Transcript Polymers MPC

Bis-Phenol A
Alkoxylates
BPA Propoxylate
H
CH 3
H 3C
O
H
O
O
n/2
O
CH 3
CH 3
n/2
BPA Ethoxylate
H
H
O
O
O
n/2
O
CH3
CH3
n/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
Atlas G 1672/4
Atlas G 1673
Atlas G 1674 BAA
Atlas G 1676
Atlas G 1680 BAA
Atlas G 1682 BAA
Atlas G 1688 BAA
Atlas G 1690 BAA
2.2 mole EO
2.4 mole EO
3.0 mole EO
4.0 mole EO
6.0 mole EO
10.0 mole EO
12.0 mole EO
18.5 mole EO
30.0 mole EO
Uniqema Commercial Products
• Propoxylated BPA
–
–
–
–
–
–
–
Atlas G 1652D
Atlas G 1652
Atlas G 1653
Atlas G 1654
Atlas G 1657
Atlas G 1663BAA
Atlas G 1665
2.0 mole PO
2.2 mole PO
3.0 mole PO
4.0 mole PO
7.0 mole PO
13.0 mole PO
15.0 mole PO
Product Specifications and
Production Locations
Table of specifications for Bisphenol A alkoxylates
Name
type of
nominal degree Colour
alkoxylate of alkoxylation
Atlas …
Gardner
Hydroxyl value type of terminal molecular
OH group
weight 1)
Viscosity
Na + K
water
content
mg KOH/g
Pas
ppm
%
Appearance
European products, commercially available
G1652A
G1652D
G1653
G1654
G1657 BAA
G1663 BAA
G1665
G1672/4 BAA
G1676
PO
PO
PO
PO
PO
PO
PO
EO
EO
2,2 mol
2,2 mol
3,0 mol
4 mol
7 mol
13,5 mol
15 mol
2,4 mol
6 mol
<3
<2
<1
< 250 Hazen
<1
<5
< 250 Hazen
< 200 Hazen
313 - 332
309 - 334
270 - 290
240 - 260
168 - 178
secondary
secondary
secondary
secondary
secondary
secondary
100 - 110 secondary
330 - 342 primary
217 - 239 primary
337 - 357
335 - 362
386 - 414
5 - 7 @ 40ºC
432 - 468 0,4 - 3,3 @ 40ºC
1,8 - 2,8 @ 25ºC
< 40
< 50
< 32
1018 - 1120
328 - 340
469 - 517 2,5 - 4,9 @ 25ºC
< 50
< 20
< 50
< 50
<
<
<
<
<
0,5
0,5
0,5
0,2
0,1
Viscous Liquid
Clear liquid @ 80ºC
Clear, viscous liquid
Clear liquid
< 0,25
< 0,1 Molten liquid at elevated temperature
< 0,5 Liquid
European products, samples available
G1672
G1673
G1680 BAA
G1682 BAA
G1688 BAA
G1690 BAA
EO
EO
EO
EO
EO
EO
2,1 mol
3 mol
10 mol
12 mol
18,5 mol
30 mol
primary
primary
primary
primary
primary
primary
Atlas point products, commercially available
G1652
G1653
G1666
G1672
PO
PO
PO
EO
2,2 mol
3 mol
16 mol
2,2 mol
secondary
secondary
secondary
primary
Asian Products, commercially available
G1672 K
G1676 K
G1680 BAAK
G1688 BAAK
EO
EO
EO
EO
2 mol
6 mol
10 mol
18,8 mol
337 - 350 primary
primary
primary
primary
320 - 332
White solid @ 20ºC
3,7 @ 25ºC 150 - 300
1,4 @ 25ºC 150 - 300
1,0 @ 25ºC 150 - 300
GC-fingerprints of BPA
ethoxylates (1)
G-1676 6 mol EO
G-1674 4 mol EO
G-1673 3 mol EO
G-1672 2 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
GC-fingerprints of BPA
ethoxylates (2)
G-1690BAA 30 mol EO
G-1688BAA 18 mol EO
G-1682BAA 12 mol EO
G-1680BAA 10 mol EO
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Provisional Product
Specifications - Asia
Name
Type of
nominal degree Colour
alkoxylate of alkoxylation Apha
Hydroxyl value Molecular Viscosity AV(mgKOH/g) Na + K
OH(mgKOH/g) weight
Pas
(One test)
200 Apha max
337 - 350
Max 0.1
Atlas …
G1672 K
EO
2.2
G1676 K *
EO
6
100 Apha max
224 - 232
3.7 @25 C
G1680BAAK*
EO
10
350 Apha max
164 - 169.5
1.4 @25 C
G1688BAAK*
EO
18.5
350 Apha max
106 -109
1.0 @25 C
G1690BAAK
EO
30
100 Apha max
70.5 - 74.5
G1653 K
PO
3
80 Apha max
* : Registered by Alain Bouvy.
