Bis-Phenol A Alkoxylates

BPA Propoxylate

CH3

CH3

OO

OO

HH CH3CH3

n/2 n/2

BPA Ethoxylate

CH3

CH3

OO

OO

HH

n/2n/2

EO or PO Distribution

• Alkoxylated products always have a Poisson distribution

• Catalysis and/or reaction temperature can help control distribution

Uniqema’s Process

• Sophisticated post-treatment technique

• Low acid number

• Gardner color consistently at 1 or below

• Very low ion content (Na/K/P)

• Tight distribution

Features of BPA Alkoxylates

• Hydroxyl termination for use as a resin or a resin intermediate

• Aromatic moiety for resistance, adhesion and toughness

• Free rotation of methyl groups between aromatic groups for flexibility

• Limitless variations in size of EO, PO or EO/PO chains

Benefits of Using BPA Alkoxylates

• Corrosion resistance

• Chemical and moisture resistance

• Flexibility

• Toughness/hardness

• Improved adhesion

• Tg variation to meet final product needs

Uniqema Commercial Products

• Ethoxylated BPA– Atlas G 1672 2.2 mole EO– Atlas G 1672/4 2.4 mole EO– Atlas G 1673 3.0 mole EO– Atlas G 1674 BAA 4.0 mole EO– Atlas G 1676 6.0 mole EO– Atlas G 1680 BAA 10.0 mole EO– Atlas G 1682 BAA 12.0 mole EO– Atlas G 1688 BAA 18.5 mole EO– Atlas G 1690 BAA 30.0 mole EO

Uniqema Commercial Products

• Propoxylated BPA– Atlas G 1652D 2.0 mole PO– Atlas G 1652 2.2 mole PO– Atlas G 1653 3.0 mole PO– Atlas G 1654 4.0 mole PO – Atlas G 1657 7.0 mole PO– Atlas G 1663BAA 13.0 mole PO – Atlas G 1665 15.0 mole PO

Product Specifications and Production Locations

Name type of alkoxylate

nominal degree of alkoxylation

Colour Hydroxyl value type of terminal OH group

molecular

weight 1)

Viscosity Na + K water content

Appearance

Atlas … Gardner mg KOH/g Pas ppm %

European products, commercially available

G1652A PO 2,2 mol < 3 313 - 332 secondary 337 - 357 < 40 < 0,5 Viscous LiquidG1652D PO 2,2 mol < 2 309 - 334 secondary 335 - 362 < 50 < 0,5 Clear liquid @ 80ºCG1653 PO 3,0 mol < 1 270 - 290 secondary 386 - 414 5 - 7 @ 40ºC < 32 < 0,5 Clear, viscous liquidG1654 PO 4 mol < 250 Hazen 240 - 260 secondary 432 - 468 0,4 - 3,3 @ 40ºC < 0,2G1657 BAA PO 7 mol < 1 168 - 178 secondary 1,8 - 2,8 @ 25ºC < 50 < 0,1 Clear liquidG1663 BAA PO 13,5 mol secondaryG1665 PO 15 mol < 5 100 - 110 secondary 1018 - 1120 < 50 < 0,25G1672/4 BAA EO 2,4 mol < 250 Hazen 330 - 342 primary 328 - 340 < 20 < 0,1 Molten liquid at elevated temperatureG1676 EO 6 mol < 200 Hazen 217 - 239 primary 469 - 517 2,5 - 4,9 @ 25ºC < 50 < 0,5 Liquid

European products, samples available

G1672 EO 2,1 mol primaryG1673 EO 3 mol primaryG1680 BAA EO 10 mol primaryG1682 BAA EO 12 mol primaryG1688 BAA EO 18,5 mol primaryG1690 BAA EO 30 mol primary

Atlas point products, commercially available

G1652 PO 2,2 mol secondaryG1653 PO 3 mol secondaryG1666 PO 16 mol secondaryG1672 EO 2,2 mol primary

Asian Products, commercially available

G1672 K EO 2 mol 337 - 350 primary 320 - 332 White solid @ 20ºCG1676 K EO 6 mol primary 3,7 @ 25ºC 150 - 300G1680 BAAK EO 10 mol primary 1,4 @ 25ºC 150 - 300G1688 BAAK EO 18,8 mol primary 1,0 @ 25ºC 150 - 300

Table of specifications for Bisphenol A alkoxylates

GC-fingerprints of BPA ethoxylates (1)

G-1676 6 mol EO

G-1674 4 mol EO

G-1673 3 mol EO

0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0 11,0 12,0 13,0 14,0 15,0 16,0

G-1672 2 mol EO

GC-fingerprints of BPA ethoxylates (2)

G-1690BAA 30 mol EO

G-1688BAA 18 mol EO

G-1682BAA 12 mol EO

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

G-1680BAA 10 mol EO

Provisional Product Specifications - Asia

Name Type of nominal degree Colour Hydroxyl value Molecular Viscosity AV(mgKOH/g) Na + K pH Appearance Mol Distributionalkoxylate of alkoxylation Apha OH(mgKOH/g) weight Pas

Atlas … (One test)G1672 K EO 2.2 200 Apha max 337 - 350 Max 0.1 5-7 White solid 1 mol : Max 0.5

at 20 deg C 2 mol : Min 90Above 3 mol:Max10

G1676 K * EO 6 100 Apha max 224 - 232 3.7 @25 C 0.01 5.5-7.5 yellowish clear liquid H2O max : 0.5%(One test)

