1

Chunliang Li (TU Eindhoven) Rafaël J. Sablong (TU Eindhoven & PTG Group) Theo Veldhuis (DSM Coating Resins) Paul Buijsen (DSM Coating Resins) Cor Koning (TU/e & DSM Coating Resins)

Novel renewable coating resins based on

limoneneoxide and CO2

Global societal trends drive DSM’s markets

Population growth

Wealth

Resources constraints

Sustainability

Urbanization Healthcare costs Energy security

Food security

Ageing population

Materials Nutrition Health

Global shiftsHealth & WellnessHealth & Wellness Climate & Energy

BRIGHT SCIENCE, BRIGHTER LIVING

Sustainability Within DSM Coating Resins the focus on innovation includes sustainable coatings solutions. • Moving away from solvent-based technologies • Investing and innovating in waterborne technologies • Partnerships and acquisitions on sustainable technologies;

- Energy curable resins (AGI) - Bio-renewable resins

DSM Coating Resins conducts LCA* studies to maintain its high-level of commitment to Sustainability. • Conducting range of LCA studies for coatings industry As a result we contribute to the coatings industry as a whole

* LCA: life cycle assessment

‘Leading the Transformation to Sustainable Coatings’

Background

O

HO O

O

O O

O

O OH

R

m n

Rafaël J. Sablong, et al. Progress in Organic Coatings 76, 2013, 1704–1711

O OH

O

O

n

CO2

OH

NCO

NCO

OCNOHOH

Urethane linkage

O CO

NH

Prepolymer

‘S’

‘R’

LO/CO2 copolymerization

NNEt

Et Et

Et

NZn

NAr

Ar

RH

O

Cis (45

%)

R =

N(SiMe3)2

Trans- and cis-

(R)-limonene oxide

Trans (55

%)

O

+

Et-BDI-H

CO2

(Et-BDI)ZnR

O O

On

Htrans Hcis

HpHHH

Geoffrey W. Coates, et al. JACS, 2004, 126, 11404

1) Only trans reacts; 2) No ether groups

Entry [R-LO]/[Zn] PCO2 Bar

Conva

% Mn

b

kDa PDIb

1 125 40 55 14.4 1.19

2 250 40 54 16.9 1.21

3 250 10 52 16.0 1.19

Bulk synthesis of poly(limonene carbonate) Catalyzed by (Et-BDI)Zn[N(SiMe3)2]

Conditions: 25 °C, 12 h, bulk reaction. a: determined by 1H NMR; b: determined by SEC in THF. • Higher zinc concentration leads to lower Mw

• Reaction pressure has little effect on the polymerization results

• Conversion max of 55%: very low reactivity of cis isomer

• Polydispersities around 1.2

120-140 oC 80-100 oC 60-80 oC

The transcarbonation agents and catalysts

O

OSn

2

Sn(Oct)2

NN

O OAlO

(salen)AlEt

N

N

NH

Triazabicyclodecene (TBD)

O

OHO

OHH

H

Isosorbide

HO OH

n = 3, 10

n

Trimethanolethane (TMP)

OH

OH

OH

HO OH

HO OH

Pentaerythritol (PE)

P1 O

O

O P2 P1 O HO P2

HOR O

OR

OHOH

Entry Catalyst Polyol Temp

oC

Time

h

[Polyol]/

[Catalyst]

Mn

kDa PDI

1 Sn(Oct)2 Decanediol 120 4 10 5.9 2.7

2 (salen)AlEt Decanediol 120 4 10 6.6 2.5

3 TBD Decanediol 60 4 10 3.7 1.8

4 TBD Isosorbide 100 8 10 6.2 1.9

5 TBD Trimethanolethane 80 1 8 3.3 1.9

Transcarbonation experiments (TBD trials in toluene, others in bulk)

0 4 8 12 16

3

6

9

12

15

Mn (k

Da)

Time / h

[M]:[Cat.] = 100:11,10-decanediol

13.8 kDa, PDI~ 1.2

1.2

1.4

1.6

1.8PD

.I. Initial fast decrease in Mw induced by decanediol

Polymer with desired Mw obtained within 3 h

Marginal drop after 1 h

Maximum PDI after 3 h then constant

Chunliang Li, et al. European Polymer Journal, 67 (2015) 449–458

TBD . 60 oC

MALDI-ToF-MS characterization after alcoholysis reaction with 1,10-DCD.

