Polyols and Powder Coating R

esins

Gary Li ( )
November 13, 2015

Pioneer Chemicals Co.

Outlines
Polyol Fundamentals
Polyol Products and Properties
Basics of Polyol Chemistry
Powder Coating Resins
Q&A

2015/11/13

for Pioneer Chemicals internal training only

Polyol Fundamentals

2015/11/13

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Terminologies
1. Do they mean the same thing?
Hydroxyl functional acrylic resin, acrylic polyol
OH%, hydroxyl value (OHV), hydroxyl number (OH#), hydroxyl equivalent weight (OH EW)
Acid value (AV), acid number (AN)
Functioanlity, functional group
Hardener, hardening agent, crosslinker, crosslinking agent, curing agent, curative
Waterborne (WB), water-based, water soluble, water dispersible
Solventborne (SB), solvent-based
Dispersion, emulsion, solution

2. thermoplastic vs. thermoset (heat cure) vs. ambient cure vs. UV cure
3. two-component (2K) vs. one-component (1K)
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Polyester Polyol and Polyether Polyol

Polyether polyol
O
H

CH2CH2C
H2

CH2CH2C
H2

O
n

CH2CH2CH O
H
2

terminal OH
groups

Polyester polyol
H
O

CH2CH2
CO

CH2CH2 C

O
n

CH2CH2CH O
H
2

O
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Acrylic Polyol
Acrylic polyol
R
CH

R
CH

COO
R

COOCH2C O
H
H2

pendant side OH
groups
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Hydroxyl Number/Hydroxyl Equivalent Weight

/ OH%
1.Hydroxyl number (value): mg KOH/g (OH content per gram of resin sam
ple)

For polyester polyol and polyether polyol , OH number is inversely proporti

onal to MW. (higher MW lower OH number)
2. Hydroxyl equivalent weight: weight of resin per mole of OH group
Hydroxyl equivalent weight

= (higher OH EW lower OH number)

3. (higher OH%, higher OH number)

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Polyol Products and Properties

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Polyester Polyols

x
x
x
x

=11220
0 11220
=
0
=11220
0 11220
=
0

MW x OH number = constant
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Pioneers PChem and HChem Acrylic Po

lyols
1. Resin solid content: 50 - 100%
2. PChem : solid acrylic polyols ; HChem: liquid acrylic polyols (resin + solvent)
3. Molecular weight: low (3,000), medium (25,000), high (400,000)
4. PChem features and benefits:
.Broad range in OHV, MW, Tg, composition; unlimited possibilities for application formulations
.React with isocyanate and melamine crosslinkers
.Low OHV resins suitable for reactive hot melt adhesives
.Easy material handling and storage
.Flexibility and wide formulation latitude: allow coating producers to choose their own solvents
.Chemical resistance and hardness due to limited amount of oligomers and residual monomers
.High DOI (distinctness of image

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Pioneer Chemicals HChem Acrylic Polyols (liquid)

Product

NonVolatiles
(%)

Viscosity
(Gardner )

Color
(APHA)

Tg ( C)

Acid #

Hydroxyl #

PA-4255

501

X-Z1

50

55

22-27

66

Tol/BA

PA-4257

601

S-W

50

10

4-6

119

Xylene

Solvent

Application
Waterborne industrial coating

Basecoat of automotive and motorcycle coating

PA-4258

601

X-Z2

50

20

2-4

63

Xylene/BA

PA-4265

651

Z2-Z5

50

45

5-8

86

Xylene/BA

PA-4265H

601

W-Z

50

30

6-9

86

Xylene

PA-4267

701

Z3-Z6

50

50

4-6

96

Xylene/BA

PA-4268

701

Z2-Z5

50

53

6-9

115

BA

PA-4270

701

Z3-Z6

50

48

6-10

139

BA

PA-4271

701

X-Z1

50

36

9-12

139

BA

PA-4273

701

Z2-Z5

50

46

5-9

126

S100

PA-4274B

751

Z3-Z6

50

47

6-10

138

BA

PA-4350

501

T-X

50

27

33

Tol/MIBK

Coatings for machinery and equipment; Metallic coating

on plastic substrates

Industrial coating, automotive refinish

Clearcoat of industrial coating, automotive refinish

Clearcoat of industrial coating, automotive refinish

Automotive topcoat

Automotive topcoat

Automotive topcoat

Automotive topcoat

Clearcoat, automotive refinish

1K, 2K plastic coating

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11

Competitor Ms Acrylic Polyols (liquid)

