching that radical polymerisation creates. The result tears and punctures far less readily than LDPE at the same density, which is why almost all stretch film and heavy sacks are made from it. Not drawn: the comonomer distribution is the design.
Low-density polyethylene
The original polyethylene, made at a few thousand atmospheres by free radicals that periodically bite back onto their own chain - backbiting, which leaves short branches every fifty or so carbons and long ones less often. Those branches block crystallisation, so the material is soft, clear and tough at low temperature: cling film and squeeze bottles. Drawn as polyethylene, because that is what it is: a structure search returns it beside HDPE and UHMWPE, and branching is the difference no repeat unit can show.
M
Macrocyclic bottlebrush
A bottlebrush with no chain ends. The backbone is grown as a macrocycle by ring-expansion polymerisation, then side chains are grown outward from every repeat by atom transfer radical polymerisation, giving molar masses into the megadaltons that can be seen directly as rings by atomic force microscopy. Removing the ends changes real behaviour and not just the drawing: a ring cannot reptate, so it relaxes and diffuses differently from a linear brush of the same mass, and it has no end groups to react or degrade from. Pal, Miao, Garrison, Veige and Sumerlin, Macromolecules 2020, 53, 9717. Structure not drawn: the repeat unit alone cannot express that the backbone closes on itself, which is the whole point of the molecule.
Maleic anhydride grafted polypropylene
Polypropylene with a fraction of a percent of anhydride grafted onto it, and the reason glass-filled and wood-filled polypropylene works at all. The polyolefin cannot wet a polar filler; the anhydride reacts with hydroxyls on glass or cellulose while the chain entangles with the matrix, so it acts as a coupling agent tying two phases that otherwise slide past each other. Not drawn: grafting is sparse and random.
Poly(maleic anhydride)
Maleic anhydride is famously reluctant to homopolymerise - its 1,2-disubstituted double bond is too crowded - so it is nearly always found alternating with styrene or an olefin. Forced to homopolymerise under free-radical conditions it gives only short chains, but hydrolysing them yields a polyelectrolyte with two carboxylates per repeat, among the highest charge densities available on a carbon backbone, used as a scale inhibitor.
Poly(maleic anhydride-alt-1-octadecene)
The same alternating trick as SMA but with a long alkene, giving a comb whose teeth are hydrophobic and whose backbone is reactive anhydride. It is the standard reagent for making inorganic nanocrystals water-dispersible: the alkyl chains interdigitate with the ligands already on the particle and the opened anhydrides face outward as carboxylates. Not drawn: the alkene is supplied as a chain-length distribution.
Metallocene polyethylene
Polyethylene from a catalyst with one kind of active site rather than many, so every chain sees the same environment and the comonomer is distributed evenly instead of concentrating in the shorter chains. Narrower distributions of both length and composition give film that is clearer, stronger and seals at lower temperature. The catalyst, not the chemistry, is the product. Not drawn: distribution is what differs.
Poly(methacrylonitrile)
Poly(3-(methacryloylamino)propyl trimethylammonium chloride)
The amide-linked cationic monomer. Because there is no ester to hydrolyse, it holds its charge in strongly alkaline conditions where the ester quaternaries lose theirs - which is why it dominates in high-pH flocculation and in hair care.
Poly(N-methacryloylmorpholine)
The methacrylamide version of the non-thermoresponsive hydrophilic standard; the stiffer backbone raises Tg without affecting its solubility at any temperature.
Poly(2-methoxy-5-(2-ethylhexyloxy)-p-phenylene vinylene)
The soluble PPV that made polymer LEDs practical to fabricate. Two alkoxy substituents - one small, one branched - keep the conjugated backbone in solution so a device layer can be spin-coated instead of grown from an insoluble precursor. The alkoxy groups also push the emission to orange-red, which is where this polymer is used.
Poly(N-(2-methoxyethyl)acrylamide)
A water-soluble acrylamide with an ether oxygen in place of a hydroxyl, so it hydrates strongly without offering a reactive site.
Poly(N-(methoxymethyl)acrylamide)
The methyl-blocked methylol amide. It deblocks at a lower bake temperature than the butoxy version but releases methanol rather than butanol.
Poly(4-methoxystyrene)
The methoxy group makes the ring strongly electron-rich, which is what matters here: the monomer polymerises readily by cationic initiation where styrene itself is sluggish, and the polymer is easily brominated or nitrated on the ring. It is also acid-cleavable to poly(4-hydroxystyrene), which is why it turns up in resist chemistry.
