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©2013, Georgia-Pacific Chemicals LLC. All rights reserved.

Advancements In NAF Adhesive

Technology

Derek L. Atkinson, Dr. Bobby L. Williamson, Dr. Feng Jing,

Georgia-Pacific Chemicals LLC

Not to be further copied, quoted, shared or otherwise distributed without permission.


Outline

2

• No-Added Formaldehyde (NAF) Resins Background

• Existing NAF Options

• Representative GP Chemicals NAF Projects

– pMDI + Soy

– PAE

– PA + Crosslinker

– Tannin + Crosslinker



Why Pursue an NAF Solution?

3

• Regulatory Drivers

– California Air Resource Board (CARB) Legislation

• Airborne Toxic Control Measure (ATCM) to Reduce Formaldehyde Emissions from Composite Wood Products introduced in 2007

– Specified allowable formaldehyde emissions levels from raw particleboard, medium density fiberboard, and hardwood plywood panels

– Implemented in two phases (Phase 1 and Phase 2)

– Ultra-low emitting formaldehyde (ULEF) and no-added formaldehyde resins (NAF) were defined

– Federal Formaldehyde Emissions Standards for Composite Wood Products Act (2010)

• Mirrors CARB ATCM emissions limits with potential exemptions for the use of NAF and ULEF resins




4Not to be further copied, quoted, shared or otherwise distributed without permission.


• Market Drivers

– Growing interest in green building

• Includes residential and commercial

• Increasing demand for “green” building materials

– Green-building certification programs offer incentives for

use of NAF technologies

• Use of composite wood made with NAF resins can help

qualify for points under the U.S. Green Building Council®

Leadership in Energy and Environmental Design (LEED®) and

other rating systems

Source: 2013 Dodge Construction Green Outlook; Freedonia Group; U.S. Green Building Council, NAHB Research Center





• Market Drivers

• Innovation to Satisfy Market Needs

– A core part of our Guiding Principles

“No matter how superior a company’s products and services,

it cannot stay in business unless it makes improvements and

innovations… To do this successfully requires that a business

apply the processes of experimental discovery and creative

destruction... All businesses must constantly innovate.”

-Charles Koch, CEO Koch Industries

Source: Koch, Charles. (2007) The Science of Success p 61


Existing NAF Options

6

1. Polymeric Diphenyl methane diisocyanate (pMDI)

2. Crosslinked polyvinyl acetate (PVAc)

3. Soy-polyamidoamine-epichlorohydrin (Soy-PAE)

• Commercialized and well known

• Have various drawbacks/limitations

―Lack of tack

―Need for release agent

―Handling, safety, and environmental concerns

―Degree of moisture resistance

―Cost

• Industry needs more selection.


Illustration Source: Georgia-Pacific Chemicals


pMDI + Soy

• Initial research into NAF was modifying pMDI

• Found the addition of soy did not significantly reduce pMDI’s properties

• US Patent Application 20020231968

Description

Press Time

(sec)

IB

(psi)

WA-24

(%)

TS-24

(%)

100 % UF 240 76 91 24

100 % UF 330 78 87 26

20% soy, 80% pMDI 240 367 68 13

20% soy, 80% pMDI 330 307 65 13

50% soy, 50% pMDI 240 250 60 16

50% soy, 50% pMDI 330 240 68 16

80% soy, 20% pMDI 240 139 82 26

80% soy, 20% pMDI 330 122 87 25

100% pMDI 240 340 62 12

100% pMDI 330 406 65 12

Particleboard conditions

Press temp (F) 330

Resin loading (%) 8

Density (pcf) 48

Internal Bond (IB)24 Hour Water Absorption (WA-24) 24 Hour Thickness Swell (TS-24)

Source: Georgia-Pacific Chemicals

7


R

HN

N

HN

O

O

R

OH

Cl

R

HN

N

HN

O

O

R

Cl

OH

R

HN

N

HN

O

O

R

Cl

OH

R

HN

N

HN

O

O

R

OH

Cl

PAE Resin

8

• Polyamidoamine with azetidinium functional group

– Used as a wet strength resin in paper making

– Azetidinium group provides crosslinking functionality


Source: Hagiopol, Cornel (2012) Chemistry of Modern Papermaking p.190. Used by permission

*


PAE + Urea

9

• Lab studies demonstrated adding urea to PAE improved

the performance on particleboard


115.6

92.8 83.5

0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

3.6% PAE + 0.4 % urea 4 % PAE 3.6 % PAE

IB (

psi

)