Nearly only α,ω-OH-end capped chains; No cyclic compounds observed

Presence of non-hydroxyl end group (not quantitative) due to rearrangement reaction LO Nearly 100 % carbonate linkage (no ether bonds observed, also not in NMR)

Polymers with 0, 1 or 2 DCD units

OOH O

O

OH

m n

Am,n

OOH O

O

OROH

m

Bm

Cm

OO O

O m

Dm

OO

O

O

mR

O

O

OROHH H

1500 1600 1700 1800 1900 2000 21000

10

20

30

40

50

60

70

80

90

100

C6,1

B7

A7,1

A8,0

% In

tens

ity

Mass (m/z)

A7,1

B7

D7,1

C6,1

Chunliang Li, et al. European Polymer Journal, 67 (2015) 449–458

Sample Polyol Mn

kDa PDI

OHV

[mgKOH/g]

Mn,titration

kDa

Tg

(oC)

1 isosorbide 3.3 1.9 28.1 3.9 96

2 1,10-DCD 3.0 2.0 29.2 3.7 71

3 1,3-PD 3.3 2.0 21.6 5.0 91

4 TMP 3.2 1.9 26.8 4.0 83

Properties of OH-ended PLCs used for toluene or tBuOAc casting and curing.

Chunliang Li, et al. European Polymer Journal, 67 (2015) 449–458

MWs calculated from titration results are higher Relevant for curing: 1) low reactivity of the tertiary OH end groups; 2) the presence of non-hydroxyl end group

PLC with 1,10-decanediol moieties has much lower Tg than others 1,10-DCD moieties act as flexible segments; isosorbide is rigid and 1,3-propanediol is stiffer than DCD

Catalyst: dibutyltin dilaurate (DBTDL)

Coating evaluation

N N

N

(CH2)6

(CH2)6 (CH2)6

NH

O O

oN N

N

(CH2)6

(CH2)6 (CH2)6

O O

o

O

NO

NHO

N

O

HN

O

N

O

I Desmodur N3600 II

Desmodur BL3272

(caprolactam

blocked)

Curing agents

OCN

NCOOCN

Curing T (oC)

Film thickness (μm)

Appearance Impact test (1 kg, 1 m)

Acetone rub test (50 acetone DR)

180 16 - 35 Transparent

Colorless- light yellow - * - *

Chunliang Li, et al. European Polymer Journal, 67 (2015) 449–458

* Irrespective of curing agent used

O O

O

n

HS R OH

O O

O

Op

O

O

n-p

S

R

OH

R= -CH2(CH2)4CH2- ,

-CH2CH2-

Post-modified PLCs with tunable thermal properties

HO *

3.7 ppm

H H

O

H

O

O

5.0 ppm

4.7 ppm

A typical NMR spectrum of the modified PLC (50 %). (Ratio C=C Hs/backbone H reduces by factor 2)

Before modification

After modification

Resins Mn

a

kDa Feeding ratio

[ene]:[OH] Target conv.

[=] % Conversionb

% Tg

c oC

Mnd

kDa PDI d

14k-E(50%)

14

2 50.0 47.5 103 19.5 1.96 14k-E(12.5%) 8 12.5 12.3 118 16.4 1.49 14k-E(6.3%) 16 6.3 6.2 117 15.3 1.41 8k-E(50%)

8 2 50.0 48.0 89 10.3 1.81

8k-E(12.5%) 8 12.5 12.3 97 9.2 1.59

Entry Mn

a kDa

Feeding ratio [ene]:[OH]

Target conv.[=] %

Conversionb %

Tgc

oC Mn

d kDa

PDId

14k-H(50%) 14

2 50.0 48.0 66 18.7 1.35

14k-H(12.5%) 8 12.5 12.3 94 17.6 1.32

8k-H(50%) 8

2 50.0 47.5 56 10.0 1.63

8k-H(12.5%) 8 12.5 12.3 84 9.6 1.69

Reactions with mercaptoEthanol

Reactions with mercaptoHexanol ( lower Tg than for ME modification)

a MW of polymers before modification. b Determined by NMR. c Determined by DSC. d Determined by GPC. Reactions conditions: 1,4-dioxane, 80 oC, [=]:[AIBN]=1:0.3

Post-modification of PLCs (8k DCD-alcoholyzed; 14k as synthesized)

Catalyst: Dibutyltin dilaurate (DBTDL)

Curing agents: Desmodur series I: N3600 II: BL3272 (ε-caprolactam blocked)

