GREEN POLYURETHANETM

The first hybrid polyurethane-based coatings, adhesives & foam that eliminate the use of toxic isocyanates from the entire production process

# Nanotech Industries, Inc. (NTI)

 HCT was started by NTI, an intellectual property development and commercialization company with a pipeline of 14 patented technologies, which began in 2008

 NTI’s focus: nano and materials science-based applications

 NTI owns the patents and process know-how for the world’s first commercial Hybrid Non-Isocyanate Polyurethane, also referred to as “NIPU”, “HNIPU”, “Green PolyurethaneTM”, or

“ Epoxyurethane ”, available as coatings, adhesives and foam

# Polymate – INRC, Israel

 NTI & HCT’s scientific partner, staffed with world-leading materials scientists

 Polymate’s co-founders: Prof. Oleg Figovsky, the co-inventor of HINIPU, and Alex Trossman , are officers as well as part owners of NTI and HCT

 Prof Figovsky: Academician of the European Academy of Sciences, Director of R&D for NTI, HCT and INRC Polymate, Editor-in-chief of journals – TOCJ and ICMS (USA), SITA (Israel) and Chairman of the UNESCO Chair "Green Chemistry”

 NTI patents originated from Polymate scientists including 6 for HNIPU (composition & method)

# Hybrid Coating Technologies

 Started July of 2010

 For the purpose of commercializing HNIPU technologies

 NTI has exclusively licensed its HNIPU coatings, adhesive and foam material to HCT

 Headquartered in Daly City, CA with offices in Berlin and Israel and toll manufacturing in South San Francisco, Israel and Los Angeles with a total capacity of over 100,000 tons

## HNIPU “ Uramine ” Hardener Technology

 Hybrid polymeric materials, which combine properties of polyepoxides and polyurethanes improve properties of epoxy-amine

materials

 Optimal method: “ Uramine ” hardeners, which contain “Hydroxy Urethane Modifiers” (“HUM”)

# “HUM” & “ Uramines ”

 “Hydroxy Urethane Modifiers” (HUM) are the patented backbone technology of HNIPU - formulated within curing agents called

“ Uramines ” (Urethane Amines)

 Developed for epoxides to enhance their properties to the level of a polyurethane or better

# Advantages of Materials Based on Uramine Hardeners

 Zero isocyanates

 Zero VOCs

 Improved physical-mechanical properties

 Improved light stability properties

 High decorative appearance

 Used for curing epoxy compositions for a wide range of materials including coatings, foam, adhesives and sealants As evaluated, Uramines are 100s of times less toxic than conventional isocyanate-based hardeners in PU

## Green PU Coatings – Zero Isocyanate/VOC Savings

 Zero isocyanates, zero VOC, and minimal odor reduce costly application safety measures:

• HVAC shut down & ventilation equipment

• Shutdown of business operations adjacent to application zone and corresponding costs to pay facilities management, movers, Health & Safety for weekend work

• Scheduling changes, emergency evacuation assessment, displacing workers, students, etc.

• Security for late evening and/or weekend work

• less layers saves in material and labor



###  Creating 30-60% in application savings as compared to other premium PU brands

## Food Packaging Manufacturing Facility Montreal, Quebec

during application

# Plastic Manufacturing Facility, Israel

during application

# Plastic Manufacturing Facility, Israel

after application

# Carmel Mizrakhi Winery, Israel

# HNIPU Coating Property Advantages

 2 times better wear resistance

 10-30% higher adhesion (depends on substrate)

 Up to 30% increased
hardness

 4 times better tensile strength Delek Gas Stations – Israel

## Green PUTM Parking Garage, Israel

# Sonoma Raceway Garage, California

Before After

# BMW Showroom, France

# Insensitive to Moisture

 Due to the absence of isocyanates and an added intramolecular hydrogen bond, Green PUTM is completely insensitive to moisture and virtually water proof

 Green PUTM is 28 times more water and HCI resistant than conventional PU resulting in greater durability, corrosion resistance and longevity of the coating

# Suggested Applications

 Protective floor coatings and paint for industrial and commercial facilities

 Marine applications

 Delivery equipment for fertilizer & other chemicals

 Military equipment

 Protective coatings inside pipelines

 Clean processing areas: food, drug, medical industries

# Commercialization of Coatings

 Currently selling in US, S. America, Canada and Europe

 Distributing hardener to multi-billion dollar coatings company in S. America

 Completed development of a new DIY product for a coatings company with distribution in over 4,000 big box stores in US

 Advanced negotiations and testing with 3 more multi-billion concerns for licensing and distribution Based on same chemistry as HNIPU coatings

 Energy savings of more than 30%

 High R-values: up to 6.0/inch

 1.5 times higher tensile strength

 No need for primer

 Fire resistance

 Greater adhesion

 Applications:

• Thermal Insulation

• Automotive

• Furniture

• Upholstery and bedding

• Seals and gaskets

• Packaging 

# Green Polyurethane TM 

# Foam

# Conventional PUF vs. HNIPU Foam

Characteristics Conventional PUF HNIPU foam

Apparent density, kg/m 3 30 - 100 30 - 100

Stress at break, MPa 0.15 - 1.0 0.2 – 1.5
Thermal conductivity, W/mK 0.8 - 1.0 0.8 - 1.0

