Polylactic Acid (PLA)- A polydisperse trail of tears.

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Many hearts have been broken in the attempt to get PLA on the market. In my case, I bailed from a tenure track asst prof slot to join a startup planning to scale up PLA production. It was quite exciting for a year and then it went belly up. These days, I’m a bit more cautious. I’m not bitter about it. It was a good introduction to polymer science and the marvels of chemical engineering.

In response to a question about PLA, I thought I’d elaborate on it a bit.

I’d be curious to find out more about the PLA experience, particularly the timing.  PLA is certainly a big hit right now.  Natureworks is sold out, and it has also found some niche applications – surgical staples for instance.   

The problem seems to be that if you develop the polymer first and the application second, then you will have a difficult sell.  If you go the other direction, it is an easy sell but you are left with lots of little applications.

Whereas we failed with PLA, Dow Cargill LLC has apparently turned it into an ongoing product called NatureWorks.

In case you haven’t heard, PLA is polylactic acid.  In its most common manifestation, it is the homopolymer of what is designated as the L enantiomer, which is produced from fermentation. Out of respect for my colleagues I won’t name the now defunct startup company.

Most everyone agrees that the marketing appeal of PLA is that it will biodegrade in the environment all the way to carbon dioxide and water, at least in principle. I qualify this assertion because it has been found that this biodegradation requires a fair amount of moisture to progress in a reasonable time. Landfills can be dry, fetid heaps that are not automatically conducive to rapid breakdown of organic materials. At least on the timescale of a few decades.  

In the microbial world, many microorganisms have the enzymatic machinery to biodegrade PLA to lactic acid (LA) and beyond.  LA is a natural compound that is judged to have a benign fate in the environment because it is such a common metabolite. In principle LA could be fully metabolized to CO2 and water once it is depolymerized from the PLA. So went the sales pitch.

In the 1990’s, people were concerned that landfills were rapidly filling to the brim with smelly disposable diapers and plastic junk.  There seems to be less public debate on this today, but I assume that the landfill issue remains largely unresolved.

PLA is made by an esterification reaction called ROP- ring opening polymerization. PLA is not made directly from LA. It is made from the ring opening polymerization of lactide, the cyclodimer of LA. This way there is no evolved water to add reversability to the polymerization.  And lactide is quite reactive.  Initiation of this highly strained monomer can be started with an initiator like an alcohol or an HO-terminated polyether in the presence of a Lewis acid catalyst (tin (II) octoate) in the lactide melt phase.

Lactide can be made by the direct cyclodimerization of lactic acid or by a back-biting reaction of oligomeric PLA made by heating LA.  I don’t know for sure, but I think that the back-biting reaction may be the major route to lactide today.

There is a lot of IP out there covering specialized applications of PLA. Medical and dental implants, sutures, timed released chemotherapy, etc.  PLA will slowly come apart in vivo over time, so it can serve as a kind of scaffold for bone or tissue regrowth or for metered drug release.  But this is a small and specialized market.

The big money is in packaging materials- blown films in particular. However, there are technical challenges here owing to a few of the properties of PLA homopolymer.  PLA has a relatively high Tg, so films will rattle and sharp package corners will crack.  PLA’s crystallinity can be good or bad depending on the application.  PLA also has a tendency to have an amber color and it’s films can block. 

Commodity polymer films have to be dirt cheap. The premium films  are colorless and low haze, have a high gloss, and have a low Tg.  There is a whole industry already producing such premium material from inexpensive feedstocks- the polyolefin industry. Sometimes people parse polystyrene and polyvinyl chloride as industries distinct from polyethylene and polypropylene. Polyethylene, polypropylene, polystyrene, and polyvinyl chloride are the predominant synthetic polymer feedstocks used by the packaging industry. They are well dug into the market with established feedstock supply lines and a global presence. 

Enter PLA.  PLA is ultimately a fermentation product. To get the right tacticity, you need enantiomerically pure LA. The best way to get it is to ferment sugars. LA must be fermented from a carbohydrate source, isolated from the broth (!!), converted to lactide, and polymerized.  Fermentation is a low space yield process. The microbes must be kept alive- excessive LA will kill them owing to low pH. You’ll need a cheap source of carbohydrates.

One of the best sources is corn starch, so a big corn wet mill will be required to produce it. The economics of PLA requires that a producer be vertically integrated from starch to fermentation to monomer production to polymerization. Energy and corn prices will have a large impact on your economics.

