Lorenz-JEC 2011-Endf Schreibgeschuetzt Kompatibilitaetsmodus PDF

Chemistry and Chemical Technology of Unsaturated Polyester Resins and Related Resins
Chemistry
y and Chemical Technology
gy
of
Unsaturated Polyester Resins and
Related Resins
(Radically Curing Resins

Resins, especially UP
UP-, VE
VE- and VU
VU-Resins)
Resins)
R. Lorenz 1 31.03.2011
Content
1. Chronology and Introduction

2
2. B i Ch
Basic Chemistry
i off UP
UP-Resins,
R i VE
VE-Resins
R i andd VU
VU-Resins
R i
3. Mechanism of Curing, Morphology and Thermal Properties
4
4. Sh i k
Shrinkage, IInternal
t l St
Stress and
dHHow tto H
Handle
dl Th
Them
5. Sheet Molding Compound and Bulk Molding Compound
(SMC / BMC)
6. Current Developments
7
7. E
Expression
i off Th
Thanks
k / Remarks
R k
R. Lorenz 2 31.03.2011
1. Chronology and Introduction
1 Chronology and Introduction

1.
• U
Unsaturated
t t d polyesters
l t b
based
d on maleic
l i or ffumaric
i acid
id were kknown since
i th
the
1920s.
• Invention by Charleton Ellis in 1936 – 1940 (Ellis & Foster Co
Co.))
It was the combination of unsaturated polyesters and styrene that gave the modern
y of UP-Resins: Products with a low viscosity,
type y a high
g reactivity
y and g
good
material properties after cure.
• In the 1960s VE-Resins came up (“Derakane”), later VU-Resins (“Modar”).
As these resins are cured by radicals, produced by UP-resin manufacturers and
applied in the same markets they are covered here, too.
• Th SMC-
The SMC and
d BMC
BMC-technology
h l iincluding
l di shrink
h i k controll were d
developed
l d iin the
h
1960s and 1970s.
• Today´ss world production volume: roughly 3 Mio
Today Mio. t
R. Lorenz 3 31.03.2011
2. Basic Chemistry of UP-, VE- and VU-Resins
2 Basic Chemistry of UP-,

2. UP VE-
VE and VU-Resins
VU Resins
Condensation of an Unsaturated Polyester

y Resin ((UP-Resin))
• Simple melt condensation of dicarbonic acids and glycols in a batch process.

• Condensation temperature between 190 and 210 °C. C.
• Typical degree of condensation: 10 – 40,
turnover of condensation reaction between 90 and 97,5 %.
R. Lorenz 4 31.03.2011
Condensation of an Unsaturated Polyester Resin (UP-Resin)
• Condensation time: 8 - 30 hours.

• Water removal is enhanced by vacuum or nitrogen stripping.
• 50 to
t 250 ppm inhibitor
i hibit are required
i d for
f stabilization
t bili ti d during
i condensation,
d ti
storage (shelf life) and reactivity adjustment.
• Mixing with styrene is done in a second reactor.
The necessary amount of styrene is filled in and preheated to 40 – 60 °C.
Most often the hot polyester melt is continuously fed to the styrene and the
temperature
p of the mixture is kept
p ≤ 80 °C by
y cooling.
g
• The optimum mixing ratio of reactive double bonds to styrene
is 1 : 2 to 1 : 2,5 (on a molar basis) for most properties.
R. Lorenz 5 31.03.2011
Raw Materials for UP

UP-Resins
Resins
A Unsaturated Dicarbonic Acids to Achieve Cross Linking with

A.
Styrene
Maleic anhydride
O • Production by oxidation of n-butane
O O
⇒ cost efficient
• Working horse of UP-chemistry
Fumaric acid
HO O • more expensive than maleic anhydride
• usedd when
h sufficient
ffi i t iisomerisation
i ti off maleic
l i anhydride
h d id
can not be achieved
or
the acidity in the early stage of the reaction must be
O OH limited.
R. Lorenz 6 31.03.2011
B Saturated Dicarbonic Acids to Control Cross Link Density and

B.
to Optimize Network Properties
HO O HO O
O
O
O
O
OH
O OH
Phthalic acid anhydride Isophthalic acid Terephthalic acid
highly cost efficient, increases chemical increases toughness

working horse in resistance and
general purpose resins and thoughness glass transition temp.
good overall performance best weathering

resistance
1 t condensation
1-step d ti 2 t condensation
2-step d ti 2 t condensation
2-step d ti
R. Lorenz 7 31.03.2011
C Standard Glycols
C.
OH HO OH O
HO O HO OH
1,2 Propylenglycol Dipropylenglycol Diethylenglycol