Conventional curing agents and catalyst

Transparent films after curing N N

N

(CH2)6

(CH2)6 (CH2)6

NH

O O

oN N

N

(CH2)6

(CH2)6 (CH2)6

O O

o

O

NO

NHO

N

O

HN

O

N

O

I Desmodur N3600 II

Desmodur BL3272

(caprolactam

blocked)

Curing agents

OCN

NCOOCN

2350 2300 2250 2200 2150 2100

0.00

0.02

0.04

0.06

Abs

orba

nce

Wavenumber (cm-1)

t = 0.5 min 1.5 min 3.5 min 7.5 min 12.5 min 20.5 min 30.5 min

0 5 10 15 20 25 300

20

40

60

80

100

Con

vers

ion

(%)

Time / min

IR spectra of the reaction mixture of resin 8k-E(12.5%) and N3600 ([OH]:NCO=1:1.1) and the NCO conversion over the time at 180 oC.

Curing kinetics

3900 3600 3300 3000 2700 2400 2100

0 min 30 min

Time / min0 5 10 15 20 25 30

0

20

40

60

80

100

Con

vers

ion

(%)

Time / min

IR spectra of the reaction mixture of 8k-H(50%) and BL-3272 ([OH]:NCO=4:1) and the conversion of the blocked isocyanate over the reaction time at 180 oC. NOTE: Faster than non-blocked system because of higher OH number of resin

Curing kinetics

R NH

CO

N R NCO R'OH RNH

CO

OR'deblocking

O

Coating tests after solvent casting (tol. or tBuOAc, 14k as synthesized; 8k alcoholyzed with DCD)

Resinsa Curing agentb

OHV (mg KOH/g)

Ratio (OH:NCO)

Acetone

resistancec

Av. film thickness

(μm)

Pencil Hardness

König Hardness

(S)

Curing T oC

8k-E(12.5%) I 45.6 1:1.1 + 28 2H 168

180 8k-H(12.5%) I 35.4 1:1.1 + 35 2H 182

14k-H(12.5%) I 31.6 1:1.1 + 38 2H 167

8k-H(50%) II 97.0 4:1 +/- 37 2H 167

180 8k-H(50%) II 97.0 2:1 + 45 2H 169

14k-H(50%) II 91.2 4:1 +/- 23 2H 168

14k-H(50%) II 91.2 2:1 + 30 2H 169 a E: mercaptoethanol used, H: mercaptohexanol used. b For curing reactions of polymer resins with low OHV, non-blocked isocyanate was used and the curing temperature was kept at 180 oC. c 50 Acetone ‘dubble rubs’ survived without visual damage

DMTA results alcoholyzed PLS (non-blocked curing agent I)

1. Higher [OH]/[NCO] ratio gives lower storage modulus in the rubbery plateau region. 2. The coatings with similar crosslink densities have comparable modulus in the rubbery plateau region. 3. Tgs of the coatings with higher concentration of mercaptohexanol moieties are much lower; Tan delta peaks are single and rather symmetric (‘single phase’ ?).

0 20 40 60 80 100 120 140 160 1800.1

1

10

100

1000

10000 8k-H(50%) [OH]:[NCO]=2:1 8k-H(50%) [OH]:[NCO]=4:1 8k-H(12.5%) [OH]:[NCO]=1:1.1

Sto

rage

Mod

ulus

/ M

Pa

Temperature / oC0 20 40 60 80 100 120 140 160 180

0.0

0.5

1.0

1.5

2.0 8k-H(50%) [OH]:[NCO]=2:1 8k-H(50%) [OH]:[NCO]=4:1 8k-H(12.5%) [OH]:[NCO]=1:1.1

Tan

Del

ta

Temperature / oC

DMTA results non-alcoholyzed PLC (non-blocked curing agent I)

20 40 60 80 100 120 140 160 180

0.0

0.2

0.4

0.6

0.8

1.0

1.2 14kE(50%) [OH]:[NCO]= 1:1 14kE(50%) [OH]:[NCO]= 2:1 14kE(50%) [OH]:[NCO]= 4:1

Tan

Del

ta

Temperature / oC20 40 60 80 100 120 140 160 180

0.1

1

10

100

1000 14kE(50%) [OH]:[NCO]= 1:1 14kE(50%) [OH]:[NCO]= 2:1 14kE(50%) [OH]:[NCO]= 4:1

Sto

rage

Mod

ulus

/ M

Pa

Temperature / oC

Less homogeneous than mercaptohexanol-modified coating system (different miscibilities of curing agent with polymer resins?; Mn may play a role in miscibility; systematic study required for explanation)

