Wednesday, November 26, 2014

Plastics and Thanksgiving

Tomorrow is Thanksgiving Day here in the US and so it will be pretty quiet on the interwebs. Friday won't be much better as many people have that day off too. Last year at this time I blogged about the netting around turkeys and how much underappreciated that product is. If you didn't read it last year, I would suggest you take a look.

This year, I'll keep it short and just mention that the American Chemical Council's blog has a great overview of how polyurethane is used in creating the giant balloons used in the Macy's Thanksgiving Day parade. (As well as a few other examples of how polyurethanes make the day more enjoyable.) It's worth a look. And making those balloons would be one cool job to have.

Previous Years

November 26, 2012 - Fantasy Images of the Great Garbage Patch

Monday, November 24, 2014

Me? An Invited Speaker? Oh, never mind

There isn't much to report yet on the job search front yet, other than this invite I received via LinkedIn:

The email was entitled Plenary Speaker Invitation: Green Chemistry-2015. Gee, that's nice, but then I read the body of the email:
"Dear John S,

We certainly don’t know each other; still, I would like to contacts
[sic] you and open a dialogue about, "2nd International Conference on Past and Present Research Systems of Green Chemistry" (Green Chemistry-2015), scheduled on September 14-16, 2015 at [sic] Florida, USA.

The main theme of the conference is “Foster Advancements in Globalization of Green Chemistry". The Organizing committee would like to invite you as a Speaker/Delegate for the conference."
There were some links and then it was signed by a person with an Anglo-Saxon name.

Of course, alarm bells immediately went off. When are spammers going to learn that grammatical errors in "professional" communications are a huge tipoff? First there is the subject/verb disagreement in a simple sentence, and then there's the misused preposition (always guaranteed to trip up non-native English speakers). There was also the nice sleight of hand, demoting me from "Plenary Speaker" to speaker/delegate in just a few lines.

Now I know English is a tough language to learn and I am more than willing to forgive errors (I need plenty of forgiveness myself) but the errors were enough to make me question everything. A little bit of digging and I found the conference to be organized by the infamous OMICS group, which was recently accused of running predatory conferences. You can read more of their tactics here and here.

So while it is is flattering to receive an invite, I will decline. As in ignore it. All of this further supports why I really don't put a lot of time and effort into LinkedIn.

Previous Years

November 24, 2010 - Corporate Cultures

November 24, 2010 - That's all for this week

Friday, November 21, 2014

Dow Chemical and Third Point reach a ceasefire

The Polyurethane Blog is reporting that Dow Chemical and Dan Loeb, the activist investor and operator of Third Point LLC., have reached a ceasefire. Loeb will lay down his weapons for a full year including taking down his flashy website [1]. On the other side, Dow will add to the Board of Directors the two candidates that Loeb wanted plus two more directors. Since the current Board of Directors is the CEO Liveris and 9 others, there will now be a 14 directors total. If Loeb had won the proxy fight, his 2 directors would have been 20% of the board. Now he has to be content with 2 out of 14 (14%). That's called dilution.

So we shall now wait and see if the ceasefire holds [2]. It is possible that the board may start causing issues for the CEO, although it is doubtful we will ever find out much about such internal fighting unless the new guys decide to kiss-and-tell. The old board members are probably too loyal to cause much trouble. Such is the case whenever the CEO is also the Chairman of the Board, which is pretty always the case.

[1] Yep, the site is totally gone. 404. Not even a note saying that the site was taken down.

[2] So now what I am going to blog about, especially regarding Dow Chemical? Geesh, Loeb was great for providing bloggable material. Well, there are the ongoing appeals over the price-fixing scheme that Dow was found guilty of. They are now trying going to the Supreme Court (lots of luck with getting them to take the case).

Previous Years

NOvember 21, 2011 - Throwing Away Books

Wednesday, November 19, 2014

Plastics to Oil? Not in my backyard!

Efforts to convert plastics to oil have been getting a lot of good press lately. People seem to like the ashed-to-ashes, dust-to-dust approach of taking petroleum-based plastics and turning them back into oil. (This is all done via the miracle of anaerobic pyrolysis, and the output is a very sweet oil since there is very little or no sulfur in the feedstock.)

But the fly in the ointment seems to be the same issue faced by any chemical plant: where to build it? And we all know the answer - not in my backyard! That was what happened in Smith Falls, Ontario the other day. Attendees at the Town Hall were 21-1 against the proposal. The facility would only process polyethylene (both high- and low-density) and polypropylene, both of which are pure hydrocarbons, so I'm not sure what the concerns are from residents "...about the possibility of a fire at the plant which they said, could potentially expose residents to toxic fumes." Pure hydrocarbons burn pretty cleanly, especially compared to say, PVC (which inherently gives of hydrochloric acid), polyurethanes which can give off isocyanates, etc.