Poly(methyl cyanoacrylate)
The original superglue, discovered twice by accident while looking for something else - once in a gunsight programme, once in a search for heat-resistant canopies. It is the fastest-setting and strongest of the family and the one least suited to skin: it degrades to formaldehyde and cyanoacetate quickly enough to irritate, which is why the medical grades all use longer esters.
Poly(methyl vinyl ether)
Poly(3-methyl-1-butene)
Branching on the carbon immediately next to the backbone forces the chain into a rigid helix, and the isotactic polymer melts near 300 C - far above polypropylene, from a monomer only two carbons larger. It is the clearest demonstration that a melting point is set by chain stiffness rather than by molecular size, and it is useless in practice because it will not melt-process below its decomposition temperature.
Poly(4-methyl-1-hexene)
A branched alpha-olefin whose side group carries a stereocentre of its own, so the polymer has chirality in the side chain independent of backbone tacticity. It was one of the systems used to establish that optically active polyolefins could be made at all, and remains a model for how side-chain stereochemistry propagates into a crystal.
Poly(4-methyl-1-pentene)
The transparent polyolefin, and the least dense solid commercial polymer at about 0.83 g/cm3. Its bulky isobutyl side group makes the crystal so loosely packed that the crystalline and amorphous phases have nearly the same refractive index, so light passes without scattering at the boundaries - a semicrystalline polymer that is nonetheless clear. It also melts near 235 C, high for a polyolefin, which is why it is used for autoclavable labware and release film.
Poly(N-methyl-N-propylacrylamide)
Another unsymmetrical tertiary acrylamide, more hydrophobic than the ethyl-methyl polymer and correspondingly lower in cloud point.
Poly(N-methylacrylamide)
The smallest N-alkyl acrylamide. It is water-soluble at all temperatures - the LCST behaviour of the acrylamide family only appears once the N-alkyl group is large enough to be genuinely hydrophobic.
Poly(N-methylmethacrylamide)
The simplest N-substituted methacrylamide; the amide N-H and the alpha-methyl together give a Tg well above poly(methyl methacrylate).
Poly(2-methylstyrene)
A methyl in the ortho position, right beside the backbone attachment, which hinders rotation of the ring and pushes the glass transition about 30 C above polystyrene's. Compared with the para isomer, which sits only a few degrees above polystyrene, it isolates how much of a substituent's effect comes from where it sits rather than what it is.
Poly(3-methylstyrene)
The third member of the methylstyrene set, and the one that changes least: a meta methyl neither crowds the backbone the way ortho does nor sits on the symmetry axis the way para does, so the glass transition barely moves from polystyrene's. Useful mainly as the control in that comparison.
Poly(4-methylstyrene)
Poly(alpha-methylstyrene)
Poly(4-methylstyrene-co-styrene)
A copolymer used mainly as a model system: the two monomers are so similar that they copolymerise almost ideally, with reactivity ratios close to one, so the composition of the chain tracks the feed exactly. That makes it the reference case against which non-ideal copolymerisations are measured. Not drawn: the composition is the variable of interest.
N
Nafion
The membrane in essentially every proton-exchange fuel cell and chlor-alkali cell. A PTFE backbone carries perfluoroether side chains ending in sulfonic acid; the fluorocarbon and the acid cannot mix, so the sulfonates cluster into water-filled channels a few nanometres across that conduct protons while the backbone keeps the film mechanically and chemically intact. Not drawn: a random copolymer whose equivalent weight is the specification.
O
Poly(octadecyl vinyl ether)
The far end of the vinyl ether series, where the eighteen-carbon side chains crystallise independently of the backbone and the polymer melts near 50 C. It behaves as a wax rather than a rubber, and the transition it shows is the side chains melting - the backbone plays almost no part, which is the general behaviour of comb polymers past about twelve carbons.
Poly(1-octene)
The next term in the alpha-olefin series and the one most used commercially, oligomerised rather than polymerised to give the polyalphaolefin base stocks of synthetic engine oil. The hexyl branch keeps it liquid and its viscosity changes far less with temperature than a petroleum fraction of the same viscosity - which is the entire commercial argument for synthetic oil.
