Methyl Formate: Being Kind To The Planet

Industrial Urethanes receives UNIDO support for environmentally-friendly blowing agent

• Blowing Agent Comparison
• Blowing Agent Evolution
• Blowing Agent Technologies for Rigid PU Foam
• Semirigid Integral Skin
• Domestic Appliances
• Other Appliances
• Thermoware: (picnic coolers & jars)
• Discontinuous Panel
• Continuous Panel
• Water Heaters
• Pipe Insulation
• General Insulation-Spray
• Conclusions

Industrial Urethanes supports rigid polyurethane foam customers with a new, locally developed and refined blowing agent technology that has zero ozone depletion (ODP), zero to low global warming potential (GWP) and zero volatile organic content (VOC) ratings.

This development represents a major breakthrough for compliance with the Montreal and Kyoto international environmental Protocols.

The United Nations Industrial Development Organisation (UNIDO) have announced that companies manufacturing the 141B blowing agent will now be incentivised to shut down their plants. In addition, UNIDO have approved Methyl Formate as an alternative blowing agent to 141B for which funding will be available.

The “cherry on the top”, according to Industrial Urethanes Technical Director Dr Peter Groome, is that customers who adopt the new technology do not need major capital investment programmes for plant modification.

He notes that there has been “considerable research and development conducted on blowing agents since ozone-depleting CFCs were phased out more than 10 years ago. HCFCs were then used but also fell short of environmental requirements.”

As a result, HCFCs such as 141b were phased out in EU and America recently. Thereafter third generation HFA blowing agents such as 245fa were developed and widely used in rigid polyurethane foam applications and Cyclopentane emerged in Europe. However, they do have GWP ratings and a major problem is the very high cost of investment in new or modified plant, a factor that prevented all but the very large world-scale plants from adopting these agents.

In South Africa, the smaller scale of plants dictated a solution that would meet the requirements of the green protocols but without the capital cost associated with new or extensively modified machinery.

Industrial Urethanes embarked on the development of a new blowing compound using a chemical that while it had proved effective with zero environmental characteristics, it was hampered by a low flashpoint.

Further research by Industrial Urethanes identified a special additive that suppresses the flashpoint of the Methyl Formate blowing agent and it is being used by major customers of Industrial Urethanes without the need for capital expenditure on equipment.

Dr Groome believes Methyl Formate will remain the primary blowing agent solution for the manufacture of rigid foams with high insulation properties in South Africa for many years to come. It is a solution that requires minimal investment by the user and achieves the same benefits without harming the environment.

Methyl Formate is environmentally benign and offers the following advantages:

• Produces thermally efficient foam insulation
• Replaces HCFCs, HFCs and HCs
• Zero ratings for ODP, GWP and VOC
• Lesser quantities lead to cost savings
• Excellent solubility
• Good foaming properties
• High foam flammability resistance
• Low volatility

Methyl Formate is also a true liquid blowing agent that has the advantage of being applicable to integral skins and flexible foams as well as rigid foams. It also ensures that users are not saddled with future “baggage”. Life cycle analysis documentation is available.

This development and local refinement has enabled Industrial Urethanes to lead the industry in terms of environmentally friendly practice in the blowing of polyurethane foams. The technology is “streets ahead” of others and, for South African scale plants, it carries the major advantage of avoiding capital investment.

Blowing Agent Comparison

Blowing agent	Water + 141b + R22	Water	water   (high risk)	Water +134a	Water +134a (high risk)	Water +134a	Water + 245fa	Water + 245fa	Water + 365mfc / 227ea	Water + iP	Water + ciP	Methyl Formate	MF/ LLBA	4th Generation HFAs
Foam Volume / m³	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15
core density	29	44	39	42	37	28	32	29	32	32	32	32	29
density injected	32	47	42	45	40	31	35	32	35	35	35	35	32
PUR foam / unit	4.8	7.1	6.3	6.8	6.0	4.7	5.3	4.8	5.3	5.3	5.3	5.3	4.8
Mix	125	140	140	140	140	134	135	130	130	130	130	130	130
MDI/kg	0.56	0.58	0.58	0.58	0.58	0.57	0.57	0.57	0.57	0.57	0.57	0.57	0.57
Polyol incl blowing agent/kg	0.44	0.42	0.42	0.42	0.42	0.43	0.43	0.43	0.43	0.43	0.43	0.43	0.43
phys. blowing agent / polyol	15%			3%	3%	9%	6%	15%	10%	13%	13%	13%	13%
polyol/system (kg)	0.38	0.42	0.42	0.40	0.40	0.39	0.40	0.37	0.39	0.38	0.38	0.37	0.37
blowing agent / system (kg)	0.07	0.00	0.00	0.01	0.01	0.04	0.03	0.07	0.04	0.06	0.06	0.06	0.06
Price of Blowing Agent	X	0,01 X	0,01 X	3 X	3 X	3 X	7 X	7 X	6 X	0,75 X	X	X	X	12 X
Investment
New machinery (Pentamat, HK650/1250,...)						2,000,000 ZAR				6,000,000 ZAR	6,000,000 ZAR		0	2,000,000
construction										1,000,000 ZAR	1,000,000 ZAR
batch preparation								1,500,000 ZAR
improved cooling of day tank				50,000 ZAR	50,000 ZAR		50,000 ZAR	50,000 ZAR
Total Investment						2,000,000 ZAR	50,000 ZAR	1,550,000 ZAR		7,000,000 ZAR	7,000,000 ZAR	30,000 ZAR	0	2,000,000
Lambda value	10.4	15	15	14	14	12	12	11	11	14	12	10.7	10.7	11
ENERGY    RATIO	1	1.66	1.66	1.55	1.55	1.33	1.33	1.22	1.22	1.55	1.33	1	1
AHAMA	1	1.36	1.36	1.27	1.27	1.09	1.09	1	1	1.27	1.09	1	1