(PG) (DPG) (DEG)
cost efficient cost efficient highly cost efficient
working horse in increases toughness increases toughness

many resin classes and styrene solubility decreases styrene
solubility
enhances isomerisation decreases the decreases the

of maleic to fumaric glass transition temp. glass transition temp.
structure of the network of the network
R. Lorenz 8 31.03.2011
D Acids and Glycols Contributing Special Effects (Part 1)

D.
O
O
1,2,3,6-Tetrahydrophthalic
1 236T t h d hth li acid
id anhydride
h d id
⇒ Air drying resins
O
O
Adipic Acid
HO
OH ⇒ Elastic Resins (glass transition
O temperatures 30 – 60 °C)
C)
HO OH Butanediol 1,3
Butanediol-1,3
⇒ UP-thermosets with high gloss
Neopentylglycol
p ygy (NPG)
( )
HO OH
UP-thermosets with
⇒ high hydrolytic resistance
⇒ high
g chemical resistance
⇒ excellent weathering resistance
R. Lorenz 9 31.03.2011

D.
Bis-(hydroxymethyl)-tricyclodecane
⇒ air drying resins
HO OH ⇒ very high hydrolytical resistance
⇒ very high chemical resistance
Group 4 according to DIN 18820 or

Group 5 according to EN 13121.
Propoxylated Bisphenol A
⇒ maximum hydrolytic resistance
HO
O O
OH ⇒ maximum chemical resistance
Group 6 according to DIN 18820 and EN 13121
R. Lorenz 10 31.03.2011

D.
O This chemistry is used in so called “DCPD”-

resins which combine low molar mass and low
OH
+ viscosityy with reasonable mechanical and
OH
thermal properties. In the US these resins
O are widely used as standard UP-resins instead
< 150 °C of ortho-phthalic-resins.
O
O OH This mono-functional maleic half ester is further
reacted to an unsaturated polyester.
O
The higher the DCPD content the lower the molar
mass of the polyester.
R. Lorenz 11 31.03.2011
The choice of the acids and glycols is determining not only the material
properties of the thermoset but also the suitability of the resin itself!
Most important is the solubility of the unsaturated polyester

in styrene. 2 obstacles may occur:
• C t lli ti off th
Crystallization the polyester
l t iin styrene.
t IIn thi
this case the
th
resin may become turbid and more viscous during storage.
Strong crystallization may cause precipitation.
• The polarity of the unsaturated polyester must be in a certain
range to make sure it is compatible with styrene.
Rule of Thumb
The more branched the carbon backbone of the glycol or acid is and
the lower their symmetry, is the better the solubility of the unsaturated
polyester.
Therefore, 1,2-propylenglycol is the preferred glycol
(but not ethylene glycol!).
glycol!)
R. Lorenz 12 31.03.2011
Chemistry of UP
UP-Condensation
Condensation
Half ester formation:
Thermal condensation:
R. Lorenz 13 31.03.2011
Unsaturated Polyesters Exhibit 2 further Important Reactions
• Isomerisation
• B
Branching
hi b by Mi
Michael
h l addition
dditi
Isomerisation: conversion of the cis maleic structure to the trans fumaric structure
The trans fumaric structure is more reactive during

g crosslinking.
g
R. Lorenz 14 31.03.2011
Michael Addition during Condensation Reaction

Nucleophilic addition of an OH-group to the maleic double bond
Roughly
g y 7 to15 % of the maleic double bonds react byy Michael addition:
• This causes branched unsaturated polyester molecules that exhibit a
functionality f > 2.
⇒ more than 2 OH-OH or COOH-groups
COOH groups per polyester molecule
• Broad molar mass distribution (MW / Mn ≈ 3 – 4,5).
R. Lorenz 15 31.03.2011
Synthesis of a VE
VE-Resin
Resin
O
n
O
O
O OH
O O
+2
OH
O 120 °C
Amine-Catalyst
OH
O O O
O
m
O
O OH with m = n + 1
Dissolution of the oligomer mixture in styrene yields the VE-Resin

R. Lorenz 16 31.03.2011
Advantageous Properties of VE
VE-Resins
Resins
• Generally higher chemical resistance than UP-networks ⇒ group 7A in EN 13121