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Competitor Ms Acrylic Polyols (liquid)

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13

Numerical
scale

For HChem liquid acrylic polyol

resins
solution viscosity is key
application property
Liquid OH acrylic resin (solution)

Alphabetic
scale

OH acrylic
polymer
solvent

Solid OH acrylic
resin (beads or
granules)
dissolving
Viscosity 500
20,000 cps

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3

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14

Pioneer Chemicals PChem Acrylic Polyol

s (solid)
Product
BM44D
BM46
BM51
BM52
BM53
BM54
BM55HB
BM260
BM261
BM262
BM268
BM655
BM666
BM667
BM716
BM751
BM754
BM755

Solid%
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100

Mw
100,000
100,000
60,000
70,000
40,000
72,500
100,000
20,000
20,000
50,000
250,000
10,000
5,000
5,000
400,000
25,000
20,000
21,000

I.V.
0.40
0.40
0.24
0.28
0.17
0.28
0.47
0.11
0.11
0.24
0.65
0.10
0.06
0.06
0.55
0.14
0.13
0.13

Tg (C)
54
82
33
63
102
52
66
50
66
50
75
62
63
63
-45
49
22
12

Acid#
<1
<1
5
67
<1
7
<1
7
7
7
5
55
7
7
<1
6
3
3

Hydroxyl #
26
13
60
22
22
40
43
35
80
80
66
24
140
128
13
9
11
11

Applications
Hot melt adhesives
Hot melt adhesives
Printing ink
Printing ink
Printing ink
Hot melt adhesives
Industrial coating, general metal coating
Printing ink,
Printing ink,
Industrial coating, automotive topcoat, automotive refinish
Industrial coating
Printing ink
Printing ink, general metal coating, furniture coating
Printing ink, general metal coating, furniture coating
Pressure sensitive adhesive, hot melt adhesives
Hot melt adhesives, printing ink
Hot melt adhesives,
Hot melt adhesives

For coatings, it is possible to use PChem solid polyol resins to

replace liquid polyol resins, or create new applications that have
advantages over solution
resins.
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Chemicals internal training only
15

How to Recommend PChem Solid Pol

yols?
Example: MB-2752 replacement?
Check OHV = 90, look for PChem Polyol that has closer OHV
Find BM261, OHV = 80
Check Mw= 17,000
Find BM261, Mw = 20,000
Check Tg = 67, AV = 7
Find BM261, Tg= 66, AV=7
Whether BM261 is a suitable drop-in replacement is subject to customer evaluation.
Although bringing in $$$ is the most important, you are encouraged to learn about custo
mer formulations/ applications as much as possible!
2015/11/13

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16

Comparison among Polyols

Property

2015/11/13

OH-acrylic resins

OH-polyester

OH-alkyd resins

Wetting

Adhesion

Physical drying

Flow and
leveling

Hold out

Gloss

Crosslinking
efficiency

Hardness

Flexibility

Chemical
resistance

Solvent
resistance

Wettability

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2 only
for Pioneer

17

Acrylic Polyols for Coatings

Mainly for paints and coatings, especially PU coatings for automotive finish due to good
chemical resistance and durability
Typical monomer composition: MMA, EA, BA, AA, ST (more hydrophobic), HEA, HBA (mo
re reactive)
Resins for SB 2K-PUR
- OH%: 0.5 3.5%, OH EW: 3,400 500
- NV (non-volatile): 40 -100%,
- solvents: xylene, naphtha, butyl acetate, 1-methoxypropyl acetate,
- solution viscosity: 1,800 9,000 mPa.s (cps)
Resins WB 2K-PUR
- OH%: 2.0 4.8%
- NV: 40 45%
- Organic co-solvent: 0 10%, solution viscosity: 200 1,500 mPa.s
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Basics of Polyol Chemistry

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19

Reaction with Isocyanate

two-component (2K) system
reaction at ambient temperature is possible

One OH only reacts

with one NCO
One water molecule
(H2O) can consume two
NCO groups

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20

Crosslinking with Isocyanate

Isocyanate Index: 85 to 110 to achieve optimum film/foam/bond pro
perties
Based on the
assumption that one
OH reacts with one
NCO