4 min press time, 330 °F, 0.5" thick, 46 pcf



PAE Resin

10

• Lab studies showed the addition of polyamidoamine (PA)

improved the performance of PAE on particleboard



Unweighted Marginal Means (some means not observed)

Vertical bars denote 0.95 confidence intervals

300 360 420 500 540 600

Press Time (sec)

0

50

100

150

200

250

300

IB (

psi)

4 % PAE

4 % PAE + 2% PAPress Temp (°F) 330

Thick (in) 0.5

Density (pcf) 45


PAE Resin

11

• Lab testing showed the PAE-PA combination performed

as well as urea-formaldehyde (UF)


Resin loading (%) 6

Press Temp (°F) 330

Density (pcf) 45


Vertical bars denote 0.95 confidence intervals

200 240 300 360 400 600

Press Time (sec)

40

60

80

100

120

140

160

180

200

IB (

psi)

UF Control

PAE+PA


PAE Resin

12

• Technology Highlights:

– Met ANSI IB standard for M-3 grade particleboard (73 psi)

– Leverages existing manufacturing capabilities

– Processing speed similar to UF-based CARB 2 resins

– US Patent 7,781,501

– Trialed industrially on particleboard

• Challenges:

– Stored at pH 3.2

– Requires pH adjustment with NaOH prior to use

– Cost-in-use expected to be higher than current technologies



Polyamidoamine + Crosslinker (XL)

13

• Using polyamidoamine backbone

• Has functionality and alkaline pH

• Wanted a crosslinker with azetidinum functionality

• Designed a crosslinker using epichlorohydrin and

ammonia with a range of functionality


R

HN

NH

HN

O

O

R




14

• Lab testing showed performance better than or equal to PAE


System IB

(psi)

MOR

(psi)

**MOE**

(psi)

Formaldehyde

(ppm)

UF 7.50 ± 0.8 416 ± 26 582,000 ± 46000 0.097

PAE 19.3 ± 2.6 595 ± 37 647,000 ± 48000 0.085

PA + XL 33.0 ± 2.6 717 ± 79 556,000 ± 46000 0.025

LD-2* 20 406 72,500

Thickness (in) 1.5

Density (pcf) 30

Press Temp (F) 380

Resin loading (%) 5.5

Press Time (sec) 600

• 8 IB blocks per panel

• 5 Modulus of Rupture (MOR)/Modulus of

Elasticity (MOE) strips

• Formaldehyde emissions measured by GP™

Dynamic Microchamber (DMC)

• LD-2 is ANSI grade for low density (< 40 pcf)

particleboard

*ANSI A208.1-2009 Particleboard Table ASource: Georgia-Pacific Chemicals



15

• Lab testing showed performance better than or equal to PAE


Resin Content 6.0%

PAE Solids 40% PAE

PA Solids 45% PA

X-linker solids 67% X-Linker

Press Temp 330 °F

Board Size 0.250” x 16” x 16”

Target Density 48 lb/ft3


GP 652G03 PAE PA+Xlinker 75/25 PA+Xlinker 80/20 PA+Xlinker 70/30

90 120 150

Press Time (s)

150

160

170

180

190

200

210

220

230

240

250

260

270

280

IB (

psi)



16

• Successful industrial trial in North America


Thickness (in) 1.5

Density (pcf) 33

Press Temp (F) 380

Resin loading (%) 5.5

• 4 IB blocks per panel• 4 MOR/MOE strips• LD-2 is ANSI grade for low density (< 40 pcf) particleboard

System IB

(psi)

MOR

(psi)

MOE

(psi)

UF 40.4 469.3 133,610

PA+XL 59.3 663.8 119,156

LD-2* 20 406 72,500

*ANSI A208.1-2009 Particleboard Table A




17

• Technology Highlights:

– Polyamidoamine better suited for industrial use

– US Pat 8,299,154

– Trialed successfully on the industrial scale

• Challenges:

– Epi+ammonia reaction is highly exothermic

– Cost-in-use expected to be higher than current

technologies



Tannin

18

• Natural product

– Typically extracted from tree bark

• Various types

– Black wattle

– Quebracho

– Pine

– Pecan

• Used industrially with

paraformaldehyde


OHO

OH

OH

OH

OH

OH

OHO

OH

OH

OH

OH



Acid/Base Catalysis to Increase Reactivity

19

OHO

OH

OH

OH

OH

H H

O OH

Alkaline condition Acidic condition

better

nucleophile

better

electrophile

OHO

OH

OH

OHH

OHO

OH

OO

OH

OH

OH

OH

H H

O O

* *

*

* Due to the presence of different flavonoids

in tannin, –OH group shown in parentheses

is optional




Boiling Water Gel Time Tests – Composition

Effect

20

0

2

4

6

8

10

12

14

16

18

0% 5% 10% 15% 20% 25%

Gel tim

e (

min

)