284 - 292
0.01
(One test)
0.17
(one test)
0.21
(one test)
Max 0.1
pH
Appearance
Mol Distribution
5-7
White solid
at 20 deg C
5.5-7.5 yellowish clear liquid
1 mol : Max 0.5
2 mol : Min 90
Above 3 mol:Max10
H2O max : 0.5%
5.5-7.5 yellowish clear liquid
H2O max : 0.5%
5-7
yellowish clear liquid
H2O max : 0.5%
5.5-7.5 solid
H2O max :0.5 %
5.5-7.5 Clear liquid
1 : no, 2 : 36.5-39.5
4: 15.5-18.5, 5: 2.5-5.5
GC-fingerprints of BPA (K)
ethoxylates (3)
150
100
G-1688 BAAK 18.8 mol EO
50
G-1680 BAAK 10 mol EO
G-1676K 6 mol EO
0
0
2
4
6
8
10
12
14
16
Some components in
ethoxylated BPA
component
G-1672
G-1673
G-1674
G-1676
G-1680
BAA
G-1682
BAA
G1688
BAA
G-1690
BAA
> 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
6.9
16.9
19
5.9
4.7
6 EO
higher ethoxylates cannot be assigned to peaks unambiguously
GC-fingerprints of BPApropoxylates (1)
G-1654 4 mol PO
G-1653 3 mol PO
G-1652A 2 mol PO
G-1652D 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
GC-fingerprints of BPApropoxylates (2)
G 1663 BAA 13 PO
G1666 16PO
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
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
Bucholz Hardness (mm)
18
PE containing BPA PO
16 mol PO
30 mol EO
17
PE containing BPA EO
2 mol EO
16
4 mol EO
15
PE without BPAA
3 mol PO
4 mol PO
2,2 mol EO
14
13
2 mol PO
12
0
20
40
60
BPAA give either a
better König Hardness
(when using lower
alkoxylation degrees)
or a better
recoverability
(herstelvermogen) at
higher alkoxylation
degrees or both!
König Hardness (sec)
Skip
conditions
Polyester composition
BPA-alkoxylate
Neopentylglycol
Hexanediol
Adipic acid
Isophtalic acid
Terephtalic acid
Parts by weight!
Reference BPA
polyester variant
0,0%
10,6%
29,6%
27,3%
11,2%
7,5%
10,8%
9,9%
24,2%
22,3%
24,2%
22,3%
Polyester composition and
differences figures
Polyester composition
by weight
Differences by weight
between both ester
Terephtalic acid
100%
Isophtalic acid
80%
Terephtalic acid
60%
Adipic acid
Isophtalic acid
Adipic acid
Hexanediol
40%
Hexanediol
Neopentylglycol
BPA-alkoxylate
20%
Neopentylglycol
0%
Reference
polyester
BPA variant
BPA-alkoxylate
-5%
0%
5%
10%
15%
Melamine curing
• Polyester / melamine ratio: 15 / 1
• Pigment / binder ratio: 12 / 11
• The coating was applied and cured for 1 minute
at 230ºC
BPAA
Uniqema’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