Poly(octyl cyanoacrylate)
The topical skin adhesive that replaced sutures for clean wound closure. Lengthening the ester to eight carbons slows hydrolysis enough that the formaldehyde released stays below the threshold that inflames tissue, and it plasticises the film so the glue flexes with the skin instead of cracking off it.
Poly(N-octylacrylamide)
A hydrophobic acrylamide used as the associating comonomer in hydrophobically modified water-soluble polymers, where the octyl groups form micellar junctions that thicken the solution.
Poly(N-tert-octylacrylamide)
A hindered, highly hydrophobic acrylamide with a high glass transition, used as the hard comonomer in hair fixative resins where the amide supplies substantivity and the bulky alkyl supplies stiffness.
P
Parylene C
The workhorse of the parylene family. One chlorine per ring roughly halves the permeability to water vapour and gases compared with parylene N, at some cost in deposition rate, which is exactly the trade wanted for a moisture barrier over electronics. It is the grade used on implantable devices and on the boards inside things that must not corrode.
Parylene N
A coating deposited from the vapour with no solvent and no liquid stage at all: the cyclophane dimer is pyrolysed to a reactive quinodimethane that polymerises on contact with any surface in the chamber. Because it grows a molecule at a time it covers sharp edges and creeps into crevices that no liquid coating would reach, which is why it protects circuit boards and implanted electronics.
Poly(pentafluorostyrene)
Polystyrene with every ring hydrogen replaced by fluorine, which inverts the ring's electronics: the electron-poor ring stacks face to face with ordinary electron-rich aromatics rather than edge to face, and the para fluorine is activated toward substitution by thiols. That second point is the useful one - the polymer is a post-polymerisation modification platform where one reaction installs almost any functional group on a well-defined backbone.
Perfluoroalkoxy alkane
PTFE that can be melt-processed. A small fraction of a perfluoroalkyl vinyl ether comonomer puts flexible ether branches along the chain, which lowers the melt viscosity enough to injection-mould and extrude while keeping essentially all of PTFE's chemical inertness and its service temperature near 260 C. That is the whole reason it exists: PTFE itself does not flow even above its melting point and has to be sintered like a ceramic. The drawn unit shows one branch point in context, not the true comonomer ratio.
Perfluoroelastomer
Every hydrogen replaced, so it has essentially PTFE's chemical resistance while remaining an elastomer - the perfluoroether comonomer is what keeps it from crystallising. It seals semiconductor process chambers and chemical reactors where any other elastomer would be consumed, at a price per O-ring that reflects how hard the cure chemistry is when there are no ordinary reactive groups anywhere in the polymer. Not drawn: a random copolymer with a small cure-site fraction.
Poly(phenylacetylene)
A substituted polyacetylene, and unlike the parent it is soluble and air-stable because the phenyl rings twist the backbone out of full conjugation - which costs conductivity and buys a material that can actually be handled. Its interest now is chirality: with the right catalyst the chain adopts a single-handed helix, giving an optically active polymer from an achiral monomer.
Poly(N-phenylacrylamide)
An aromatic acrylamide. Conjugation between the ring and the amide reduces the nitrogen's hydrogen-bond donation, so it behaves less like an amide than its structure suggests.
Poly(p-phenylene vinylene)
The polymer that made light-emitting devices from plastic plausible. Alternating rings and vinylenes conjugate along the chain and the band gap lands in the visible, so a film between electrodes electroluminesces - the 1990 result that opened polymer LEDs. Unsubstituted PPV is insoluble and is made through a soluble precursor that is cast and then eliminated to the conjugated form in place, which is a recurring trick for conjugated polymers.
Poly(N-phenylmethacrylamide)
A rigid aromatic methacrylamide. The combination of amide hydrogen bonding and an aryl group on nitrogen gives one of the highest Tg values in the acrylic family.
Poly(alpha-pinene) resin
A tackifying resin from turpentine, made by cationic polymerisation. The bicyclic monomer rearranges as it adds - the strained four-membered ring opens under the carbocation - so the product is a mixture of rearranged units rather than a single repeating structure, which is why no structure is drawn. It is the resin that gives natural-rubber pressure-sensitive adhesives their grab.
Poly(N-propylacrylamide)
The linear C3 isomer of poly(N-isopropylacrylamide), with an LCST near 22 C - about ten degrees below the branched isomer, showing that the transition responds to side-chain shape as well as size.
