ATELIER INTERNATIONAL DEDIAGNOSTIQUE DE L´INDUSTRIE DES

RÉSINEUX DE SECONDETRANSFORMATION

“LA COLOPHANE ET SON AVENIRDANS LE DOMAINE DU SUDOE”

BORDEAUX (France), OCTOBRE 2012

CHEMICAL DIVISION

RosinRosin isis aa solid form of naturalsolid form of naturalresin obtained from conifers andresin obtained from conifers and

mainly pine treesmainly pine trees

CHEMICAL DIVISION

WhatWhat isis RosinRosin??

CHEMICAL DIVISION

RosinRosin SourcesSources●● GUM:GUM:Tapping the Oleoresin of LivingTapping the Oleoresin of LivingPine TreesPine Trees

●●Tall Oil Rosin (TOR):Tall Oil Rosin (TOR):ByBy--product of Kraft Pulpingproduct of Kraft PulpingProcessProcess

●● StumpwoodStumpwood:: Extraction/SpecialExtraction/SpecialProcessing of Oleoresin fromProcessing of Oleoresin fromStumpsStumps

CHEMICAL DIVISION

RosinRosin compositioncompositionRosinRosin isis mainlymainly composedcomposed(>90%) of(>90%) of resinresin acidsacids withwith

similarsimilar basicbasic structuresstructures

TwoTwo commoncommon familiesfamilies ofof resinresin acidsacids::CHEMICAL DIVISION

●● AbietaneAbietane skeletal class:skeletal class:

●● PimaranePimarane skeletal class:skeletal class:

RosinRosin, as natural, as natural resinresin, has a, has avariablevariable compositioncomposition

dependingdepending onon::

CHEMICAL DIVISION

●● Origin of the Rosin (sources)Origin of the Rosin (sources)

●● Types of the trees (species)Types of the trees (species)

●● Location of the trees (geographical area)Location of the trees (geographical area)

Typical composition of resin acids in rosin byTypical composition of resin acids in rosin by sourcessourcesCHEMICAL DIVISION

ResinResin AcidAcid(% of(% of acidacid fractionfraction))

GumGumrosinrosin

TallTall OilOilrosinrosin

WoodWoodrosinrosin

AbieticAbietic 3232--3737 4040--4545 2525--3535PalustricPalustric//LevopimaricLevopimaric 1818--2323 55--1010 55--1010NeoabieticNeoabietic 1515--2020 11--66 55--1515DehydroabieticDehydroabietic 88--1010 2727--3232 2020--2525PimaricPimaric 77--1212 55--1010 33--55IsopimaricIsopimaric 66--1111 44--99 22--66SandarcopimaricSandarcopimaric 11--33 <2<2 11--33

Principal resin acids of gum rosin byPrincipal resin acids of gum rosin by speciesspeciesCHEMICAL DIVISION

Species(origin)

Resin acid (%)

P. pinaster(France)

P. halepensis(Greece)

P. sylvestris(Russia)

P. massoniana(China)

P. elliotti(Brazil)

P. merkusii(Indonesia)

Abietic 35 45 35 39 37 28

Isopimaric 10 11 7 2 17 16

Neoabietic 15 13 15 16 16 5

Palustric/Levopimaric

20 23 23 25 15 27

Dehydroabietic 9 5 10 7 5 4

Pimaric 10 9 10 5

Communic 4

Mercusic 11

Principal resin acids of gum rosin from P.Principal resin acids of gum rosin from P. pinasterpinaster bybygeographical areageographical area

CHEMICAL DIVISION

P. pinastertree location

Resin acid (%)

P. pinasterFrance

P. PinasterPortugal

P. PinasterSpain

P. pinasterUSA

Abietic 35 34 26 14

Isopimaric 10 7 5 12

Neoabietic 15 19 27 18

Palustric/Levopimaric

20 21 22 39

Dehydroabietic 9 9 6 4

Pimaric 10 8 9 8

Sandarocopimaric 2 2 2 2

Rosin is not an homogenous substanceRosin is not an homogenous substance

CHEMICAL DIVISION

Typical physical andchemical properties of

rosin by sources

Gumrosin

Tall Oilrosin

Woodrosin

Acid number 164 167 166Saponificaction index 172 174 172Unsaponifiable matter 8% 7% 6%Fatty acids - <5 -Color, U.S. rosin grade WW WG WGSoftening point (R&B) 76 ºC 77 ºC 76 ºCRefractive index 1.541 1.540 1.545Density 1.07 1.07 1.07

Typical physical and chemical properties of gum rosinTypical physical and chemical properties of gum rosin

CHEMICAL DIVISION

Typical physical andchemical properties of

gum rosin by types

Cleartypes

Middletypes

Darktypes

Acid number 165-171 160-170 155-163Saponificaction index 171-177 170-176 165-174Unsaponifiable matter 4.3%-5.5% 5.3%-8% 7%-10%Color, U.S. rosin grade XC-WW WG-I H-DSoftening point (R&B) 76 ºC 77 ºC 76 ºCAshes 0.041-0.02% 0.041-0.02% 0.01-0.17%Refractive index 1.541 1.540 1.545Density 1.07 1.07 1.07