While Canada is a net exporter of oil, eastern Canada has some gaps in its pipelines with western Canada and so the east has to import some oil. Hence the potential use for a project such as this. Putting such in a facility in say, Edmonton would be the equivalent of setting up an ice factory in Fairbanks, Alaska.

I wonder how much a similar project here in the US would face similar resistance. We will find out as this trending technology will not disappear anytime soon.

Previous Years

November 19, 2013 - Your Plastic Waste is Valuable

Tuesday, November 18, 2014

Wait, you lost this too?

This appears to be the week to lose things. I lost my job, the only known sample of ε-polypropylene was lost and now the world's smallest 3D-sculptures are lost too. Granted, these sculptures would be pretty easy to lose. Take a look at one:
There are additional pictures in the linked article.

These sculptures were made with 2-photon absorption photochemistry, although the details are sadly lacking in the report. You start with a volume of photoreactive monomers such as an acrylate. UV light will polymerize the liquid turning them into a solid, but the problem with using UV light is that it will polymerize everything along the path of the light beam from the outside in. To selectively polymerize just a certain volume of material that is located well inside the mass of liquid, you need to a 2-photon absorption. Take a beam of photons each with half the energy of the UV light and send them into the sample at right angles to each other. Neither beam has the energy to initiate the polymerization, but where the two beams do intersect, there is enough. Viola! You can now polymerize the material at exactly whatever internal volume you want (subject to diffraction limits and a whole bunch of other experimental details that I won't get into) and nowhere else. This polymerization continue until all the appropriate sites have been solidified, after which the unreacted monomers are removed. It's then time to enjoy your beautiful creation.

But be really, really careful about losing it, o.k? No sneezing, coughing or "[ing] the mirror to better see the artistry." Better yet, make it a bas relief sculpture with a large base so that you can't lose it.

Previous Years

November 18, 2013 - 73 Quarters of Losses - And Still in Business

November 18, 2011 - An All Plastic Road Bridge

November 18, 2011 - Marine Pollution

November 18, 2010 - Why the Cox-Merz Rule?

November 18, 2009 - Perfect Fluidity

November 18, 2008 - Natta's still waging a patent war

Monday, November 17, 2014

Unemployed and looking for a job

Short and sweet: I am looking for employment. My previous employer, an unnamed Minnesota-based mining and manufacturing company gave me a severance package (pretty small compared to what I got 13 years ago when I was also let go from them, but times change). And so I am looking for a job in the Twin Cities area, particularly on the east side and into western-most Wisconsin. Advice and leads are nice, but names of hiring managers are solid gold.

I also am available as an expert witness. I was one 5 times in a previous employment situation, and also twice this past year as a side gig. I enjoy the work and have been able to make significant contributions to whichever side I'm assisting.

I would also be available for consulting, but that is one tough row to hoe, and I don't plan to actively pursue it into retirement. Not only do you have to hustle hard to get into a place, but once you do, there is the animosity towards you from the technical people who really feel challenged by your presence. I saw this many times while working at Aspen Research. We weren't consultants, just contracted technical personnel (who actually did lab work instead of just talking about doing lab work) but there was still more than one occasion where it felt like Mr. Freeze and the Freezies were at the table when we sat down to talk with them about a problem they couldn't solve.

As noted above, I've been in the situation before. There are some projects that I've wanted to take on but haven't had the time, and there is that extra weight around my middle that I will be able to whack away at making me, my wife and my doctor happy (that's a nice trifecta). I have learned to make the most of this forced time off and so the usual steps of "denial, bargaining, depression, acceptance..." just aren't there. I know there will come the day when I start employment again. If I knew what that exact day was, I would really sit back and enjoy everything until that day arrived, as would anyone in such a situation. So why should not knowing the day change that outlook?

Wish me luck and yes, I will keep blogging.

Previous Years

November 17, 2011 - A boat that is completely solar powered

November 17, 2010 - ANTEC Craziness

November 17, 2008 - Logical Conclusions

Friday, November 14, 2014

Is Dow Chemical going to have a proxy fight?

Every time I keep thinking that Dow Chemical may have finally been able to tell activist investor Daniel Loeb to take a hike, he keeps coming back. What a glutton for punishment.

Loeb's latest effort is this flashy website which makes yet another logically inconsistent attempt to acheive changes that he desires at Dow. This website is designed to inform stockholders of his opinions and push for a proxy fight to get two of his handpicked directors on the board.

I'm guessing that Loeb hopes that the impressive visuals of the website will hide the desperateness of his throw-everything-I-can-think-of-and-hope-something-sticks approach. He's using performance issues from as far back as 2006 to justify his proposal. Such an approach always generates internal inconsistencies, such as his insistence that Dow is a petrochemical company [1], and yet when comparing performance to other companies lists not a single petrochemical company [2]. Strange, isn't it? I could go on list lots of other inconsistencies, but what's the point? He's looking to fool naive investors and nothing more.