Polypropylene
The melting point here is for ordinary commercial isotactic PP; Odian's Table 1-3 gives 176 °C, which is closer to the perfectly isotactic crystal than to a moulding grade. The glass transition moves with tacticity too — that table quotes −1 °C against the −10 °C here.
Polypropylene impact copolymer
Not a block copolymer despite the name, but a rubber phase grown inside the polypropylene particle in a second reactor - so the toughening rubber is dispersed at a scale no melt blending achieves. It keeps polypropylene serviceable well below zero, which is why bumpers and battery cases are made from it. Not drawn: a reactor blend with two phases.
Polypropylene random copolymer
A few percent of ethylene distributed randomly along a propylene chain, which interrupts the crystal just enough to improve clarity and low-temperature toughness while lowering the melting point. It is the standard material for hot and cold water pipe, where the balance between pressure rating and brittleness in the cold decides everything. Not drawn: the comonomer distribution is the specification.
Poly(N-propylmethacrylamide)
The linear C3 methacrylamide, the counterpart to poly(N-propylacrylamide) with its cloud point shifted upwards by the alpha-methyl.
S
Poly(sodium 4-styrenesulfonate)
The standard strong polyanion. The sulfonate is fully ionised at any usable pH, so charge density does not depend on pH the way a carboxylate's does, which is why it is the reference polyanion for layer-by-layer assembly, for polyelectrolyte complexes and as the counter-ion that carries PEDOT into water. Drawn here as the free acid; it is normally handled as the sodium salt.
Poly(sodium vinyl sulfonate)
The shortest strong polyacid there is - a sulfonate bonded straight to the backbone with no spacer. That gives the highest charge density per gram of any common vinyl polyelectrolyte, though the same crowding makes the monomer polymerise reluctantly to low molar mass. Used where charge density matters more than chain length, in scale control and as a proton conductor. Drawn as the free acid.
Polystyrene
Ordinary atactic PS is amorphous, so only Tg applies; the 250 °C melting point in Odian's Table 1-3 is for the crystalline (stereoregular) form.
Poly(styrene-alt-maleic anhydride)
Maleic anhydride will not homopolymerise but alternates almost perfectly with styrene, so the composition is fixed by the chemistry rather than by the feed. The anhydride opens with amines or alcohols to give acids and half-esters, which is how the polymer becomes a dispersant, and hydrolysed SMA is the reagent that extracts membrane proteins into native nanodiscs without detergent.
Poly(styrene-b-ethylene oxide-b-styrene)
A triblock with a water-soluble middle and glassy ends, which in water gives a physically crosslinked hydrogel rather than micelles - the polystyrene blocks aggregate and the PEO bridges between aggregates. It is the amphiphilic counterpart of the styrenic thermoplastic elastomers, and a standard model for how block sequence changes assembly. Not drawn: a block copolymer.
Poly(styrene-co-acrylonitrile)
A rigid, transparent, solvent-resistant copolymer; the acrylonitrile raises chemical resistance and stiffness over polystyrene.
Poly(styrene-co-divinylbenzene)
The bead that solid-phase synthesis and ion exchange are built on. Suspension polymerisation gives spheres whose crosslink density controls everything: lightly crosslinked gel beads swell and let reagents reach the interior, heavily crosslinked macroporous ones keep a permanent pore structure and do not. Merrifield's peptide synthesis and every water softener use one or the other. Not drawn: a crosslinked network.
Styrene-maleic anhydride imide
Alternating styrene-maleic anhydride with the anhydride converted to an imide, which raises the glass transition well above 200 C while keeping the polymer melt-processable. It is blended into ABS and polycarbonate to raise their heat distortion temperature - a heat-resistance additive that happens to be a polymer. Not drawn: imidisation is partial and the amine varies.
Poly(sulfur nitride)
A polymer containing no carbon at all, alternating sulfur and nitrogen, and the first polymer found to conduct like a metal - and then, below 0.3 K, to superconduct. It was the result that made a metallic polymer conceivable and set the stage for doped polyacetylene a few years later. It is also shock-sensitive and decomposes slowly at room temperature, so it remains a landmark rather than a material. Not drawn: an inorganic backbone outside this library's element set.
Syndiotactic polypropylene
Methyl groups alternating regularly from side to side, which also crystallises but into a different lattice - and the result is clearer, tougher and more elastic than the isotactic form, if lower melting. It could not be made with useful control until metallocene catalysts arrived, which is why it is decades younger than its isotactic sibling despite being just as regular. Same repeat unit, same connectivity; the regularity is in how one unit follows the next.