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21

Crosslinking Efficiency in 2K PUR System

Polyisocyanate crosslinker (HDI
trimer)
3 NCO/molecule
BM262 (acrylic
polyol)
MW=5000
70 OH/molecule

OH
NCO

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22

Acrylic Polyols (crosslinking with isocyanates)

1. Reaction rate of isocyanates: aromatic > aliphatic at primary C atoms > alip
hatic at secondary C atoms> aliphatic at cycloaliphatic rings> aliphatic at terti
ary C atoms
2. Aromatic isocyanate crosslinker primers, indoor coatings due to poor we
atherability
3. Best-known crosslinkers: biuret trimer of hexamethylene diisocyanate, isoc
yanurate trimer of hexamethylene diisocyanate and isophorone diisocyana
te
4. Catalysts: organic salts of heavy metals, tertiary amines, hetrocyclic nitro
compound (e.g. di-n-butyl tin dilaurate DBTL, organo-vanadium salts or organ
o-zinc salts/heterocyclic N compounds)
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Acrylic Polyols (crosslinking with isocyanates)

5. Pot life (same hardener, same viscosity) depends on monomer selection
2-hydroxypropyl methacrylate (2-HPMA) > 2-hydroxypropyl acrylate (2-HPA) > 2- hydroxyethyl methac
rylate (2-HEMA) > 2-hydroxyethyl acrylate (2-HEA) > 4- hydroxybutyl acrylate (4-HBA)
6. OH value
50-90 mg KOH/g (2K industrial coatings, wood finishes, less expensive paints)
80-120 mg KOH/g (better resistance)
120-160 mg KOH/g (high solids system)
acid value < 10 mg KOH/g (thus, COOH will not catalyze the crosslinking)
7. Tg: lower for plastic coatings, higher for metal coatings
8. Applications
wood finishes, metal paints (machines, appliances), plastics , leather, automotive repair finishes, autom
otive OEM coatings (topcoats and clear coats, can outperform acrylic/melamine )
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Hydroxyl-Functional Acrylic Resins

(crosslinking with blocked polyisocyanates)
Pot-life for 2K system is an hindrance
for some applications, although spray
guns might work.
But restrictions on blocking agents du
e to issues with health, environmenta
l risks, solubility.
Combination of blocked polyisocyana
tes and melamine resins to achieve hi
gher hardness and lower cost , e.g. A
uto OEM clear coats (excellent weath
erability, optimum chemical resistanc
e, balanced hardness and flexibility)
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Blocking agent

Effective reaction
temperature (oC)

-Caprolactam

160

1,2,4-Triazole

155

Methyl ethyl ketoxime

150

3,5-Dimethyl-1,2pyrazole

145

Ethyl acetoacetate

140

Diethyl malonate

130

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25

Crosslinking with Melamine Resins

methylol
group

methylol
ether group

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26

Hydroxyl-Functional Acrylic Resins

(crosslinking with amino resins)
Reaction at elevated temperature (125-200oC), or 80oC with acid catalyst (e.g. p-tol
uenesulphonic acid, PTSA), or free acid monomer in resins to provide catalytic effe
ct
MW: 3,000-8,000, OH value: 60-130 mg KOH/g, acid value: 10-25, Tg: -10-50oC, solid
: 50-70% in aromatic HC
Applications: baking enamels for industrial appliances, automotive OEM finishes
Majority of such resins from solution polymerization (how do solid resins compete
with solution resins?)

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27

Acrylic polyols could be water-based

Acrylic polyol: Ottopol 522 is a hydroxyl
Functional acrylic emulsion
Hardener: Cymel 303 is an
amino crosslinker

Acrylic polyol: Ottopol 522 is a hydroxyl

Functional acrylic emulsion
Hardener: Bayhydur XP-7063 is a
water dispersible polyisocyanate
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Powder Coating Resins

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Powder Coatings

Coating application process: continuous or batchwise

Substrates: metal or non-metal or heat-sensitive
Unused powder is recoverable
Suitable for parts and modules prior to assembly
2015-2018 CAGR for is 6%