I've pointed out in the past that Loeb has forgotten his calculus (shame on him, as his degree was in economics), but it also looks like he could use a little help with his organic chemistry:
This image is also from the bottom of the "Facts" tab. It seems like a mashup of molecules, so I won't fault him for the images overlapping poorly, but it does have some fragments that are begging for a keto-enol rearrangement. At least the webpage lacks those slow-motion videos of Liveris that make him look stupid/arrogant/insensitive such as we see in our political ads.

It's not as if I am a big fan of Dow. I've lodged lots of complaints against Dow Chemical on this blog, but I really dislike the approach that Loeb is taking. He's looking to cash in on a short-term investment and then leave to cause trouble elsewhere. The chemical industry has enough problems without having to worry about this type of "activism". Fortunately, proxy fights seldom succeed unless a company is really in trouble. Dow isn't, as the most recent results show, so I expect this to (once again) change nothing.

[1] As seen at the bottom of the "Facts" tab.

[2] As seen on the "Underperformance" tab

Previous Years

November 14, 2011 - An Extreme Connection between Fracking and America's Cup

Tuesday, November 11, 2014

ε-Polypropylene - "And now I've lost it."

Crystalline polypropylene (PP) has always been one of the more interesting polymers because it is polymorphic - there are multiple crystalline phases that can form. Without any special processing, the α- phase dominates. This is the one that melts at about 170 oC or so. In the past few decades, nucleating agents for the β-phase have become commercialized. I've not worked with any β-PP, but it according to literature reports, it melts at about 150 oC or so. If the crystals are drawn during processing, they will revert to the α-phase, so you need to be careful about that. I'm not aware of any commercial applications, but there is probably something out there. There is also the the γ-phase, of which even less is known.

Those three phases have been known for about 20 years and are at least mentioned in passing on most books on PP. So imagine my surprise last week to find that they have now discovered the ε-phase! Wait - I didn't even know about the δ-phase Did I miss something?

Apparently I did. Or maybe not. I'll let you decide. A frantic Google search for the delta phase turned up nothing, but one of the introductory paragraphs of the ε-phase article mentions that the δ-phase occurs for copolymers of propylene and hexene or pentene when the comonomer content is great than about 10%. So is that really a polypropylene crystalline phase? Before you decide, consider what we know about the ε-phase.

Just like with the δ-phase, the ε-phase doesn't occur with stereotactic, defect-free polypropylene, but requires specially prepared material, where "...the polymers produced have progressively lower melting transition temperature, lower homosteric pentad sequence population, and higher solubility in low-boiling solvents, indicating frequent stereochemical inversion in monomer enchainment." In other words, this polypropylene has some significant "issues". ("Normal" polyproplyene has a high melting temperature as noted above, high pentad regularity, and is insoluble in low-boiling solvents.) Somehow the defects are not enough to make this completely amorphous. So again I ask, is this really a polypropylene crystalline phase?

My opinion (which comes with a full-money-back guarantee if not completely satisfied): No, the δ- and ε-phases are not part of the polypropylene polymoprhs. For "normal" polypropylene, you can make the α-, β-, and γ-phases from the same starting material, but you can't make the δ- and ε-phases and so they are not part of the set.

Before I finish, consider this example of life imitating art:
"Unfortunately, both the details of the material and the material itself were lost when our laboratory moved to its new location."
Que up the theme from "The Medicine Man". I can only imagine the scene within the new lab: " I've lost it. Haven't you ever lost anything doctor Bronx? Your purse? Your car keys? Well, it's rather like that: Now you have it and now you don't." That would be pretty painful to discover and hats of to the researchers for being upfront about it.

Previous Years

November 11, 2011 - Birefringence in Polycarbonate

November 11, 2011 - Flashing Labels

November 11, 2010 - Olefin Metathesis

Monday, November 10, 2014

As silly of a silicone product as you will ever find

Courtesy of Chemjobber, comes this silly idea: the Silibagz - a silicone bag that is pretty hard to take seriously.

It's not as if silicone bakeware doesn't already exist. It does. So this is merely a bag instead of a muffin pan. And in fact, you can already buy silicone bags (which makes me wonder about the people behind this fundraiser and their supporters). What makes this funding effort silly are so many of the claims.