Synthetic mucin mimic
What happens when the natural bottlebrush lubricants are copied rather than harvested. Mucin and lubricin both work by holding a water layer on a surface and refusing to interdigitate with the layer opposite, and both are hard to produce in quantity with consistent glycosylation. A synthetic version keeps the architecture - a hydrophilic, often charged brush with an end group that binds the surface - and drops the sugars for something easier to make, which is enough to recover much of the lubrication. Reported mimics are used on cartilage, contact lenses and antifouling coatings, sometimes paired with a surface-binding protein to improve wear protection. The composition is deliberately open here: this is an architecture with a design brief, not one compound.
T
Polytetrafluoroethylene
Multiple sub-ambient and near-ambient transitions are reported instead of a single clean Tg. Standard handbook tables (Brandrup, Odian's Table 1-3) nonetheless quote a Tg near 117 °C.
Poly(tetrafluoroethylene-alt-propylene)
The one fluoroelastomer that survives strong base and steam, because it has no vinylidene fluoride and therefore no acidic hydrogen for a base to abstract - the dehydrofluorination that destroys ordinary FKM in amine-treated oilfield fluids. It is standard for downhole seals, and its electrical insulation is good enough for oilfield cable jacketing.
Poly(tetrafluoroethylene-co-hexafluoropropylene)
The first melt-processable relative of PTFE. Hexafluoropropylene puts a trifluoromethyl branch on the chain often enough to stop the crystal packing, so the polymer flows and can be extruded as wire insulation and heat-shrink tubing - at the cost of a service temperature about sixty degrees below PTFE's. Not drawn: a random copolymer whose comonomer ratio is the design.
THV fluoroterpolymer
The softest and lowest-melting of the melt-processable fluoropolymers, and the only one that bonds to hydrocarbon elastomers without surface treatment - which is why fuel hose has a THV liner inside a rubber cover. No single structure is drawn because the three monomers are placed at random and the ratio, not the connectivity, is what distinguishes one grade from another.
U
Ultra-high-molecular-weight polyethylene
The same molecule as HDPE taken to several million grams per mole, at which point the chains are so entangled that the melt will not flow at all and parts are sintered rather than moulded. Those entanglements give abrasion resistance beyond any other thermoplastic and, when gel-spun into aligned fibre, a specific strength greater than steel. It is the bearing surface of most hip and knee replacements. Drawn as polyethylene, since chain length rather than structure is what defines it; a structure search finds it with the other grades.
V
Poly(vinyl acetate)
Poly(vinyl alcohol)
Poly(vinyl alcohol) high-tenacity fibre
Poly(vinyl alcohol) drawn into a fibre and then surface-acetalised with formaldehyde so it does not dissolve in hot water. It was developed in Japan as a cotton substitute when petrochemical feedstocks were unavailable, and survives as the fibre used to reinforce cement, where its alkali resistance beats the alternatives. Drawn as poly(vinyl alcohol), since processing and surface treatment define it rather than a different repeat unit.
Poly(vinyl alcohol-co-vinyl acetate)
Poly(vinyl alcohol) is never made from vinyl alcohol, which does not exist as a stable monomer - it is made by hydrolysing poly(vinyl acetate), and how far that hydrolysis is taken is the specification. Fully hydrolysed grades crystallise and need hot water to dissolve; leaving twelve percent of the acetate on disrupts the crystal enough to dissolve cold. Not drawn: the residual acetate is the point.
Poly(vinyl benzoate)
The aromatic member of the vinyl ester family, and far stiffer than the aliphatic ones - the glass transition rises to about 70 C where poly(vinyl acetate) sits near 30. It also serves as an alternative protected precursor to poly(vinyl alcohol) when the acetate route's transesterification chemistry is inconvenient.
Poly(vinyl butyl ether)
A member of the poly(alkyl vinyl ether) series, all of which are made cationically because the electron-rich alkene will not polymerise by radicals. Its glass transition sits around -55 C, and the series from methyl through butyl to octadecyl is a clean demonstration of side-chain length lowering the transition until the chains become long enough to crystallise.