I’ll spare you the details going forward. Suffice it to say that PLA can’t compete with polyolefins on a price per pound basis at the present time.   PLA is boutique polymer at best for the forseeable future. My former company, the defunct PLA startup, felt that the best market segment for PLA was the market occupied by nylon films, due to the comparable cost and food contact and barrier properties. I have no idea what the economics look like now, 10 years later.

I wish all of the players well in the PLA business. It is a worthwhile endeavor and I wish that my experience had turned out differently. So it goes.

For an updated post on PLA, follow this link.

     

 

 

Startups and the elusive spondulix

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In the previous post I poured on the platitudes regarding working for a large company. Today I write about the other end of the spectrum- The startup company.

I encounter startup companies frequently in my work. Since I am not in the pharma business or fabulous biotech, my exposure to startups is limited to specialty and fine chemical feedstocks or reagents.

When you start a chemical company, it is assumed that you want to make lots of money. It turns out that you must have considerable cash flow just to pay the expenses of being in business, so you must be focused on cash flow. Chemical companies can have fairly high overhead costs, partly due to expensive staff (chemists and business managers) and partly due to the unique and expensive requirements of the physical plant.

Starting a chemical company is not a task for the timid.  You have lots of strikes against you from the very start. You see, a company is like a big angry animal. It has to be fed constantly with generous inputs of cash. Cash is King. Remember that. It’s all about the elusive spondulix. Investors can either give their money to Warren Buffett or to you.

I have seen many startups devolve into smoldering, groaning trainwrecks. Fortunes are lost, litigations burn like the fires of Mordor, and careers are lost or at least seriously stunted. Certainly no one starts a company with the intent of crashing it. So, how does it happen?

Usually, they run out of cash. There are many reasons that people use to justify the startup of a company. What they all have in common is the unwavering certainty that people will throw money at what they hope to offer. And if they have a patent- Lordy.  Nothing is meaner than an inventor in the thoes of patent sickness trying desperately to revive a dead one-act pony.

Many people start up a company with a one-act pony.  That is to say, a patented technology based on a highly specialized material or a process.  There are several ways to put a one-act pony or technology to work.  You can license out the technology. You can make certain compositions for sale. Or, you can make the pony do it’s one trick. 

If the pony’s one trick is good but not spectacular, selling licenses may be difficult. It is expensive and risky to upgrade technologies. There has to be a clear advantage and fairly rapid return on investment for the licensee.

If the materials made by the technology are “Me Too” products that are adequate but not exciting, you’re in for tough sledding. Especially if they’re commodities.  Companies in the polymer business know this. It is fantastically hard to get a new polymer to catch on in the market. Even giant companies have a hard go of it with exceptional products. The polymers market isn’t expanding very fast, so if you want market share, you have to take it based on price. Then it is a race to the bottom of the lake.

I was once roadkill along the trail of tears called PLA- Polylactic Acid.  It’s a great polymer for numerous applications. But low MW and the tendency to turn amber were problems that eventally caused us to flame out like a North Korean missile.

I’ve seen a lot of one-act pony startups fail because the pony died.  A startup may fail because show stoppers appeared that couldn’t be fixed, or the demand didn’t pan out. 

If you’re going to start a company, it is desirable to get cash flow going as soon as possible.  Use a plow horse to get some cash flow while you’re training the new pony.  Let existing products pay for the development of new technologies.  Learn how to make or formulate niche products that no one else is interested in. Plow the money back into product development and get into advanced technologies that way. Minimally, you’ll get to retain more of the ownership.

Another reason to build a business this way is to try to stay away from venture capitalists. But that is for another day.

Post post graduate

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Making the transition from grad school to industry is a big deal.  Most people dive into the embracing bosom of a large company. A few choose the riskier startups. 

Large organizations have something called infrastructure.  This is truly a fabulous concept. The hireling lands on an organizational sleep number mattress where all of the necessary bureaucratic mechanisms are in place. Job descriptions are etched in the finest Italian marble and loving administrative assistants sing their sweet, tender songs of service to you like the Sirens on the rocks of Scylla. Your company credit card arrives in the mail one day and you sit there imagining the possibilities.

And lo! For the first few years life is grand. You become accustomed to the benefits package and the commute. Your responsibilities become clear. You forge alliances and carefully note the treacherous characters. Your spouse finds work and you sign a mortgage. Your lunchtime conversations are discussions of local school districts and churches and mill levees. Older relatives will begin to die of old age and you’ll be attending funerals.