Glutaraldehyde (wt%)

pH 8

pH 9

pH 10




Particleboard Studies

21

Black wattle tannin: glutaraldehyde = 88:12 on a 100% solids basis; resin loading: 10%; press temperature: 400°F (204°C); pH: 10.3; wood furnish species: Southern Yellow Pine; board construction: single-layer; targeted board thickness: 5/8”; mat moisture content: 14.5%; targeted density: 48 pcfSource: Georgia-Pacific Chemicals

49.9

pcf49.9

pcf

49.0

pcf

49.5

pcf



Other Tannins and Other Crosslinkers

22

• A wide variety of tannin types have been tested

– North American

– South American

– African

– Lab extracted

• A wide variety of crosslinkers have been tested

– Non-provisional patent application filed

• Boards require a higher mat moisture content

• Selected tannin and proprietary crosslinker

combination for industrial demonstration trial



Tannin Industrial Trial


Photo Source: Georgia-Pacific Chemicals


Tannin Industrial Particleboard Trial

24

• Successful trial in South America


Hour Thickness

in

Density

pcf

IB

psi

MOR

psi

TS-24

%

A-24

%

MC

%

HCHO

Emissionmg HCHO/100 g dry wood

14:14 0.591 41.8 69.6 2103 10.9 55.3 6.6

15:15 0.591 43.7 78.3 2509 26.5 94.2 6.4 0.09

12:12 0.591 42.3 56.6 2045 13.9 51.6 6.9

13:13 0.591 41.7 60.9 2002 9.8 47.8 8.0

14:14 0.591 41.5 63.8 1987 19.4 71.2 7.3 0.12

14:30 0.591 40.2 52.2 1885 17.1 63.7 8.2

16:16 0.591 42.2 49.3 1885 15.1 52.0 6.4

17:17 0.591 41.9 60.9 2234 11.0 47.1 7.4

17:30 0.591 43.0 63.8 2553 11.1 48.6 8.1 0.08

Thickness

in

Density

pcf

IB

Psi

MOR

psi

TS-24

%

A-24

%

MC

%

HCHO emissions mg

HCHO/100 g dry wood

0.5906 39.95 ± 1.25 73 ± 22 2176 ± 218 < 25 < 90 8 ± 3 < 8

Standard Requirements for E1 grade particleboardFace resin (%) 8.8

Core resin (%) 6.6

Press Factor (sec/in) 406



Tannin Pilot Scale MDF Trial

25

• Successfully demonstrated that GP proprietary formulation can be used in a blowlinesystem

• Multiple blends made over variety of conditions

• MDF boards made with acceptable properties for IB, MOR/MOE, and 24-hour water soak


Photo Source: Georgia-Pacific Chemicals


Conclusions and Future Plans

26

• Georgia-Pacific Chemicals has demonstrated three

NAF technologies on an industrial scale

• Georgia-Pacific Chemicals has IP on all three

technologies

• Further NAF industrial and lab solutions continue

to be developed



Acknowledgements

27

• GP Chemicals NAF Program team

• GP Chemicals Wood Adhesives R&D group

• GP Chemicals Analytical group

• GP Chemicals Wood Adhesives Business, Sales, &

Marketing groups

• Non-GP Trial Partners


©2013, Georgia-Pacific Chemicals LLC. All rights reserved. 28

Derek Atkinson, M.S.

Associate Chemist

Phone: (770) 593-5905

2883 Miller Road, Decatur, GA 30035

Fax: (770) 322-9973

Email: [email protected]

The Georgia-Pacific logo and bonds that last. advancements that work. are trademarks owned by or licensed to Georgia-Pacific Chemicals

LLC. The information and technical data herein is believed to be accurate. It is offered for your consideration, investigation and verification.

Buyer assumes all risk of use, storage and handling of the product. NO WARRANTY, EXPRESS OR IMPLIED, IS MADE INCLUDING, BUT NOT

LIMITED TO, IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE WHICH ARE SPECIFICALLY EXCLUDED.

Nothing contained herein shall be construed as a license to operate under or recommendation to infringe any patents.

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