Storage modulus in the rubbery plateau region in accordance with the crosslink density

Mechanical failure observed above Tg for [OH]/[NCO] ratio of 4 (too low crosslink density/ weak network)

Crosslinking reactions using thiol-ene chemistry

SHHS

SH

SS

SS

S

S

S

S

S

or

HO O

O

O O

O

O OH

R

m n

R. Sablong et al. Progress in Organic Coatings (2013) 76, 1704–1711

Mats Johansson,et al. Polym. Chem., (2014), 5, 3245-3260

Properties of PLC resins

Sample Mn / kDa PDI Tg / oC

P1 6.0 2.2 83

P2 2.8 1.8 70

Photoinitiator: Irgacure@ 651

Curing agent: TMPMP (Thiocure®)

Thermal initiator: AIBN

Themal initiator: dicumyl peroxide

t1/2 = 10 h, 70 oC in toluene

t1/2 = 10 h, 115 oC in toluene

1800 1600 1400 1200 1000 800

0 min

1 min

2 min

5 min

10 min

15 min

20 min

25 min

30 min

Wavenumber (cm-1)

900 890 880 870 Wavenumber (cm-1)

FTIR for kinetic study

1650 1640 1630 Wavenumber (cm-1)

FTIR spectra of curing reaction mixture using dicumylperoxide ([=]/[SH]=1) maintained isothermally for various times at 180°C

0 5 10 15 20 25 30

102030405060708090

100

[=]/[SH] = 1 [=]/[SH] = 2 [=]/[SH] = 4

%

Time / min

180 oC

0 5 10 15 20 25 30

102030405060708090

100 [=]/[SH] = 1 [=]/[SH] = 2 [=]/[SH] = 4

%

Time / min

160 oC

0 5 10 15 20 25 300

102030405060708090

100 [=]/[SH] = 1 [=]/[SH] = 2 [=]/[SH] = 4

%

Time / min

140 oC

Curing kinetics (DCP) % indicates % C=C left

Conversion versus time plots for isopropenyl groups cured with various amounts of TMPMP at different temperatures More curing agent (lower [=]/[SH]) yields higher

conversion of double bonds as expected. The curing reaction at 180 oC finished in 5

minutes. Conversions dependent on temperature

Resins Stoichimetry [=]:SH

Acetone resistance

Av. film thickness

(μm)

Pencil Hardness

König Hardness

(s)

Curing conditions

P1 1:1 + 28 3H 96

Thermal curing

DCP/160 oC

P1 2:1 + 35 3H 116

P1 4:1 + 38 2H 148

P2 1:1 + 25 3H 118

P2 2:1 + 28 4H 132

P2 4:1 + 29 3H 147

P1 1:1 + 37 3H 153

UV curing 130 oC

P1 2:1 + 36 3H 158

P1 4:1 + 25 2H 167

P2 1:1 + 45 2H 109

P2 2:1 + 50 2H 146

P2 4:1 + 28 2H 158

Coating tests (solvent casting)

-60 -40 -20 0 20 40 60 80 100 120 140 160 180 200

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 4

Tan

Del

ta

Temperature / oC-40 -20 0 20 40 60 80 100 120 140 160 180

10

100

1000

[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 4

Sto

rage

Mod

ulus

/ M

Pa

Temperature / oC

DMTA results from films after curing (160 ºC, Dicumyl peroxide)

1. Initiator type greatly affects the homogeneity of the curing system Initiator with higher T to reach t1/2 gives more homogeneous films (More time to homogenize (?))

2. Films obtained with lower [=]/[SH] ratio show more elastic behavior. Higher peak intensities of tan δ reflect great energy loss/ more viscous behavior

3. Storage modulus increases with lower [=]/[SH] ratio

Mn=2.8 kDa; PDI=1.8

-40 -20 0 20 40 60 80 100 120 140 160 180 200

0.0

0.2

0.4

0.6

0.8

1.0

Mn = 2.8 KDa, PDI=1.8

[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 4

Tan

Del

ta

Temperature / oC

-40 -20 0 20 40 60 80 100 120 140 160 180 200

10

100

1000

[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 4

Sto

rage

Mod

ulus

/ M

Pa

Temperature / oC

Mn = 2.8 KDa, PDI=1.8

-40 -20 0 20 40 60 80 100 120 140 160 180 2000.0

0.3

0.6

0.9

Mn = 6.0 KDa, PDI=1.7

[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 8

Tan

Del

ta

Temperature / oC

-20 0 20 40 60 80 100 120 140 160 180

10

100

1000

Mn = 6.0 KDa, PDI=1.7

[=]:[SH] = 1 [=]:[SH] = 2 [=]:[SH] = 8

Sto

rage

Mod

ulus

/ M

Pa

Temperature / oC

DMTA results from films after UV thiol-ene curing (130 ºC, Irgacure 819)

Phase-separation for higher amount of Thiocure® (curing too fast to homogenize?)