Poly(vinyl butyral)
The interlayer in laminated safety glass, and the reason a windscreen holds together after it cracks. The same acetal chemistry as the formal, but with a propyl group hanging off each ring, which keeps the polymer soft and enormously tough while retaining enough residual hydroxyl to bond tightly to glass. Commercial material is deliberately incompletely reacted: the leftover alcohol groups are what stick to the glass, so the degree of acetalisation is specified rather than maximised.
Poly(vinyl butyrate)
Poly(vinyl acetate) with a longer acyl group, which pushes the glass transition down by roughly 50 C - the ester acts as a built-in plasticiser. It is useful mostly as a term in the series: comparing the vinyl esters from acetate through propionate to butyrate isolates the effect of side-group length on chain packing with everything else held constant. Not to be confused with poly(vinyl butyral), the acetal used in laminated glass.
Poly(vinyl carbazole)
The first photoconductive polymer, and the material that made electrophotography a polymer technology. The carbazole side group is electron-rich and transports positive charge by hopping from one ring to the next, so a doped film discharges where light strikes it - the basis of the photoreceptor drum in a photocopier. It survives in organic LEDs as a hole-transport layer and as a wide-gap host.
Poly(vinyl chloride)
Commercial PVC is nearly amorphous (only slight crystallinity), so it is used for its Tg; the 273 °C melting point in Odian's Table 1-3 is for the crystalline form.
Poly(vinyl chloroacetate)
Poly(vinyl acetate) with a chlorine on the acetyl methyl, which turns an inert ester into an alkylating handle: the chloride displaces with amines or azide to give functional polymers, and the ester still hydrolyses to poly(vinyl alcohol) if that is wanted instead. Two independent chemistries on one repeat unit.
Poly(vinyl cinnamate)
The first practical negative photoresist, and still a textbook example of photocrosslinking. Cinnamate double bonds on neighbouring chains undergo a two-plus-two cycloaddition under ultraviolet, tying the chains into a network wherever light falls, so the exposed regions become insoluble. It patterned printed circuit boards for decades before chemically amplified resists arrived.
Poly(vinyl ferrocene)
A polystyrene-like backbone carrying a ferrocene on every repeat, giving a polymer with a clean, fully reversible one-electron redox couple at an accessible potential. That makes it the standard redox-active polymer for modified electrodes and, more recently, for the organic redox-flow batteries that avoid vanadium. Not drawn: iron sits outside the element set this library draws.
Poly(vinyl fluoride)
Handbook values for the glass transition disagree sharply: Odian's Table 1-3 quotes 41 °C where this entry carries −20 °C. PVF is about half crystalline and shows more than one relaxation, so the two numbers come from different assignments rather than from one of them being wrong. Treat either as approximate and say which you used.
Poly(vinyl formal)
Poly(vinyl alcohol) whose hydroxyls have been paired up into six-membered acetal rings by formaldehyde. Closing the rings removes the hydrogen bonding that makes PVA water-soluble and intractable, leaving a tough film-former that is the classic support film for transmission electron microscopy grids and, mixed with a phenolic, the enamel on magnet wire.
Poly(vinyl formate)
The smallest possible vinyl ester, and a route to poly(vinyl alcohol) that hydrolyses under far milder conditions than poly(vinyl acetate) needs. It also leaves no acetate residue, which matters when the alcohol is destined for a use where the residual ester groups would show up as a defect.
Poly(vinyl laurate)
A vinyl ester with a twelve-carbon tail, internally plasticised so far that it is tacky at room temperature. Copolymerised with vinyl acetate it lowers the film-forming temperature of an emulsion paint without any added plasticiser to migrate out later, which is the whole argument for using it.
Poly(vinyl methyl ether-alt-maleic anhydride)
Another perfectly alternating anhydride copolymer, and the polymer in denture adhesive and many toothpastes. The anhydride opens in water to a dicarboxylic acid that binds calcium and sticks tenaciously to mucosa and to tooth mineral; in its ester forms it is the film former in hairspray, where the acid groups let it be washed out again.
Poly(vinyl methyl ketone)
Poly(vinyl pivalate)
The bulky tert-butyl group beside the ester makes this polymerise with unusually few head-to-head placements and very little chain transfer to polymer, so it gives the most stereoregular and least branched precursor to poly(vinyl alcohol). Hydrolysing it yields a PVA of higher crystallinity and strength than the usual acetate route can reach - which is how high-tenacity PVA fibre is made.