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Powder Coating Formulation

Binders (resins, crosslinkers)
Pigments
Extenders (fillers)
Flow or leveling agents
Additives (e.g. degassing agent)
No solvent, no volatile, no small molecules that cause blocking o
r migration problems
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Classical Process Flow for Manufacturing Powder C

oatings

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Types of Powder Coatings

By function
Protective
Decorative
By hardening mechanism
Thermoplastic
Thermoset (discussed today)
UV curable
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Thermoset Powder Coatings

1. Polyester powder coatings
Workhorses of the powder coatings market
More than 60 percent of the market uses polyester-based powder coating
s, which hold up very well to standard outdoor exposure
Polyesters give the coater a broad application field
Polyester (carboxyl functional, - COOH)/TGIC (triglycidyl isocyanurate, har
dener) is the primary choice
Polyester TGIC-free powder coatings are gaining ground (Hydroxyalkyl A
mide, HAA hardener : Primid XL-552)

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Thermoset Powder Coatings

Polyester (hydroxyl functional, -OH) /isocyanate (hardener) based polyure
thane coatings are used for exterior applications. Allow formulation of m
ore stabilized low-gloss powder coatings for exterior applications.
Polyester (-OH) /isocyanate based polyurethane coatings also show bette
r chemical resistance than standard polyester/TGIC products and are use
d for anti-graffiti coatings. Slower cure is part of this chemistry because o
f de-blocking of the isocyanate hardener. Unfortunately, that results in so
me VOCs during evaporation of the blocking agent.
Super-durable polyester resins have grown immensely in the American c
oatings market in last decade, dominating much of the coastal and south
ern U.S. markets due to elevated color stability and gloss retention. key
monomer in resin: IPA
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35

Thermoset Powder Coatings

2. Epoxy powder coatings
Interior applications, excellent chemical and corrosive resistance
A strong protective primer layer under a polyester coating to dram
atically increase salt spray resistance.
Applications for epoxy systems include pipeline and concrete reba
r because of their flexibility and corrosion-protection properties.
Hybrid powder coatings are a mixture of both polyester (-COOH) a
nd epoxy resins or polyester and acrylic resins, mainly for interior
applications, most commonly applied to furniture.
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36

Thermoset Powder Coatings

3. Silicone powder coatings
high-heat applications
first level modified polyester resins, providing a stabilized exposure te
mperature as high as 400600 oF (204316 oC), allowing spike temperatur
es around 800oF (427oC) for a short period of time
second level exposure from 600 to 800oF (316427oC), allowing spike te
mperature around 9001,000oF (482538oC)
third level : 100% silicone system, exposure at 1,0001,100 oF (538593oC)
Common issue: Since most silicone powder coatings require curing at te
mperatures above 400oF (204oC) for an extended amount of time, iron an
d zinc phosphate pretreatments often fail at temperatures higher than 40
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37
0oF (204oC).

Thermoset Powder Coatings

4. Acrylic powder coatings
Carboxyl (-COOH) functional acrylic resin
COO
COO
COOH acrylic: AV 100 - 200 mg KOH/g
H
H
Binder: Epoxy resin + epoxy hardener + COOH acrylic matting additive (ha
rdener)
COOH acrylic usage: 2-10% on epoxy resin
OH
OH
Coating film gloss: 5-30%
Hydroxyl (-OH) functional acrylic resin
OH acrylic: OHV 50 - 150 mg KOH/g, reactive with isocyanate hardener in
PU powder coating
OH
Hydroxyl/epoxy functional
acrylic
resin
for Pioneer
Chemicals
internal training only
2015/11/13

38

Thermoset Powder Coatings

GMA acrylic resins
Primarily in the automotive sector as clear coat materials.
Very smooth clear coat with exceptional clarity, also very hard
surface that is highly chip-resistant.
Glycidyl methacrylate (GMA) acrylics are highly contaminating,
could result in craters in the finish of parts using the other pow
der chemistries.

