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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