Then the economy stalls or your companies blockbuster drug is found to have unexpected mortalities. Management announces that there is a hiring freeze and restraints are placed on spending.  Then one friday morning it is announced that there will be downsizing.  They’ll say that they hope to accomplish it with early retirements and attrition.  A few months pass and then they’ll announce a restructuring or continued downsizing. You find yourself looking at the ads in C&EN with increased interest.

But it could just as easily go the other way. Your team could produce a new class of compounds that turn the business on its head.  You could find yourself on a horse giving you the ride of your life. Your group could find itself keeping teams of patent lawyers busy writing Markush claims covering thousands of molecular permutations.

On this ride, you could be involved in scaleup with engineers asking questions about space yields, calorimetry, side products, and all manner of process improvements.

There is a great deal of luck involved in any successful project. I know people who have participated in or lead actual paradigm shifts in chemical technology. I can’t mention their names. Believe me, they are very talented people. But they are talented participants in a field of talented people.  Their personal successful outcome also had a large dollop of luck in the making. They were at the right company in the right time interval.

At conferences they’ll strut around like roosters, and that is OK. They genuinely deserve their time in the spotlight. But they know, like you do, that you’re only as good as your last accomplishment.  In the end, few of us have much control of anything.  Whether you reach the highest achievement or you plod on in anonymity, your fate is largely woven into the web of commerce.

Atomic Bob and his Gravity A-Waves

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Imagine my surprise when I look a little deeper into United Nuclear and find that its founder is none other than Bob Lazar.  In the previous post I mildly endorsed United Nuclear as a supplier of low level radioactive sources for experimentation. They appear to be a legitimate supplier of safe to handle sources. I haven’t changed my mind about the need for such suppliers but I am cautious about their grasp of physics.

It turns out that Bob Lazar has quite a reputation in certain circles concerned with extraterrestrial visitors. Lazar does get quite a bit of airplay.  Just this morning while in a groggy half sleep I heard Lazar interviewed on a UFO program on the Travel Channel.

It turns out that Bob Lazar claims to be a nuclear physicist and claims to have been involved in work aimed at understanding the flight mechanisms of a flying saucer disc in storage at Groom Lake, Nevada, in what is called Area 51. 

In a secret underground laboratory Lazar and others discovered the secret to the flying disc’s power source. Element 115 is transmuted to Element 116 by proton absorption, followed by the emission of two antiprotons. These anti-protons form a flux that travels down a tube whereupon they undergo annhilation with gasses found there. A great amount of thermal energy is liberated which is then converted to electric energy. But wait, this isn’t even the fun part.

The reaction of element 115, Ununpentium, also evolves a type of gravity wave that follows the curved shape of the flying saucer disc, which Lazar refers to as a “tuned wave guide”. This gravity wave propels the flying saucer disc through space-time by warping space.

Golly, that explains a lot. It always struck me that the saucer shape with it’s high surface to volume ratio must have put a real crimp on luggage space for the aliens. Also, what are the aerodynamics of a saucer shape? Man, this kind of stuff is perfect for the unedited internet.

So, I’ve driven my Jeep off the road into this Lazar swamp and now it is time to get back on the road.

This Lazar guy is pretty creative. But perhaps he should’ve taken a cue from Joseph Smith and started a religion instead. Lazars craziness physics is falsifiable if you wanted to go to the trouble. But religion uses the supernatural interface which is not falsifiable with physics. So, a religious wild-assed scheme is far more durable than one based on natural phenomena. 

Klaatu Berada Nickto.

Vlad the Irradiator

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The curious tale of murder by radiolysis becomes more convoluted each day. A Google search reveals an expanding table of accusations and denials, each party having some kind of axe to grind. There are the British authorities, anti-Putin exiles, Russian oligarchs, a diminishing group of fearless Russian journalists, angry and indignant ex-Soviet KGB patriots, and of course, Tsar Putin.  This case is beginning to reveal that there may be no perfectly clean parties, radiologically or otherwise. 

This is a fleeting glimse of a struggle takig place between bitter Russian ex-patriots and the Putin regime.  Some sketchy reports indicate that this disturbing battle involves an underworld of operatives working for both oligarch wise-guys and organs of the state secret police. It’s just creepy. There is no other way to put it.