RosinRosin ColorColorCHEMICAL DIVISION

WhyWhy RosinRosin DerivativesDerivatives??CHEMICAL DIVISION

NotNot suitablesuitable rosinrosin propertiesproperties::

●● LowLow softeningsoftening pointpoint (70(70 -- 80ºC)80ºC)●● OxidationOxidation trendtrend●● HighHigh acidityacidity ((IIaa= 155= 155 –– 170)170)●● CrystallizationCrystallization trendtrend●● LowLow viscosityviscosity●● QuiteQuite darkdark colorcolor●● HighHigh solventsolvent retentionretention●● OtherOther

OxydationOxydation testtest CHEMICAL DIVISION

0

0,5

1

1,5

2

2,5

1 day 2 day 3 day 4 day 5 day 6 day 7 day

Gum RosinDismutated RosinGlycerol esterPentaester

Time

% Weight Increase

((21 Kg. of21 Kg. of pressurepressure of Oof O22 forfor 77 daysdays))

HeatHeat stabilitystability testtestCHEMICAL DIVISION

Color Gardner

Time

(Color evolution at 170 ºC)

RosinRosin ChemistryChemistryCHEMICAL DIVISION

RosinRosin ReactivityReactivityCHEMICAL DIVISION

■■ ReactionReaction ofof DoubleDouble BondsBonds::●● AdductionAdduction●● HydrogenationHydrogenation●● DisproportionationDisproportionation●● PolymerizationPolymerization●● Etc.Etc.

■■ReactionReaction ofof CarboxylicCarboxylic AcidAcid::●● EsterificationEsterification●● SaltSalt FormationFormation ((SoapsSoaps,, ResinatesResinates))●● PhenolicPhenolic modifiedmodified rosinsrosins●● Etc.Etc.

RosinRosin ResinsResins UsesUsesCHEMICAL DIVISION

RosinRosin ResinsResins IndustrialIndustrialApplicationsApplications

CHEMICAL DIVISION

RosinRosin goodgood oror poorpoor??It depends on the particular industrial use

CHEMICAL DIVISION

some examples:some examples:

Brazilian rosin (P.Brazilian rosin (P. elliottiielliottii) is suitable for depilatory waxes) is suitable for depilatory waxes

Indonesian rosin (P.Indonesian rosin (P. merkusiimerkusii) is suitable for inks) is suitable for inks

Chinese rosin (P.Chinese rosin (P. massonianamassoniana) is suitable for adhesives) is suitable for adhesives

SUDOE rosin (P.SUDOE rosin (P. pinasterpinaster) is suitable for most uses (versatile)) is suitable for most uses (versatile)

CHEMICAL DIVISION

EUEU RosinRosin ProductionProduction ((ForecastForecast 2012)2012)

GumGum RosinRosin ++ TallTall--OilOil RosinRosin = 147,500 MT= 147,500 MT

15,3 %

84,7 %

UE Gum Rosin Production = 22,500 MT.(15.3%)UE TOR production = 125,000 MT. (84.7%)

Gum RosinTOR

EUEU RosinRosin demanddemand ((ForecastForecast 2012)2012)

GumGum RosinRosin ++ TallTall--OilOil RosinRosin = 325,000 MT= 325,000 MT

CHEMICAL DIVISION

58.5 %

41.5 %

UE Gum Rosin market= 190,000 MT.(58.5%)UE TOR market =135,000 MT. (41.5%)

Gum Rosin

TOR

EUEU RosinRosin BalanceBalance ((ProductionProduction vs.vs. DemandDemand))

DeficitDeficit == -- 177,500 MT177,500 MTEUEU DeficitDeficit ofof GumGum RosinRosin == -- 167,500 MT. (94.4%)167,500 MT. (94.4%)EUEU DeficitDeficit of TOR =of TOR = -- 10,000 MT. (5.6 %)10,000 MT. (5.6 %)

CHEMICAL DIVISION

EuropeanEuropean RosinRosin marketmarket byby applicationsapplicationsGumGum RosinRosin ++ TallTall--OilOil RosinRosin = 325.000 MT= 325.000 MT

CHEMICAL DIVISION

SourceSource: PCA International: PCA International ConferenceConference, Boston, Boston SeptemberSeptember 20122012

EuropeanEuropean RosinRosin AdhesivesAdhesives andand SealantsSealants marketmarketGumGum RosinRosin ++ TallTall--OilOil RosinRosin = 130.000 MT= 130.000 MT

AverageAverage annualannual marketmarket growthgrowth : 4: 4--5%5%

CHEMICAL DIVISION

SourceSource: PCA International: PCA International ConferenceConference, Boston, Boston SeptemberSeptember 20122012