Poly(vinyl propionate)
Poly(vinyl stearate)
A vinyl ester with an eighteen-carbon tail, long enough that the side chains crystallise among themselves independently of the backbone. That side-chain crystallisation gives a sharp melting transition near 45 C that has nothing to do with the main chain - the basis of comb-like phase change materials and of pour-point depressants for waxy oils.
Poly(vinyl trifluoroacetate)
A vinyl ester whose acyl group is electron-poor enough that the ester hydrolyses under far milder conditions than acetate - mild enough to convert to poly(vinyl alcohol) without the alkaline treatment that degrades sensitive block copolymers. It is used chiefly as that protecting group rather than for its own properties.
Poly(vinyl versatate)
A vinyl ester of a branched acid whose carboxyl carbon carries no hydrogen at all, so the ester is shielded from hydrolysis by pure steric bulk. Copolymerised with vinyl acetate it is what lets an emulsion paint survive on an exterior wall, where plain poly(vinyl acetate) would slowly saponify in alkaline masonry.
Poly(N-vinylacetamide)
A secondary amide on the backbone, so unlike poly(N-vinylpyrrolidone) it has an N-H to donate hydrogen bonds. It is water-soluble at all temperatures with no cloud point, extremely hydrophilic, and hydrolyses to poly(vinylamine) under forcing conditions - which is how that polycation is usually reached.
Poly(vinylamine)
The amine directly on the backbone rather than on a pendant arm, which gives a higher charge density than poly(allylamine) at the same mass. Vinylamine itself does not exist as a stable monomer - it tautomerises to acetaldimine - so the polymer is made by polymerising N-vinylformamide and hydrolysing off the formyl groups afterwards, which means the product is really a copolymer with whatever amide survived.
Poly(4-vinylbenzyl chloride)
The benzylic chloride is reactive enough to be displaced by almost any nucleophile at mild temperature, which makes this the standard platform for post-polymerisation modification. Quaternise it with a tertiary amine and it becomes an anion-exchange membrane; treat it with a phosphine, an azide or a thiolate and it becomes whatever else was wanted.
Poly(vinylbenzyl trimethylammonium chloride)
The anion-exchange counterpart to poly(styrene sulfonate), made by quaternising poly(vinylbenzyl chloride). Permanently charged whatever the pH, which is what an anion-exchange membrane needs - though the benzylic quaternary ammonium is its own weakness, degrading by Hofmann elimination in the hot alkali of a fuel cell. Drawn as the cation; the chloride is not shown.
Poly(4-vinylbiphenyl)
Two rings in a row rather than fused, so the pendant group is long and can rotate about the bond between them. That gives a glass transition near 145 C and a very high refractive index, and the twist between rings makes the polymer a useful host for phosphorescent emitters, where a rigid but non-planar spacer keeps the triplet energy high.
Poly(N-vinylcaprolactam)
Poly(vinylcyclohexane)
Polystyrene with the aromatic ring hydrogenated to cyclohexane, made that way because vinylcyclohexane itself polymerises poorly. Removing the aromaticity raises the glass transition slightly and removes ultraviolet absorption entirely, giving an optically transparent glassy polymer with no chromophore - and it is the standard hydrogenated block in saturated styrenic block copolymers.
Poly(vinylene carbonate)
Better known as the additive than the polymer: vinylene carbonate is added at a percent or two to lithium-ion electrolytes, where it reduces on the anode before the solvent does and polymerises into exactly this film. That film is the solid-electrolyte interphase - it passivates the graphite, stops further solvent decomposition, and is most of the reason a cell survives hundreds of cycles.
Poly(vinylene fluoride)
A conjugation-free fluorinated backbone with a double bond in every repeat, which makes it unlike the saturated fluoropolymers: the alkene is a site for addition chemistry and for crosslinking that PTFE and PVDF simply do not offer. It is a research material rather than a commercial one, studied for how backbone unsaturation changes a fluoropolymer's dielectric behaviour.
Poly(N-vinylformamide)
Poly(vinylidene chloride)
Odian's Table 1-3 gives 200 °C for the melt against the 190 °C here; the two glass transitions agree. PVDC decomposes close to its melting point, so measured values depend on how fast the scan was run.
Poly(vinylidene cyanide)
Two nitriles on the same carbon give one of the largest dipole moments per repeat of any polymer, which is why its copolymers with vinyl acetate are studied as piezoelectric films that need no poling stretch the way PVDF does. The monomer is violently reactive toward any nucleophile, including water and amines, so it has to be handled dry and is polymerised anionically almost on contact.