Blowing Agent Evolution

• ODP – Ozone Depleting Potential
• GWP – Global Warming Potential

Blowing Agent Technologies for Rigid PU Foam

Two different class of blowing agents available today to replace HCFC-141b

• Zero ODP substances (HFC-134a; HFC-365/227; HFC-245fa)
• Zero ODP and Low GWP substances (water, formic acid, HCs, methylal, methyl formate)

Processing Cautions		Zero ODP			Zero ODP Low GWP
Blowing Agent Flash Point		NO	NO	NO	NO	NO	YES	YES	YES
Potential Metal Corrosion		NO	NO	NO	NO	YES	NO	NO	NO
Important Foam Properties	HCFC 141b	HFC-134A low level	HFC-134a – 365/227	HFC – 245fa	Water	Formic Acid	HC	Methylal	Methyl Formate
Applied Density	Ref	-	-	+	--	-	= /+	--	--
Compressive Strength	Ref	+	= /+	+	++	+	= /	++	++
Foam K-Factor	Ref	--	-	= / +	---	---	-	---	---
Skin Hardness (Wood imitation)	Ref	-	+	-	--	n.a.	n.a.	n.a.	n.a.
Demoulding Time	Ref	-	-	-	--	--	+	--	--
Max Operating Temperature (Pipe)	Ref	n.a.	n.a.	=	++	n.a.	=	n.a.	n.a.
Aesthetics	Ref	+	=	+	=	++	n.a.	n.a.	n.a.
Change/Additional process equipment requirements	Ref	Likely	Yes	Likely	No	Yes	Yes	Likely	Unlikely

An Important Note:

The general properties can be considered as a guideline for selecting the right blowing agent. However, each application is unique and the knowledge on the physical properties will help to decide the right choice.

For example, for those applications driven by thermal insulation, fully water blown solution will not be the most effective one

Semirigid Integral Skin

Applications

• steering wheel
• Furniture (armrest, headrest, seat)

Key Requirements

• Skin formation
• Aesthetics
• Good abrasion resistance

Blowing agent options

• Zero ODP:
• HFC 134a and HFC 245 fa/365 mfc-227
• Zero ODP/Low GWP
• Present: Water, Hydrocarbon
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

Domestic Appliance

Key requirements

• Foam insulation properties (K-factor)
• Fast productivity

Blowing Agent Options

• Zero ODP:
• HFC 245 fa
• Zero ODP / Low GWP:
• Present: Cyclo Pentane
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

Other Appliances

Application

• supermarket counters
• horizontal freezer
• Visi-coolers
• Food service equipment

Blowing agent options

• Zero ODP
• HFC 134a low level, HFC 245 f and HFC 134a/HFC 365 mfc/227ea
• Zero ODP / Low GWP
• Present: Water, formic acid, Hydrocarbon, Methyl formate
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

Thermoware: (picnic coolers & jars)

Key requirement

• Fast productivity
• Low cost

Blowing Agent options

• Zero ODP
• HFC-134 low level
• HFC-134a/FA
• HFC-245fa
• HFC134a/365/227
• Zero ODP / Low GWP
• Present: Water, Hydrocarbon
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

Discontinuous Panel

Application

• cold store
• building panel
• telecom shelter

Key requirements

• Low k-value
• Faster productivity
• FR

Blowing Agent Options

• Zero ODP
• HCFC 134a, HCFC 134a/FA, HCFC 134a/HFC 365Mfc/227ea
• Zero ODP/Low GWP
• Present: water, water/FA, HC, Methyl Formate
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

Continuous Panel

Application

• Building panel
• Cold room Telecom Shelter

Key requirements

• faster production
• FR

Blowing Agent options

• Zero ODP
• HCFC 134a, HCFC 134a/HFC 365
• Mfc/227ea, HFC 245 fa
• Zero ODP/Low GWP
• Present: water, n-pentane, c-pentane
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

Water Heaters

Key requirements

• faster production
• Low energy consumption

Blowing Agent options

• Zero ODP
• 134 a, HFC 134 fa/HFC 365-227 ea, HFC 245 fa
• Zero ODP/Low GWP
• Present: water, Hydrocarbon
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

Pipe Insulation

Key requirements

• Good mechanical Properties
• Max operating temperature
• Thermal insulation

Blowing Agent options

• Zero ODP
• HFC 245 fa
• Zero ODP/Low GWP
• Present: Hydrocarbon, water blown
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

General Insulation-Spray

Applications

• Walls, crawl spaces, enclosed attics, roof decks

Key requirements

• Good foam mechanical properties
• Good foam insulation properties
• Low moisture vapor resistance
• Low flame spread
• Low smoke generation

Blowing Agent options

• Zero ODP
• HFC 134a, HFC 134a/HFC 365 mfc & 245 Fa
• Zero ODP/Low GWP
• Present: water
• Future: Methyl Formate, FEA 1100, HBA2 and AFA-L1

Conclusions

Blowing Agent Options

1. HFA’s
• Short term future. Due to environmental impact of emissions.
2. Hydrocarbons
   • Dubious long term future. Atmosphere pollution concerns
   • VOC
   • RSA Air pollution act 2004/2010
3. MF
• Long term candidate
4. New generation HFA
• Long term candidate
5. New generation HFA & MF
• Long term future
6. MF & Formic acid
• Long term future

For any queries, please contact:

• Dr Peter Groome – Technical Director 082 307 0691 / peter.groome@indur.co.za
• Natasha de Lange – Sales Manager 082 417 1657 / natasha.delange@indur.co.za