Such as
"We use platinum silicone exclusively, as we believe the only reasonable solution is a highly durable, safe and eco conscious solution [sic] (platinum silicone is the highest grade silicone available)."
That's a whole lot of misstatements in a short span. First, there is no such thing as "platinum silicone" and it is not the highest grade available. This whole "platinum silicone" concept makes it seem like it's a Platinum Album or a Platinum Visa Card. It's not. It's actually a "platinum-cured silicone" which has platinum as a catalyst and it typically used in 2-part silicones. But now let's look at the whole "eco conscious solution [sic]" statement. First you have silicone polymer, made from silica. But you can't just dump silica sand into a reactor and voila! out jumps silicone polymer. Instead, the silica is first reacted with an organic chloride over a copper catalyst to make dimethyldichlorosilane. Then you throw in some water to create hydrochloric acid and some low molecular weight oligomers that can be separated and polymerized. So just in terms of raw materials, you already have the silica, the (toxic) organic chloride, and the copper and platinum metals which need to be mined (oh, there's an environmentally clean operation that is sustainable).

But just the energy required to pull this off is also considerable. Distillation columns everywhere. "Outside of the petroleum industry, Dow Corning Corporation maintains the largest distillation operation in the world! " So how is this an "eco conscious solution[sic]"? Running that many distillation columns takes a whole lot of energy derived from the combustion of petroleum fuels (or maybe even coal!). Those energy costs are a huge contribution to silicone polymers costing so much compared to organic polymers even though the starting material is so much cheaper.

No, this whole effort is just plain stilly, start to finish. I don't think that the project initiators are proceeding in bad faith, but only that they have deceived themselves.

Previous Years

November 10, 2011 - Give me a photon! No, you better make it 2!

November 10, 2010 - Flow-Induced Crystallization #4

Tuesday, November 04, 2014

How many polymers are there?

It was suggested in another social media site this last weekend that the big chemical companies have tucked away in their vaults the results of polymerizing "...every molecule with a double bond has been treated with a free radical initiator, and every difunctional molecule has been tested as well." To which I say hogwash.

Let me give a hint as to the magnitude of the polymer world. Let's start with something simple like making a polyurethane. This is a "simple" case because the stoichiometry is pretty limited. You usually try to have an equivalent amount of isocyanate groups and hydroxyl groups (or something close to 1:1). We'll get into crazy stoichiometry in a minute. And for no particular reason other than the breadth of their offerings, let's look at all the isocyanates offered by Bayer and all the polyols offered by Perstorp. (There are lots of other suppliers of isocyanates and polyols - I'm making no particular endorsement here of any kind.) If my counting is correct, Bayer has 135 commercial isocyanate offerings and Perstorp has 34 commercial caprolactone based polyols. Just pairing each isocyanate with each polyol would results in 135 x 34 = 4,590 polymers. To further complicate matters however, sometimes 2 isocyanates are used, as are 2 polyols. So now you can have 135 x 134 x 34 = 615,060 OR 135 x 34 x 33 = 151,470 or even 135 x 134 x 34 x 33 = 20,296,980. All told that is 4590 + 615060 + 151470 + 20296980 = 21,068,100 polymers using the materials from just these 2 companies.

Now let's go for the really big numbers. Consider alkyl (meth)acrylates, a nice subsection of unsaturated compounds but by no means all the options available. Alkyl (meth)acrylates are available between methyl (C1) and at least dodecyl (C12), and the acids are nice to have as a weapon too. So that is 26 monomers available. My personal experience is that I've seen as many as 6 (meth)acrylate monomers used. That means there are 26 homopolymers, 26 x 25 = 650 copolymers, 26 x 25 x 24 = 15,600 terpolymers, 26 x 25 x 24 x 23 = 358,800 tetrapolymers, 26 x 25 x 24 x 23 x 22 = 7,893,600 pentapolymers and 26 x 25 x 24 x 23 x 22 x 21 = 165,765,600 hexapolymers potentially available for just alkyl (metha)acrylates. All told, that is 174,034276 alkyl (meth)acrylates.

But that number would rapidly be dwarfed if we included any of the common options available when polymerizing acrylates, such as
  • their ability to be used in pretty much any ratio (I've seen cases where changing one monomer by as little as 2 percentage points make a big difference in the final properties)
  • the concentration of the initiator (which alters molecular weight)
  • chain transfer agents (which also alter molecular weight)
  • reaction conditions (bulk, UV-initiated, thermal-initiated, solution, emulsion) all which have tremendous influence on the final product

Over 174 million polymers! If you had a machine setting up 1 reaction a second 24/7/365, that is still 5 1/2 years or solid work. And setting up the reaction is the easy part. You would still need to initiate the polymerization and (potentially) keep it going. And you still wouldn't be even close to the end of what polymers are available.

So how many polymers are there? I have no idea, but it is a tremendous number. It reminds me of the old joke of a young person looking at a starlit sky and asking an older person how many stars are out there. The answer: "All of them".

Previous Years

November 4, 2013 - Who's Been Eating My Ocean Plastic?

November 4, 2010 - Plastics in the "Economist"