G1680BAAK* EO 10 350 Apha max 164 - 169.5 1.4 @25 C 0.17 5.5-7.5 yellowish clear liquid H2O max : 0.5%(one test)

G1688BAAK* EO 18.5 350 Apha max 106 -109 1.0 @25 C 0.21 5-7 yellowish clear liquid H2O max : 0.5%(one test)

G1690BAAK EO 30 100 Apha max 70.5 - 74.5 5.5-7.5 solid H2O max :0.5 %

G1653 K PO 3 80 Apha max 284 - 292 Max 0.1 5.5-7.5 Clear liquid 1 : no, 2 : 36.5-39.54: 15.5-18.5, 5: 2.5-5.5

* : Registered by Alain Bouvy.

GC-fingerprints of BPA (K) ethoxylates (3)

0

50

100

150

0 2 4 6 8 10 12 14 16

G-1676K 6 mol EO

G-1680 BAAK 10 mol EO

G-1688 BAAK 18.8 mol EO

Some components in ethoxylated BPA

component G-1672 G-1673 G-1674 G-1676 G-1680BAA

G-1682BAA

G1688BAA

G-1690BAA

> BPA 1.7 2.1 0.8 2.7 1.3 1.1 2.8 0.9

BPA 0.2 1.8 0.1 0.1 0.1 0.1 0.1 0

1 EO 1.2 8.7 2.4 1.3 0.2 0.1 0.1 0.2

2 EO 85 28.7 10.7 5.9 0.9 0.4 0.1

3 EO 9.1 30.7 25.2 9.5 2.1 1.3

4 EO 1.2 15.7 28.3 18.3 3.4 2.1

6 EO 6.9 16.9 19 5.9 4.7

higher ethoxylates cannot be assigned to peaks unambiguously

GC-fingerprints of BPA-propoxylates (1)

G-1654 4 mol PO

G-1653 3 mol PO

G-1652A 2 mol PO

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

G-1652D 2 mol PO

GC-fingerprints of BPA-propoxylates (2)

G 1663 B AA 13 PO

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34

G 1666 16PO

Current Uses

• Unsaturated polyester resins for fiberglass reinforcement, glass sizing and corrosion resistance– Use PO derivatives from 2.0 to 16.0– Provide moisture and chemical resistance,

adhesion, corrosion resistance

• Toner resins– Use EO and PO derivatives 2.0 - 2.2– Control of Tg (glass transition temperature)

Current Uses

• Electodeposition coatings– Use 6.0 EO derivative– Provides hardness for stone resistance and

adhesion

• Radiation curable monomers– Use EO derivatives from 2.2 to 30 moles– Provide resistances, hardness/flexibility and

adhesion

Current Uses

• Urethane foam and adhesives– Use various EO and PO derivatives– Provide adhesion to metal

Effect of BPAA in metal coating polyester system

• Polyester melamine system– solvent based– building blocks used

• Neopentylglycol, Hexanediol, Adipic acid, Isophtalic acid, Terephtalic acid

• Hexanediol and Neopentylglycol were used as reference and partially replaced with BPAA

Performance testing

• Hardness– König Hardness represents the visco-elastic

behaviour of a coating– Buchholz Hardness represents deformation

elasticity, i.e. a kind of recoverability (nail test), required for metal coating in particular

• Some applications require both properties

Coating properties improvement by using BPAA

12

13

14

15

16

17

18

0 20 40 60

König Hardness (sec)

Bu

cho

lz H

ard

nes

s (m

m)

PE containing BPA PO

PE containing BPA EO

PE without BPAA

BPAA give either a better König Hardness (when using lower alkoxylation degrees) or a better recoverability (herstelvermogen) at higher alkoxylation degrees or both!

2 mol PO

16 mol PO

4 mol PO

3 mol PO

2 mol EO

30 mol EO

4 mol EO

2,2 mol EO

Skip conditions

Polyester composition

Reference polyester

BPA variant

BPA-alkoxylate 0,0% 10,6%Neopentylglycol 29,6% 27,3%Hexanediol 11,2% 7,5%Adipic acid 10,8% 9,9%Isophtalic acid 24,2% 22,3%Terephtalic acid 24,2% 22,3%Parts by weight!

Polyester composition and differences figures

0%

20%

40%

60%

80%

100%

Referencepolyester

BPA variant

Terephtalic acid

Isophtalic acid

Adipic acid

Hexanediol

Neopentylglycol

BPA-alkoxylate

-5% 0% 5% 10% 15%

BPA-alkoxylate

Neopentylglycol

Hexanediol

Adipic acid

Isophtalic acid

Terephtalic acid

Polyester compositionby weight

Differences by weightbetween both ester

Melamine curing

• Polyester / melamine ratio: 15 / 1

• Pigment / binder ratio: 12 / 11

• The coating was applied and cured for 1 minute at 230ºC

BPAAUniqema’s business focus

• Commitment to & focus on the polymer market– Dedicated Polymer SBU– dedicated sales & marketing, TSS & application people

• Polymer di-functional building block experience

• Resin synthesis capability– e.g. polyester

• Developing application data & knowledge – polyester metal coatings

• Plants in more than one region – Europe and USA

• Potential to tailor make EO and PO products in both regions