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39

Key Properties of Each Generic Type of

Thermoset Powder Coating

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Reaction of GMA Acrylic Resins

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Key Properties for GMA Acrylics

1. EEW (epoxy equivalent weight)
Weight of resin / one mole of epoxy functional group
The amount of required hardener depends on EEW
2. Melt viscosity
The melting behavior of powder coating depends on resin viscosi
ty
The leveling and smoothness for coating film depends on melt vi
scosity
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42

Developmental Products GMA Acrylics

1. GA-003
- General purpose, epoxy functional acrylic resin (GMA acrylic)
- Clear coat with high gloss, smoothness and clarity
- Typical applications: wheel, automotive trims, primer/surfacer

2. GA-0266
- Crosslinker for polyester resins
- Gloss control agent in matte powders
- Typical applications: automotive trims, architecture metals, high-end patio furniture

3. GA-0254
- Film forming resin
- Excellent flow property, high DOI (distinctness of image)
- Typical applications: automotive wheels, parts and brass hardware
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Tentative GA-003 Specifications

Property
Molecular Weight
Glass Transition Temperature
(oC)
Epoxy Equivalent Weight
Melt Viscosity (@ 150 oC, poise)
Volatiles %
Color (Gardner)

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Value
6,000 14,000
46 50

for Pioneer Chemicals internal training only

510 - 560
200 - 240
< 0.5%
<2

44

Tentative GA-0254 Specifications

Color
Property
(Gardner)
Molecular Weight
Glass Transition Temperature
(oC)
Epoxy Equivalent Weight
Melt Viscosity (@ 150 oC, poise)
Volatiles %
Color (Gardner)

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Value
<2
46 - 52
505 - 545

45

Tentative GA-0266 Specifications

Property
Molecular Weight
Glass Transition Temperature
(oC)
Epoxy Equivalent Weight
Melt Viscosity (@ 150 oC, poise)
Volatiles %
Color (Gardner)

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Value
44 - 48
595 - 635

46

Classical Process Flow for

Manufacturing Solid GMA
Acrylic
Resin
1. Monomers/solvent
feed
If our bulk
polymerization
process offers the
same or better
quality of products,
we will definitely
have cost
advantage!

2015/11/13

2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.

Polymerization reactor
Holding tank
Storage tank
Heating medium 170oC
Evaporating extruder or
thin-film evaporator
Melting resin tank
Steam
Cooling belt
Crushing machine
Packaging
Vacuum
Cold water
Solvent recycle system

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47

Future Prospects on New Product Development for

Solid Acrylic Powder Coating Resins

OH
Glycidyl (epoxy) functional acrylic

COO
COO
H acrylic
H
Carboxyl
functional

Dual functional acrylic

OH

OH

Hydroxyl functional acrylic

Pioneer Chemicals existing manufacturing process is capable, with

minimal process change.
- It is in line with our new business development strategy for high-margin
specialty resins, such as powder coating binders, matting additives, flow
2015/11/13
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control agents, crosslinkers
etc.
-

48

More reasons not to overlook the opportunity for

acrylic power coating resins
In 2014, global powder coating market is worth 10 billions USD, in which
acrylic powder coating accounts for about 400 millions USD. In China, the
acrylic powder coating market value is estimated 200 millions USD.
Power coatings formulated with resins like GA-003 is estimated to have 810% compound annual growth rate (CAGR) between 2015 and 2020.
For two decades, global supply for the acrylic resins to powder coating m
anufacturers has been limited to very few producers. It is a great opportu
nity for Pioneer Chemicals to get into this market.

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49

Tests
Q: Which coating property does acrylic polyols perform better than polyester polyols?
A: 1. Adhesion, 2. Physical drying, 3. Gloss, 4. Crosslinking efficiency, 5. wetting
Q: Does lower hydroxyl number mean higher hydroxyl equivalent weight?
A: Yes
Q: What two types of crosslinkers (hardeners) are commonly used with acrylic polyols?
A: melamine (amino) and (poly)isocyanate
Q: What is the first thing youd like to know before recommending our acrylic polyols as replacemen
t?
A: 1. molecular weight, 2. Tg, 3. hydroxyl value (number), 4. acid value
Q: What is the functional group in our current developmental acrylic resins for powder coatings?
A: 1. hydroxyl, 2. carboxyl, 3. epoxy, 4. vinyl
Q: If acrylic polyol is formulated with amino crosslinker, what type of system is this?
A: 1. WB, 2. ambient cure, 3. 2K (two-component), 4. 1K (one-component)
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Q&A

Thank you !
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51