Number of closed cells, at least % 30 - 90 30-90

Water absorption, vol. % 2.5 - 3.5 2.5 - 3.5

Field of use Non-dwelling housing No restrictions

# Development of HNIPU Foam

 Pourable rigid and flexible foam prototypes manufactured

• Variations contain up to 40% vegetable oil

• Open and Closed cell (30-90% closed cell)



###  SPF in development and, with proper equipment and investment, expected to be ready for market in next 1 – 1.5 years

• With equal or better properties and conventional industry application methods, e.g., Graco spray reactors


###  Patent application for forming HNIPU SPF submitted

# HNIPU SPF Development Priorities

• Partnership with US University to support final development in US

• Funding to support research and equipment plus optimal eco-friendly retardants and blowing agents

• Development of Pilot HNIPU SPF technology

• Optimization and development of commercial scale production

# Proprietary Chemistry of Green PUTM

 NIPU networks are obtained through a reaction between polycyclic carbonate oligomers and aliphatic or cycloaliphatic polyamines with primary amino groups. This forms a crosslinked polymer with β

- hydroxyurethane groups of different structure resulting in a polyhydroxyurethane polymer.

 Since NIPU is obtained without using highly toxic isocyanates, the process of synthesis is relatively safe for both humans and the environment compared to the production of conventional polyurethanes.

# Proprietary Chemistry of Green PUTM

Above: β - hydroxyurethane fragments of polymer chains formed as difunctional starting materials with two options: secondary hydroxyl groups (A) and primary hydroxyl groups (B)

# Proprietary Chemistry of Green PUTM

 NIPU is not sensitive to moisture in the surrounding environment.

 Hydroxyl groups formed at the β -carbon atom of the urethane moiety increase adhesion properties.

 Plurality of intra and intermolecular hydrogen bonds as well as an absence of unstable biuret and allophanate units seem to be responsible for increased thermalstability and chemical resistance to nonpolar solvents.

# Hydroxyalkyl Urethane Modifier (HUM)

HUM is obtained as a result of a reaction between a primary amine and a cyclic carbonate compound at stoichiometric ratio, and can be represented by the formula:

wherein R 1 

### is a residue of the primary amine, R 2 

### and R 3 

### are the same or different and are selected from the group consisting of H, alkyl, hydroxyalkyl , and n satisfies the following condition: n ≥ 2 (US Patent 7,989,553, 2011).4,4'-(1-methylethylidene) bis-cyclohexanol based epoxy resin

Trimethyol Propane Triglycidyl Ether Neopentyl Glycol Diglycidyl Ether

28 Cycloaliphatic and aliphatic non-BPA based epoxy resins Cyclohexanedimethanol Diglycidyl Ether 

# Preferable Epoxy Resins

# Possible Cyclic Carbonates

29 Carbonated epoxidized unsaturated fatty acid triglyceride Propylene carbonate Polyoxypropylene tricyclic carbonate

# Raw Amines

PPGs amine terminated di - and tri-amines with MW up to 5000

Bio-based polyamines – idealized chemical structures

# New Long Chain Epoxy-Amines

 NTI recently submitted a US patent application for new hybrid epoxy- aminehydroxyurethane network polymers with lengthy epoxy-amine chains and pendulous hydroxyurethane units, described in the following scheme:

• where R` and R`` are residues of epoxy resins,

• E is a converted epoxy group, i.e., –CH 2 –CH(OH)–CH 2 –O–,

• N is a nitrogen atom,

• A is a residue of an amine,

• U(OH) is a hydroxyurethane group.

##  Cured linear hybrid epoxy-amine hydroxyurethane -grafted polymer with its novel structure of long epoxy-amine chains, pendulous hydroxyurethane units and a controlled number of cross-links result in:

• Increased flexibility (70-275% elasticity in coatings)

• Well balanced physical-mechanical (12.0 MPa tensile strength in coatings) and physical-chemical properties of conventional epoxy-amine systems

• Potential use in multiple applications including: synthetic leather and monolithic flooring for athletic facilities 

# New Long Chain Epoxy-Amines

# New Hybrid Polyhydroxyurethane Network on a Base of Vegetable Oil

Hybrid epoxy-hydroxyurethane compositions cross-linked at ambient temperatures were obtained on the base of renewable raw materials. Networks of hybrid polyhydroxyurethane were formed from carbonated-epoxidized soybean oil, without the use of isocyanate intermediates. Compositions can apply to the preparation of curable coating materials and curable polymeric foams.

33

# New Radiation-Curable Bio-Based Composition

A radiation-curable composition comprising (meth)acrylic monomers and/or oligomers, photoinitiators , and a nonreactive composite additive, wherein the nonreactive composite additive comprises a) a biobased hydroxyurethane additive of formula (1):

R 1 [

− NH

− COO

− CR 2 H

− CR 3 H(OH)] 2 (1) wherein R 1 is a residue of the biobased primary diamine, and R 2 and R 3 are the same or different and are selected from the group consisting of H , alkyl, and hydroxyalkyl ; and b) a silane -based hydroxyurethane additive of formula (2):

(R 6 ) 3-n (OR 5 )

n Si

− R 4

− NH

− COO

− CR 2 H

− CR 3 H(OH) (2) wherein R 2 and R 3 are the same as stated above, R 4 is generally an aliphatic group having from 1 to 6 carbon atoms, R 5 and R 6 , independently, are hydrocarbon radicals containing from 1 to 20 carbon atoms and selected from the group consisting of aliphatic, cycloaliphatic , and aromatic groups or combinations thereof, and n is equal to 1, 2, or 3 (US Application 14/160,297, 2014).

34