Benefits of Cyclohexanoate Plasticizers in Silicone...

Benefits of Cyclohexanoate Plasticizers in Silicone Hybrid Systems; Part II

Adhesives and Sealants Council Fall 2016 Convention

Valtris: Who We Are

Created with HIG acquisition of Ferro Polymer Additives December, 2014

Headquarters and laboratories in Independence, Ohio, USA

Seven manufacturing sites – USA, Mexico and United Kingdom

Sixty years of operations & product development of Polymer Additives

Extensive range of Plasticizers, Lubricants, Stabilizers and Additives

Silyl-Terminated Hybrids

Attempts to take the benefits of both silicones and polyurethanes, without many of the negatives of either

Developed in Japan in the 1970’s

Formulating flexibility for properties including cure speed, translucence, 1K or 2K, flowability/sag, etc.

Notable advantages include better adhesion and wide operating temperatures

Silyl-Terminated Hybrid Benefits

Vs. Silicones• Better adhesion profile to

difficult substrates• Paintability• Methanol cure product,

as opposed to oxime or acetic

• Better tear strength

Vs. Polyurethanes• No residual isocyanates• Better adhesion profile to

difficult substrates• Higher performing in low

temperature environments• Less shrinkage from cure• Better UV resistance

Hybrid Applications

• Construction sealant and adhesive• Bathroom sealant and adhesive• Vibration insulating• Marine applications• Flooring adhesive• Roofing sealant/adhesive

Hybrid Type Chemistry Differences

– Polyurethane• Better chemical resistance

– Polyether• More stable• Larger service

temperature range

Si O CH3

CH3

OCH3

(CH2)3OSiOH3CCH3

OCH3

(CH2)3 O CH2 CHCH3

n

n

Si O CH3

CH3

R3NH

CO

OR2OCO

NH

SiOH3CCH3

OCH3

R3 NH

CO

O R2 O CO

NH

R1

OCH3nm

Cyclohexanoate Plasticizers

• Similar performance properties to phthalates

• Interacts differently in metabolic processes

• Different toxicological profile than phthalates

O

O

O

ORCH2

O

O

O

ORCH2

Cyclohexanoate Plasticizers In Hybrid Sealants

• Hybrids need a plasticizer

• Low microbiological growth potential

• Low water solubility

Cyclohexanoate Structures Evaluated

OO

O

O

Benzyl Butyl 1,2 cyclohexyldicarboxylate (BBCH)

Di-isononyl 1,2 cyclohexyldicarboxylate (DICH)

OO

O

OBenzyl Isononyl 1,2 cyclohexyldicarboxylate (BINCH)

OO

O

O

O

O

Benzyl 2,2,4-trimethyl-1,3-pentanediolmono(2-methylpropanoate)cyclohexyldicarboxylate (BXCH)

Cyclohexanoate Plasticizers Properties

BBCH BBP BXCH BXP BINCH BINP DICH DINP DOTP ASE

Viscosity(cP @ 25 C)

30 70 682 860 85 100 60 102 100 140

SpecificGravity

1.04 1.12 1.07 1.09 1.03 1.06 0.95 0.97 0.98 1.07

Volatility(% EPA 24)

2.2 2.3 0.1 0.1 0.1 0.3 0.2 0.1 0.5 0.3

Previous Work (Part I, ASC Fall 2015)

• High and low modulus formulas• Filled and Unfilled• Properties

– Mechanical (tensile strength, elongation)– Water sensitivity– Skin times/Tack free time– Paintability– Microbial growth– Plasticizer efficiency

• Compared phthalate and non-phthalate derivatives, in addition to non-phthalate chemistries

Silyl-Terminated Polyether Testing – Formula B

• Higher Modulus Formula• 1K RTV Sealant• Filled• Pigmented white, thixotropic paste (no sagging observed)• Primerless; Aminosilane Adhesion Promoter• Plasticizer loading at 18%• Looked at comparing between non-phthalate plasticizers

– New cyclohexanoate added to study (BXCH)• No sign of incompatibilities

Silyl-Terminated Polyether Testing – Methods

• Rheometry– Structure recovery– Thixotropic behavior

• Adhesion – Lap shear– Aluminum – Rigid PVC– Wood

• Weathering– UV exposure– Periodic Water Washes

Silyl-Terminated Polyether Testing

• Rheology – Restructuring– All

Silyl-Terminated Polyether Testing – Formula B; Part II

2250 25 50 75 100 125 150 175 200

� (s)

10 2

10 3

10 4

10 5

� (P

a)


• Rheology – Restructuring– DINP and DICH (phthalate and cyclohexanoate analogs)


DICH

DINP

2250 25 50 75 100 125 150 175 200

� (s)

