synthetic organic chemist experienced in monomer and polymer

John Mastrangelo

Presentation to Hughes Research Lab

November 18, 2019

• Ph.D. Chemical Engineering, University of Rochester 1996

• Classical undergraduate Chem. E. education, B.S. 1990

• Research experience as synthetic organic/polymer chemist

– Academic (U of R), esoteric small scale

– Government (Naval Research Lab, 4 yr), application oriented

– Industrial (G.E., Albemarle 1 yr ), market driven

– Start up company (AdaptivEnergy, 1 yr) polyimides and more

– Shaw Floors-(11 yr, problem solving, asking the right question)

• Original design of novel small molecules and polymers

– Synthesis “from scratch”, literature searching (Beilstein, patents…)

– 50 mg to 3 kg scale

– 2 to 10 reactions in linear sequence

– Analytical instruments, polymer processing equipment, laboratory setup, pre-pilot plant

• Synthesis projects

– A thiol terminated molecular wire for asymmetric conductivity

– A thiol terminated oligomer for nanoelectronic connection

– A smectic liquid crystal for video display

– A transparent conducting polymer to compete with ITO

– A new engineering thermoplastic

– A membrane for crude oil fractionation

– A copolymer using a monomer derived from corn

– Polyimides as hot melt adhesives

– Reactive phosphorus-containing flame retardants

• Novel flooring products

A new engineering thermoplastic

• Work done at GE, no proprietary information

• PEK, high temperature, solvent resistant, inert to extreme pH

– Next generation Ultem

• Automotive, oil well, inert substrate/membrane

• Molecular weight by intrinsic viscosity in H2

SO4

(IV = 0.87

g/dL)

• Product composition has required thermal properties and critical molecular weight (similar commercial materials exhibit IV 0.8 to 1.5 g/dL), pilot scale monomer

• Conventional reaction used but temperature too high for existing equipment, laborious isolation

• An alternate process/synthesis method needed

• Melt phase polymerization, only byproduct is volatile (recycle to make more bis(trimethylsilyl ether) monomer), catalytic Membrane for crude oil fractionation

• Work done at GE global research center, deliberately vague

• Thick film (4-10 mil) on porous substrate, separate aromatic and aliphatic components of crude oil

• Variation on existing patents (Dupont, US 5,550,199)

• Crosslinker is key, switch from isocyanate to aziridine followed by formulation work, DoE

• Improved separation selectivity at the same time as increased flow rate

• Tight timeline, procedure written for large scale test at remote facility, processing window

• Pilot scale roll, four liters of suspension, 1500 ft2

• Subject of patent disclosure letter 2005

Modification of conventional polyester

• Work done at GE, no proprietary information

• Use diol derived from renewable source as comonomer

• Try to find extra value from excess agricultural product, corn

• Increase glass transition temperature of

poly(butylene)terephthalate by 20 K

• Classical transesterification (high temp, low pressure, extremely high viscosity), one pound scale

• Grinding, extrusion, injection molding

• Polymer microstructure (13

C-NMR to determine degree of

block structure)

• Optimized formulation with respect to glass transition temperature, tensile strength, and rate of crystallization Polyimide adhesives for laminated piezoelectric

actuators

• AdaptivEnergy, pre-IPO startup company

– Chemistry, engineering, design, testing, etc.

• Polyimide film for use as hot-melt adhesive

– Devices are a laminate of steel and ceramic

• Thermosetting copolymer crosslinkable with dopant

(semi-interpenetrating polymer network)

– Low viscosity flow during device assembly, light crosslinking at peak temperature of cycle

– Adequate for most demanding set of properties

• Batches 5-500 gram polyamic acid,

– 5 grams PI sufficient for 50-100 devices

• Tier I manufacturer for large scale film production

– Communicate technical and safety requirements with partner/customer Flame retardants

• Work done at Albemarle lab

• Synthesis of phosphorus–containing flame retardants

• Reactive compounds for reduction of polymer flammability

• Want high flame quenching at low concentration of P as well as low cost

(< 10 $/kg)

• PCl3

chemistry

• Safety and “industrial-style” reactions and purification

• Laboratory set up

– Assembly of lattice in hoods

– Plumbing of circulating oil bath

– Gas line connections on gas chromatographs

• Daily experience at major chemical manufacturing facility (Houston, TX) Experience and Skills from Shaw

• Support manufacturing operations in carpet industry

– Interact with plant, laboratory personnel at all levels

• Importance asking questions...

– Identify root cause of problems, not just symptoms

• Innovation within diversified manufacturing company

– Shaw need to measure composition of carpet mixtures:

• simple DSC process measurement

– “Green Label” certification requires recycled materials:

• Renewable filler US 2014/0287184 A1

– Depolymerization process to serve two functions

• Recycle PET carpet, supply plasticizer for vinyl tile

• US 9981902 B2

• Laboratory work

– Design and run experiments whenever justified

• Lean Six-sigma Black belt

– Mintab use and interpretation of statistics

• Trained in TRIZ problem solving methodology

Novel color changing flooring product

● New products for a traditional industry

● Prototype carpet

Passive color at edges

Activated color in middle

● Prototype engineered wood veneer

●

TAD-succinate to compliment the reactivity of TAD

15

● TAD is a light stabilizer for

condensation polyamide

● Polyamide has end groups which

are NH

2

or COOH

● NH

2

on TAD reacts with COOH end

group of polyamide

● Modify TAD with COOH to enable

reaction with NH

2

group on COOH

end of polyamide

● Succinate made in 80-90% yield, good

purity, melting point >270C

● Stabilization equal to TAD at 5250 ppm

● 6000 ppm succinate is soluble in damp

molten capro at 160C

● 1 full scale bench reaction to make

enough for 150 Lb polymerization

About 360g succinate/ 150 Lb N6

Largest possible reaction with lab

equipment

● Why terminate polymer with inert

group? Use something functional

instead!

Light or oxidation stabilizer, other?

Minimized add-on-cost for RV-preserving

AO’s (two solutions offered)

● Existing plant process can’t

produce first quality (high RV)

product

● Cure for symptom of main

problem determined

● Conventional AO-25 is too

expensive

● Simpler, cheaper solutions found

● Can preserve RV for << 1 cpp

● Want 2+ choices for ability to

negotiate price, screening

continues

● Main job is for plant EG is to

optimize wetting of fiber,

uniformity

AO-25

0.8-1.8 /Lb

ShawGuard Ox

0.5-1.1 /Lb

Cu(OAc)

2

0.07-0.14 /Lb

Gallic acid

0.14-0.67 /Lb

Actual add-on-cost

3-5X due to

application losses

16

What I offer to Hughes Research Lab

• Experience in academic, government, large research labs, small company

• Design of chemical structure to meet property requirements

– Polymers (imide, ester, thiophene, phenyl(acetylene), arylene ether)

– Small molecules (flame retardants, liquid crystals, monolayers, asymmetric electrical conductivity)

• Synthesis of novel materials from commercially available ones

– Comfortable with reaction scheme of wide range of scale and complexity

• Classical training as a chemical engineer coupled with pilot plant experience, scale up, statistical analysis of existing processes

• Used to working with a team on complex projects

•

• Independently finding solutions to problems (Beilstein, SciFinder, PatSnap, etc., patent searching/understanding)

• Numerous patent disclosures

• Recognize when chemistry is not the answer…

• Step outside of “comfort zone” (i.e. debug code, learn to program laser cutter and CNC router)

Contact this candidate