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POLYOLS FOR HIGH-STRENGTH AND DURABLE POLYURETHANE
ADHESIVES
AA
Polyurethane adhesives are highly versatile
materials used in high-performance
applications. Polyurethanes allow a wide
range of raw materials to modify properties,
and can be made moisture-curing, two
component reactive or non-reactive hot melt.
Two of the key trends driving market growth
are a growing emphasis on sustainability
plus a continuing need to enhance
performance and longevity. Croda has now
extended its range of bio-based polyols with
an innovative technology, to meet this
industry need for adhesives of the future.
This paper will demonstrate the higher
performance and durability with these new
polyols in reactive polyurethane adhesives
and PU dispersions.
The advanced polyols bring polyurethane
adhesives with excellent strength while
offering high flexibility. The polyols are based
177
 
on natural oil chemistry, offering (low
temperature) flexibility to the bond to allow
shock absorption or adhesion of flexible
substrates. Low adhesive viscosity provides
ease of application, while enhanced wetting
brings good adhesion to a variety of
substrates.
Innovation has brought a step-change in
strength in addition to the high adhesive
flexibility. The strong mechanical
performance is combined with excellent
durability. This is highly relevant for
demanding applications like automotive and
electronics adhesives. The technology is
suitable for multi-material design, offering
versatile adhesion and coping with variations
in thermal expansion. This allows use in
laminate structures and lightweight
construction, combining metal with
composites and plastics.
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POLYOLS FOR HIGH-STRENGTH AND DURABLE POLYURETHANE

ADHESIVES

P olyols for high-strength and durable polyurethane adhesives

Dr . Angela Smits In-adhesives conference 2016
Munich

Market trends & Renewable materials

1. Reduce environmental impact:
• Reduce energy or fuel consumption
• New power solutions: wind, solar
• Insulation
• Weight reduction
• Thinner and lower density materials
• Substitution of steel and glass
• Plastics & composites add design freedom: Aerodynamics
¾ Adhesives for bonding (multi-material, instead of welding etc.)

• Renewable raw materials

• Less reliant on petrochemicals plus offering new chemistries
• Industry targets (building & construction; automotive – BMW-i, Ford)
• Brand image (sporting goods, electronics)

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ADHESIVES

Market trends & Our solution

2. Enhanced performance & longevity:
• Resistance to difficult environments
• High continuous-use temperature
• Longer service intervals

• Croda:
• Naturally derived speciality chemicals and sustainable products
[ !"SiedasInteresseIhrerLesermiteinempassendenZitatausdemDokument,
oderverwendenSiediesenPlatz,umeineKernaussagezubetonen.UmdasTextfeldan
• Priplast™ polyols:
• Versatile strong adhesion
einerbeliebigenStelleaufderSeitezuplatzieren,ziehenSieeseinfach.]
• Enhanced durability: HO ---- E--E ---- OH
n
• Excellent moisture protection
• Combined stability to hydrolysis, thermal oxidation and UV
• Biobased polyols
• High flexibility, BUT limited material strength
¾ NEW: Priplast XL for high strength

Polyurethane adhesives
Versatile technology; typical ingredients
• Polyester polyol – usually crystalline for fast setting
• Disadvantage: susceptible to hydrolysis Priplast XL
• Polyether polyol – to increase flexibility Hydrolytic-, thermal
oxidative and UV-stability
• Disadvantage: susceptible to UV/oxidative degradation Flexibility plus internal
• Polycarbonate polyols – for weather stability strength
• Disadvantage: poor processing / flow

• Isocyanate – usually MDI

• Catalyst – tin octoate, DBTL
• Additives – anti-oxidant, pigments etc.

Various PU adhesive technologies:

• Reactive adhesives (moisture cured or 2K)
• Thermoplastic PU hotmelt
• Waterborne PUD
• Hybrid technology (with acrylate, epoxy, urea, silane etc.)

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ADHESIVES

Polyurethane adhesives evaluation

Novel excelling polyol technology

• New semi-crystalline Priplast XL polyol grades:

• Priplast XL 101 : Mw 2000 / functionality 2
• Priplast XL 102 : Mw 3000 / functionality 2

• Evaluated in moisture cured and in PUD adhesives:

• Excellent strength combined with high elongation

• Low adhesive viscosity for ease of application
• Versatile adhesion allowing use on multiple substrates
• Improved weathering stability vs. conventional polyols
• Faster strength development

R eactive adhesives – 1K moisture cured

Evaluation of single polyol systems

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ADHESIVES

Polyurethane adhesives evaluation

Polyols in comparison

• Reactive Polyurethane adhesives in this study

• Prepared with excess solid MDI, moisture cured at 60°C (48h) / 25°C
• NCO:OH = 2
• Single polyol systems
• No additives, not formulated
• Lap-shear adhesion ISO 4587

Comparative polyols (Mw 2000, functionality = 2.0):

• Hexanediol based polycarbonate polyol
• PTMEG polyether polyol
• Hexanediol-adipate polyester polyol
• Priplast 3192 semi-crystalline polyol
• Priplast XL 101 (Mw 2000) and XL 102 (Mw 3000)