10 2

10 3

10 4

10 5

� (P

a)




DICH

DINP

100 120 140 160 180

� (s)

1420.04

3519.33

� (P

a)


• Rheology – Restructuring– DICH, BBCH, BXCH (cyclohexanoates)


BBCH

BXCH

DICH

2000 25 50 75 100 125 150 175

� (s)

10 2

10 3

10 4

10 5

� (P

a)




BBCHBXCH

DICH

16090 100 110 120 130 140 150

� (s)

1707.70

3220.93

� (P

a)


• Rheology – Restructuring– DICH, DOTP (Non-phthalate GPs)


DICH

DOTP

2000 25 50 75 100 125 150 175

� (s)

10 2

10 3

10 4

10 5

� (P

a)




DOTP

DICH

100 120 140 160 180

� (s)

2009.35

4522.72

� (P

a)


• Rheology – Restructuring– BBCH, BXCH, ASE (High solvating, non-phthalates)


BBCHASE

BXCH

2000 25 50 75 100 125 150 175

� (s)

10 2

10 3

10 4

10 5

� (P

a)




BBCH

ASEBXCH

14090 100 110 120 130

� (s)

1665.90

2577.93

� (P

a)


• Rheology – Thixotropic Behavior– All


3.5x10 -35.0x10 -4 1.0x10 -3 1.5x10 -3 2.0x10 -3 2.5x10 -3 3.0x10 -3

S (1/s)

100

20

30

40

50

60

70

80

90

A (P

a)




DICHDINP

3.5x10 -35.0x10 -4 1.0x10 -3 1.5x10 -3 2.0x10 -3 2.5x10 -3 3.0x10 -3

S (1/s)

100

20

30

40

50

60

70

80

90

A (P

a)




BBCH

BXCH

DICH

2.75x10 -35.00x10 -4 7.50x10 -4 1.00x10 -3 1.25x10 -3 1.50x10 -3 1.75x10 -3 2.00x10 -3 2.25x10 -3 2.50x10 -3

S (1/s)

100

20

30

40

50

60

70

80

90

A (P

a)




DICH

DOTP

2.75x10 -35.00x10 -4 7.50x10 -4 1.00x10 -3 1.25x10 -3 1.50x10 -3 1.75x10 -3 2.00x10 -3 2.25x10 -3 2.50x10 -3

S (1/s)

100

20

30

40

50

60

70

80

90

A (P

a)


Silyl-Terminated Polyether TestingSilyl-Terminated Polyether Testing – Formula B; Part II

BBCH

ASE

BXCH

2.75x10 -35.00x10 -4 7.50x10 -4 1.00x10 -3 1.25x10 -3 1.50x10 -3 1.75x10 -3 2.00x10 -3 2.25x10 -3 2.50x10 -3

S (1/s)

100

20

30

40

50

60

70

80

90

A (P

a)

• Adhesion – Lap Shear on Aluminum – All Adhesive Failure


GPs High Solvators

Analogs Analogs

• Adhesion – Lap Shear on Wood – Even Failure Modes


GPs High Solvators

Analogs Analogs

• Adhesion – Lap Shear on Rigid PVC – Mostly Cohesive Failure


GPs High Solvators

Analogs Analogs

• Weathering – Color Generation – Delta E


400 hours 800 hours

DOTP 1.24 1.03

DINP 0.95

DICH 0.81 1.43

BXCH 0.89

BBCH 0.35 4.56

BBP 0.78

ASE 3.43

GPs

HighSolvators

Analogs

Analogs

• Weathering – Mechanical Properties Loss


Tensile Strength Loss Elongation Loss

400 hours 800 hours 400 hours 800 hours

DOTP -9 PSI 28 PSI 41% 191%

DINP -46 PSI 43%

DICH -58 PSI -21 PSI -9% 127%

BXCH -2 PSI 109%

BBCH -42 PSI -15 PSI 45% 157%

BBP -20 PSI 75%

ASE 49 PSI 199%

GPs

HighSolvators

Analogs

Analogs

Closing Summary

• Cyclohexanoates show very similar performance characteristics to phthalate analogues with less regulatory considerations.

– Slightly less shear thinning– Better adhesion to some substrates (wood and PVC)– Better weathering resistance (color)

• Cyclohexanoates offer some advantages over some competitive non-phthalate chemistries.

– Versatility in selecting performance capabilities

Thank You for Your Attention

Thanks to:– ASC for the opportunity to present today.– Valtris for the use of facilities and resources.– Kaneka for the materials to run evaluations.– Karla Hilbert for help with analysis.

Ron RaleighMarketing and Tech. Service ChemistValtris Specialty ChemicalsIndependence, [email protected]

Benefits of Cyclohexanoate Plasticizers in Silicone...

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