Thermoset UV powder coating

Advantage: 1. Environmentally friendly; No solvent nor water needed. 2. Energy consideration: low curing temperature (180 ºC is standard) 3. High efficiency: no drying process, powder waste recyclable

Film Mn (kDa) a PDI a Curing agent Stoichimetry [=]:[SH]

Curing T (oC)

F1 6.0 2.2 TMPMP 4:1 130

F2 2.8 1.8 TMPMP

4:1 130

F3 3.1 1.8 TMPMP

2:1 130

Polymer resin properties and formulation

Compounds Weight %

Function

TMPMP - Curing agent

Irgacure @651 2 Photo-initiator

Resiflow PV 5 1.5 Flow agent

Benzoin 0.754 Degassing agent

Coatings on Al plates

a Determined by GPC. The polymer resins used in the powder coating were obtained after breaking down the high molecular weight PLCs with 1,10-decanediol.

Films F1 F2 F3 Av. film thickness (micrometer) 64 75 84

PCI powder smoothness rating (1-10) 5-6 5-7 5-7 Adhesion to metal (ASTM D3359) 5B (100%) 5B (100%) 5B (100%)

Pencil hardness (ASTM D3363) 2H 3H 3H Falling dart impact (ASTM D2794) - - -

König hardness (ASTM D4366) 199 s 190 s 174 s Cupping test (ISO 1502) 1.8 mm 0.8 mm 1.8 mm

Acetone resistance (ASTM D4752) + + +

Higher application temperature helps to achieve good leveling

Low toughness. as indicated by the fast impact test and slow deformation cupping test

Good adhesion and acetone resistance

Hard coating

Powder Coating Tests of film F1 (Mn=6 kDa; 130 ºC. [=]:[SH] = 4:1)

NOTE: Collaboration with Paul Buijsen / Gert Dijkstra at DSM CR, Zwolle, NL

1. The curing reaction of α,ω-dihydroxyl PLCs with multifunctional non-blocked and blocked isocyanates after solvent casting is not complete because of the low reactivity of the secondary and tertiary OH end groups. 2. Post-modification of PLCs with primary hydroxyl functionality by thiol-ene chemistry enhances the reactivity with multifunctional isocyanates and improves the performance of the resulting cured coatings, which have tunable thermal properties. 3. Direct thiol-ene chemistry curing of PLCs using a trifunctional thiol compound is both possible using thermal and UV initiators and both curing methods seem to give sufficiently cross-linked films exhibiting good properties.

4. The UV curable powder coatings from PLCs with Mn ranging from ca. 3 to 6 kDa show promising properties like good metal adhesion, acetone resistance and high hardness. As for the solvent-casted coatings the toughness is poor.

Summary

15-10-2015 32

Eindhoven University of Technology Department of Chemical Engineering and Chemistry Laboratory of Polymer Materials T +31 40247 2175 / 5197 F +31 40246 3966 c.li@tue.nl / rafael.sablong@ptgeindhoven.nl c.e.koning@tue.nl / cor.koning@dsm.com www.fp7-refine.eu

Contact

Acknowledgement

Chunliang Li

Dr. Rafaël Sablong

Martin Fijten

Carin Dietz

Liliana Gustini

Other SPM group members

Susana Torron Timhagen (KTH, Sweden)

Prof. Mats Johansson (KTH, Sweden)

Dr. Paul Buijsen (DSM, Zwolle)

Dr. Gert Dijkstra (DSM, Zwolle)

REFINE (network, funds)

Elham Hosseini Nejad, et al. Macromolecules, 2013, 46 (3), pp 631–637

Rearrangement reaction of limonene oxide and MPVO reaction.

OO O

O mH

The structure was introduced after the copolymerization of LO and CO2 because of the rearrangement reaction and thus appeared as an unexpected structure after the transcarbonation reactions.