Excellent strength with high elongation

PU elastomer sheet example instead of moisture-cured PU
60 #$%&'$ ( ) *+,-+, 700
2 Butane diol
3.1 MDI boost flexibility
50 600
Tensile strength (MPa)

500
40
Elongation (%)

400
30
300
20
200

10
100

0 0

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ADHESIVES

Low viscosity for ease of application

Priplast XL gives low adhesive viscosity

Low adhesive viscosity gave easier spreading and application of the PU adhesive

100

80
Viscosity @ 60°C (Pa.s)

60

40
Priplast are waxy solid
(Tm 35-45°C)
20 PC diol and HDO-
adipate are solid flakes
(Tm 50-55°C);
0

Versatile adhesion – plastics

Priplast XL shows good adhesion to various plastics
10

8
Adhesive strength ( MPa)

6
PC
PVC
4
PA
ABS
2 PS

10

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ADHESIVES

Versatile adhesion – polyolefins

Priplast XL shows improved adhesion to low energy substrates
0,7

0,6
Adhesive strength ( MPa)

0,5

0,4

0,3 PE
PP
0,2

0,1

11

Adhesion in composites or electronics

Priplast XL shows good adhesion to metals and reinforced epoxy

30
NB
25
Adhesive strength ( MPa)

20

Epoxy glass
15
Cupper
10 Steel
Aluminium
5

12

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ADHESIVES

Hydrolysis resistance to retain adhesion

Priplast XL retains adhesion to aluminium in severe conditions
6
Before C./01 21304560
After hydrolysis on aluminium
5 NCO:OH = 2.0
Adhesive strength ( MPa)

4 1 week in water
at 90oC

3 Retention of
lap shear
adhesive strength
2

1
W573 8C159: 2;1
0 PTMEG moisture
absorption gives
delamination

13

Strength development
Priplast XL develops good strength at room temperature
7

6 PTMEG
HDO-adipate
Adhesive strength ( MPa)

5 Priplast XL 102

4
Priplast XL 101

3 PCdiol (HDO)
faster at Priplast 3192
strength
2

0
0 2 4 6 8 10 12 14
Time (days)

14

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POLYOLS FOR HIGH-STRENGTH AND DURABLE POLYURETHANE

ADHESIVES

< aterborne dispersion adhesives – 1K PUD

Evaluation of single polyol OH-PUD as uncross-linked 1K systems

15

PUD adhesives evaluation

Formulation used to compare polyols

• OH functional polyurethane dispersions in this study

• Prepared with IPDI at NCO:OH = 0.96, using acetone process

PUD
• Single polyol systems
• 110 gram Polyol plus 7.5 gram DMPA with 23.6 gram IPDI
• 110 gram XL 102 (Mw 3000) plus 7.2 gram DMPA with 19.3 gram IPDI
• DMPA = dimethylol propionic acid allows water dispersibility; neutralised with TEA = triethylamine
• PU Dispersion particle size 25 – 40 nm

• No additives, not formulated, not cross-linked

• Dried at 20°C and re-activated at 80°C ; Lap-shear adhesion ISO 4587

16

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ADHESIVES

Strength development in OH-PUD

Priplast XL 102 develops fast strength at room temperature
1,2

HDO-adipate fast
1
Priplast XL 102 strength
build-up
Adhesive strength (MPa)

PCdiol (HDO)
0,8
PTMEG
higher
0,6
green
strength
Priplast XL 101
0,4 slow
Priplast 3192 strength
build-up
0,2
N97 2:: =024./01
at 5 minutes
0
0 20 40 60 80 100 120
Time (minutes)

17

Open time allows bond adjustments

Priplast XL 102 gives long working time, while is fast at strength

• Time when no paper strip could be bonded anymore

• PUD applied 150µm wet on glass
• Paper strips applied after various time intervals

O>?@ BEF?
PCdiol (HDO) 5 – 20 min
PTMEG 3 – 4.5h
HDO-adipate 5 – 15 min
Priplast 3192 > 4.5h
Priplast XL 101 > 4.5h remains sticky

Priplast XL 102 1 – 2h

18

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POLYOLS FOR HIGH-STRENGTH AND DURABLE POLYURETHANE

ADHESIVES

Versatile adhesion
Priplast XL 102 shows good adhesion to metal and plastic
6

5
Adhesive strength (MPa)

4 Aluminum
Steel
3
PC
PET
2

1
8/5G:247 HI JKJ 54
too slow in 1K PUD;
0 therefore weak bond
and tacky film

19

Summary of the novel polyol in

high-strength polyurethane adhesives
Priplast XL polyols:

• Unique combination of excellent tensile strength and high elongation

• Good mechanical properties: internal strength and strength development
• Low adhesive viscosity for ease of application
• Versatile adhesion to multiple substrates
• Exceptional weathering stability for high durability

• To obtain stronger adhesives

• To adhere a range of different substrates
• Transportation, fibre reinforced systems, construction
• To improve adhesion to low polarity substrates (plastics)
• For long-lasting performance in demanding environments

187