Poly(vinylidene fluoride)
Odian's Table 1-3 quotes 185 °C for the melting point against the 170 °C here. PVDF is polymorphic — the α, β and γ crystal forms melt at different temperatures — so a single figure is always a simplification of which phase was measured.
Poly(vinylidene fluoride-co-hexafluoropropylene)
PVDF with enough hexafluoropropylene copolymerised in to break up its crystallinity. The result keeps the chemical and electrochemical resistance of the fluoropolymer but becomes flexible and soluble, which is why it is the standard binder and gel-electrolyte host in lithium batteries rather than PVDF itself. Higher HFP content takes it from a tough plastic to a true fluoroelastomer. Not drawn as one repeat: it is a random copolymer whose properties are set by the comonomer ratio, so a single unit would misrepresent it.
Poly(vinylidene fluoride-co-trifluoroethylene)
The ferroelectric polymer that does not need stretching. Plain PVDF only becomes piezoelectric after mechanical drawing forces it into the polar beta phase; adding trifluoroethylene makes that phase form on its own from the melt, so a spin-coated film is piezoelectric as cast. That is what makes flexible printed sensors and ultrasound transducers practical. Not drawn: the comonomer ratio sets the Curie temperature.
Poly(N-vinylimidazole)
A weak polybase that buffers around pH 6, the same imidazole that does the job in histidine. That pKa sits in the endosomal range, so it is used to add proton-sponge behaviour to a delivery vehicle, and the free nitrogen also coordinates metals, which makes it a polymeric ligand for catalysis and for metal capture.
Poly(vinylimidazolium)
An ionic liquid with its cation tied into a chain - a poly(ionic liquid). Fixing the cation leaves only the anion mobile, which is what makes these useful as single-ion conductors and as anion-exchange membranes, and swapping the anion changes solubility and thermal behaviour without touching the backbone. Drawn as the cation; the counter-ion is not shown.
Poly(2-vinylnaphthalene)
Polystyrene with a second fused ring, which raises the glass transition to about 150 C and the refractive index above 1.68 - high for an all-hydrocarbon polymer. The naphthalene also forms excimers between neighbouring side groups, so its fluorescence reports on how close the chain segments are, which made it a standard probe for chain conformation and for miscibility in blends.
Poly(4-vinylphenylboronic acid)
Boronic acids form reversible cyclic esters with any adjacent pair of hydroxyls, which means this polymer binds sugars - and binds glucose in proportion to its concentration. That is the basis of the synthetic glucose-responsive insulin depot: as blood sugar rises it displaces the crosslinks and the gel releases its cargo. Making the response fast enough at physiological pH is the standing difficulty.
Poly(vinylphosphonic acid)
A polyacid with two ionisable protons per repeat and two well-separated pKa values, so its charge climbs in two steps rather than one. Phosphonates also bind calcium and metal oxide surfaces far more strongly than carboxylates, which is why the polymer is used as a scale inhibitor, a bone-targeting group and an adhesion promoter on metal.
Poly(4-vinylpyridine N-oxide)
The N-oxide is a zwitterion at the ring nitrogen, giving a strongly polar, water-soluble polymer that is neither acid nor base. Its historical interest is medical: it was shown to protect lung cells from silica dust by binding to the particle surface ahead of the cell membrane, one of the earliest polymer treatments proposed for silicosis.
Poly(2-vinylpyridine)
The ring nitrogen makes it pH-responsive and metal-coordinating; a common block-copolymer segment.
Poly(4-vinylpyridine)
Poly(2-vinylpyridinium)
Poly(2-vinylpyridine) with the ring nitrogen alkylated, converting a weak base whose charge depends on pH into a permanently charged polycation. Quaternising a block copolymer's pyridine block is a standard route to an amphiphile that cannot lose its charge, used for micelles that must survive the pH changes inside a cell.
Poly(N-vinylpyrrolidone)
Poly(vinyltoluene)
The industrial material behind the methylstyrenes: commercial vinyltoluene is a mixture of the meta and para isomers because separating them is not worth the cost. The mixture is deliberately useful - the isomer distribution frustrates crystallisation and gives a slightly higher glass transition than polystyrene at a similar price. Not drawn: it is an isomer mixture, not one structure.