45%

22%

11%

20%Packaging

PSA Labels

Construction

Other

EuropeanEuropean RosinRosin PrintingPrinting InksInks marketmarketGumGum RosinRosin ++ TallTall--OilOil RosinRosin = 100.000 MT= 100.000 MT

AverageAverage annualannual marketmarket growthgrowth : 3: 3--3,5%3,5%

CHEMICAL DIVISION

SourceSource: PCA International: PCA International ConferenceConference, Boston, Boston SeptemberSeptember 20122012

CHEMICAL DIVISION

PinePine treestrees

PinePine tappingtapping

CrudeCrude GumGum

DistillationDistillation

GumGumRosinRosin

GumGumturpentineturpentine

ChipsChips--woodwood

KraftKraft ProcessProcess

BlackBlack liquorliquor

SulfateSulfateturpentineturpentine

TallTall OilOilRosinRosin

TerpeneTerpene ResinsResins RosinRosin ResinsResins

PetrochemicalPetrochemical

FeedstockFeedstock(Nafta, etc.)(Nafta, etc.)

CrakingCraking ProcessProcess

ByBy--productsproducts ofoffractionationsfractionations lineslines

C5, C9, DCPDC5, C9, DCPD

HydrocarbonHydrocarbonResinsResins

RosinRosin ResinsResins areare notnot alonealone

SoapSoap AcidulationAcidulation

CTOCTO

DistillationDistillation

GlobalGlobal ResinResin ProductionProduction ((ForecastForecast 2012)2012)

CHEMICAL DIVISION

53.5%

3.3%

43.2%

Total world resin production = 2,430,000 MT- Rosin resins = 1,300,000 MT.- Hydrocarbon resins = 1,050,000 MT.- Terpene resins = 80,000 MT.

Rosin resins

Terpene resins

Hydrocarbon resins

SoureSoure: PCA International: PCA International ConferenceConference, Boston, Boston SeptemberSeptember 20122012

GlobalGlobal ResinTrendResinTrend CHEMICAL DIVISION

SourceSource: PCA: PCA InternationalInternational ConferenceConference, Boston, Boston SeptemberSeptember 20122012

• Moderate growth production of hydrocarbon resins (2%)• Moderate growth production of hydrocarbon resins (2%)• Slightly more sharper growth production of rosin resins (3%)• Slightly more sharper growth production of rosin resins (3%)• Stable production of• Stable production of terpeneterpene resins (0%)resins (0%)

CHEMICAL DIVISIONRosinRosin ResinResin TrendTrendGum Rosin

• Production is closely linked to the market price and theincrease in living standards (labor costs).• Moderate growth of production in the short term (3%)and increased market demand as a renewable raw material.• Long term limited availability of crude gum rosin(Eucaliptus vs. Pinus, salary increases, etc.)

.

Wood RosinSharp decline of wood rosin production in the long term.

Small and irrelevant proportion of total rosinproduction.

Tall Oil,• Production limited by the unavailability of crudetall-oil, linked to the price of energy (biodieselproduction).• Stable production in the short and medium termand longer-term shortages.

CHEMICAL DIVISION

WorldWorld RosinRosin ResinResin TrendTrend● Moderate growth of Gum Rosin production in the coming years(3% p.y.), but high risk of decline in the longer term.

● TOR production expectied to remain flat because production ofsoftwood kraft pulp also will be flat in the long term.

● Market demand for Rosin Resins 4 to 5 % p. y., leaded byemerging countries (China, India, Brazil, etc.)

●At longer term Trend, demand for Rosin Resins will exceed theoffer.

Higher prices and limited availability in the future

CHEMICAL DIVISION

RosinRosin resinsresins advantagesadvantages● Rosin market demands the more and more for ecological,biological and green products.

● Current economy requires development of products fromrenewable resources for sustainable industrial activities.

● Development of friendly environmental products (pinechemicals industry helps to preserve pine forests and reducecarbon footprint).

Clear advantage of Rosin resins overHydrocarbon resins

CHEMICAL DIVISIONConclusionsConclusions

●● Pine chemical industry in EU has a growing raw materialPine chemical industry in EU has a growing raw materialdemand, limited only by supply difficulties. This limiteddemand, limited only by supply difficulties. This limited

availability of rosin and turpentine will probably increase in nearavailability of rosin and turpentine will probably increase in nearfuture.future.

●● The geographic pine forest area ofThe geographic pine forest area of SUSTSUST--FOREST (Portugal,FOREST (Portugal,Spain and France), has enough resources to meet their ownSpain and France), has enough resources to meet their own

industrial needs.industrial needs.

●● Pine chemical industry is sustainable and environmentallyPine chemical industry is sustainable and environmentallyfriendly.friendly.

●●Pine chemical industry generates economic, social andPine chemical industry generates economic, social andenvironmental benefits.environmental benefits.

CHEMICAL DIVISION

Aujourd'hui est de bon sensAujourd'hui est de bon sensd'encourager le gemmaged'encourager le gemmage

dans le domaine dudans le domaine duSUDOESUDOE

merci beaucoup!merci beaucoup!