But, it could easily be that the murder of Litvinenko was pulled off without the knowledge or sanction of the official security apparatus and was executed by freelancing bad guys.

Switching subjects now, a company in New Mexico called United Nuclear has an interesting commentary on it’s website, though I’m not sure that it makes any actual conclusions.  But, you can get a Polonium-210 coffee mug.  A 0.1 microCurie Po-210 source will run ya about $69.00. United Nuclear claims that their sources couldn’t have been used in the Litvinenko killing.  Assuming that their comments are accurate, I would have to agree with that conclusion.

I hasten to add that it is important that there be a commercial source of such things.  In order for people to invent new products using radiation, we need suppliers like United Nuclear.  We also need radiation sources for teachers to educate students and the public about radiation.  These people have some pretty cool stuff and it is my sincerest wish that pointy headed fools in DC do not try to clamp lots of extra constraints on to companies like United Nuclear because of the Litvinenko murder.  Gosh, it’s a good thing that Po-210 wasn’t found in somebody’s shoe. The TSA would be making us scan our feet at the airport.

Chemistry Blogs

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There has been a significant uptick in the number and quality of chemistry related blogs during the fall of 2006.  In my case, I was motivated to start by following the blog “Tenderbutton” maintained by Dylan Stiles, a Trost grad student. This genuine and charming blog was abruptly discontinued earlier in the fall.  The blog was somewhat revealing- though never negative- with regard to the lab culture and the chemical supplies of this world-class research group.  In all likelihood, the advisor called a “come to Jesus” type of meeting where he was reminded of his pending thesis defense. I could be completely wrong, but it is the kind of thing a research advisor would do.

Some blogs are operated as a node- that is, the blogger will collect and comment on interesting links elsewhere on the web.  Other blogs are more pedagogical in nature. The blogger will write on various topics with the intent of carrying on a kind of blog lecture series.  There are more than a few blogs that follow the chemical literature, publishing analyses of chemical transformations.  I think that these in particular are great blogs, but they do seem to be a lot of work for the blogger. The blog “Totally Synthetic” is a good example of a solid meat and potatoes style of synthesis blog. You leave this satisfying blog feeling like you’ve been in the literature that day.

Some blogs seem to be platforms for broadcasting various kinds of outrage. I have even done this myself. Sometimes a person just has to vent. But you also need to know when to stop. It is easy to step across the line from amusing to pathetic.

Some bloggers are prodigous writers, shoveling out great steaming heaps of output on whatever topic catches their fancy. Obviously, this is where “Lamentations on Chemistry” is parked.  My interest is in writing essays on science and politics.  Others are more talented at reviewing the chemical literature than I.  I view the human enterprise as a kind of tragic comedy and I take no small delight in reducing slices of it to words.

Dealey Plaza

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I had the bad judgement to visit the Texas Book Depository in Dallas a day after Christmas last year. What an incredible downer. Anyway, after paying the fee to go into what is now a museum, we made our way to the famous corner on the sixth floor by the window, behind stacks of boxes, and had a look down range to see the line of fire enjoyed by Oswald.  After a lifetime of watching programs on the JFK shooting and listening to endless drivel about it, there it was. It was evident to me that the distance from the window to the presidential limo, while not so short, isn’t really so long either. I would believe that a circle the size of a torso at that range could contain 90 % 0f the shots fired at the center of the circle. Randomness is a funny thing.  Oswald might have just been lucky that day. 

The Coming Nuclear Caliphate

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So, here we go. You know the nauseating feeling and that metallic tang sensation you get on your tongue when you’ve narrowly averted a car crash or had some other close call? Well, a recent news article has left me with the same feeling.  

According to an article in the Jerusalem Post, a group of middle eastern countries have signalled to the IAEA that they are interested in establishing a “common program in the area for nuclear energy for peaceful purposes”. 

The subtext of the Israeli article is that this move is a kind of equilibration by Sunni populations in response to Iranian/Persian Shi’ite nuclear development.  The countries in question are Egypt, Morocco, Algeria, Saudi Arabia, Tunesia, and the United Arab Emirates. 

According to the IAEA, 29 nuclear reactors are under construction in the world today.  Seven of them are in India, which plans to increase their number 8-fold by 2022. China has four reactors under construction and reportedly plans a 5-fold expansion in the next 15 years.  The IAEA keeps a handy list of new and retired reactors around the world.

Here is a nuclear joke you can tell to entertain your friends! Question: How many nuclear engineers does it take to replace a lightbulb? Answer: Fifty! One to replace the bulb and forty nine to figure what to do with the old one! 

On the one hand, it is logically and morally precarious to deny others what you yourself have enjoyed since the end of WWII. That would be the reassuring hum of nuclear electricity and prospect of security through the overwhelming firepower afforded by fission. 

On the other hand, the existing nuclear states have built infrastructure for the safe movement of nuclear materials through the system and folding new states into it may not be so hard.  However, the existing nuclear states have a compelling interest in avoiding disruption of the nuclear fuel cycle. More demand means higher prices.  Maybe the existing nuclear states should form something like OPEC to regulate the supply of nuclear fuel? 

I’ll admit that I’m a bit nervous about the prospect of Middle Eastern states becoming handy in the nuclear arts.  Any given “Atoms for Peace” program could degrade into a shell game that could hide a nuclear weapons effort. 

A plain reading of history seems to show that if someone else is helping with some of the enrichment, straight fission bombs are not as hard to develop as one might have supposed. It’s hard if you start ab initio with a pitchblende mine, a cloud chamber,  and F=ma.  But if you can outsource reactors and fuel, it’s a lot easier. The art in bomb design appears to be wringing out the biggest bang for the smallest amount of fissile material. Fortunately for everyone, thermonuclear bombs seem to be substantially trickier to make- my conclusion based on the open literature. 

If you think about it, a pre-nuclear state will almost certainly conclude that not having a nuclear weapon is tantamount to suicide. So the pressure to build nuclear weapons is irresistable to many regimes.

A nuclear arms buildup among the theocratic states seems especially worrisome, even though secular states like the USSR and North Korea make a poor case for secular stewardship.  Like it or not, the notion of MAD- Mutual Assured Distruction- did provide balance in the cold war between NATO and the Warsaw Pact.  Maybe what we are seeing is a nascent MAD in the middle east.

The worst case would be where the much desired Islamic Caliphate would have a “nuclear option”.  We can only hope that islamic theocratic fever is quenched by the pragmatics of economic prosperity. This is where a levelheaded US government could lead the way.

He leadeth me to walk beside the radiant pastures …

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Chins are wagging over the what is being called a slip-up by Israeli Prime Minister Ehud Olmert.  According to the New York Times, during an interview with a German cable news channel, Olmert reportedly said–

“Iran openly, explicitly and publicly threatens to wipe Israel off the map. Can you say that this is the same level, when they are aspiring to have nuclear weapons as America, France, Israel, Russia?” [Italics by Th’ Gaussling]

Oops! How do you say “Faux pas” in Hebrew? 

It’s kind of silly that this is even an issue.  For quite some time the only real questions have been- 1) How many coats of Turtle Wax are on the bomb casings? And, 2) Did they buy the extended warranty?

It’s an open question as to whether or not speaking publicly about its nukes enhances their deterrent effect for Israel. Look at that fetid Stalinist shrimp, Kim Jung Il.  He waves his nuclear capability around like a brain damaged test monkey with a turd on a stick. And, of course, we afford him the courtesies alloted to a brain damaged test monkey. A’hem.

Going postal over patents

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There was intellectual property-related death and mayhem in Chicago recently. A couple of patent attorneys and an office assistant were blown away by a disgruntled client. The 59 year old inventorhad evidently invested a considerable sum in lawyers fees trying to get a patent on his improved toilet for truck drivers.  At some point the inventor learned that he had been pooper scooped by others who had been issued a patent.

The client crossed the tipping point somewhere and went non-linear.   The enraged inventor entered the law offices and murdered 3 people. He was taken out by a SWAT shooter.

There is some interesting buzz over at the Volokh Conspiracy related to this matter.

Some posts back I made the plea for inventors to be more knowledgeable about the patenting process.  The attorney should be asking the question- “What’s next?”, not the client. That is to say, the client really needs to take a more hands-on approach to patent research and prosecution.  When it becomes a black box for the client, and the only part of it you can understand is the law firms invoice, it is a set up for misunderstanding.  Every inventor seeking a patent should spend time at the USPTO website doing a prior art search themselves. 

The attorney has ethical obligations in representing the client and they are institutionalized.  On the other hand, an inventor has some obligation to be informed about the basics of patenting and what constitutes realistic expectations.