(
(exeptt those
th based
b d on bi
bisphenol
h lAdderivatives).
i ti )
This effect is especially pronounced in the presence of alkaline media and
oxidizing media (like hydrogen peroxide and bleaching agents).
This effect is also pronounced at higher temperature.
• But: UP-resins based on isophthalic acid and neopentyl glycol still exhibit
the better weathering properties. Therefore, they are preferred for gel coats.
• Increased toughness and elongation compared to UP-networks.
• Substituting the bisphenol A epoxide by a novolac epoxide increases the
glass transtion temperature
g p of the network from ~130 °C to ~160 °C but
reduces toughness.
Chemical resistance at elevated temperatures is increased
(⇒ group 8 in EN 13121)
13121).
• Methacrylate monomers allow an easy substitution of styrene!
R. Lorenz 17 31.03.2011
Scheme of Synthesis for a VU

VU-Resin
Resin
HPMA 2,4´-MDI Chain Extender
NCO
O
2 OH + 2 + R
HO OH
O
NCO
Sn-Catalyst
80 °C
O
O solvent: styrene
O N
O H
O
R
N O O
H
O N
H
O
O
N O
H O
R. Lorenz 18 31.03.2011
Advantageous Profile of VU-Resins
• VU-resins
VU resins offer many possibilities for chemical modification (different
isocyanates, different chain extenders and mixtures of both).
• This chemistry gives access to a broad range of material properties

with respect to:
glass transition,
toughness and elongation
elongation,
chemical resistance and
mechanical properties.
⇒ Tailor-made solutions for different applications!
pp
• Excellent adhesion to glass fibers and other substrates.
• Commercial methacrylate monomers allow easy substitution of styrene!
R. Lorenz 19 31.03.2011
3 Mechanism of Curing,
3. Curing Morphology and Thermal Properties
After curing with a thermal initiator (or an light initiator) 3-dimensional

amorphous and isotropic networks are formed.
As an example
p the most simplep network based on a maleic acid-
propylenglycol resin is shown:
R. Lorenz 20 31.03.2011
The Characteristics of Curing (or Crosslinking)
• Radical copolymerization of fumaric double bonds and styrene is

characterized by a donor-acceptor-effect
donor acceptor effect (styrene acting as donor).
and by the so called gel-effect (reduction of chain termination).
• This copolymerization is much faster than the homo polymerizations
of styrene
y or fumaric double bonds: UP-resins can be cured within minutes!
• The curing is exothermic: ~80 kJ / mole double bond are liberated.
temperature
T max
t curing time
R. Lorenz 21 31.03.2011
The Characteristics of Curing (Part 2)
• Depending on the crosslink density and the cure conditions roughly

7 – 15 % of the fumaric double bonds survive the cure.
• Nevertheless, the residual styrene content can be reduced to almost zero,
if correct cure and postcure conditions are chosen.
• A lot of free radicals survive in the network!
• UP-networks exhibit
densely crosslinked volume elements
and
less densely crosslinked volume elements.
This is caused by the low molar mass components in the
unsaturated polyester and by the statistics of radical polymerization.
• In most cases the volume elements with low crosslink density are dispersed
in the higher cross linked matrix.
• This situation is responsible for the very broad glass transition observed by
DMA investigation of UP-networks.
R. Lorenz 22 31.03.2011
DMA Measurement of a Cured UP-Resin

UP Resin based on Isophthalic-Neopentylglykol
Isophthalic Neopentylglykol
R. Lorenz 23 31.03.2011
DMA Measurement of a Cured UP-Resin

UP Resin based on Isophthalic-Neopentylglykol
Isophthalic Neopentylglykol
R. Lorenz 24 31.03.2011
The best way to measure the glass transition temperature (TG)

• Run a DMA at 10 Hz or use a torsion pendulum and evaluate the maximum
of tan δ.
• DSC measurements often yield broad transitions that can not be evaluated.
The most important parameters influencing TG of an UP-network

UP network
• The crosslink density of the unsaturated polyester (characterized by the
molar mass of unsaturated polyester per double bond).
• The stiffness of the backbone of the unsaturated polyester
polyester.
• The mean molar mass of the unsaturated polyester that controls the number
of free chain ends in the network.
State of the Art

• Commercial UP-resins exhibit glass transition temperatures between ~30
undd ~185
185 °C.
°C
• Some products, based on high levels of DCPD, achieve
TG ≈ 200 – 220 °C when being post cured in air
at 180 – 200 °C for a longer period of time.
R. Lorenz 25 31.03.2011
4. Shrinkage, Internal Stress and How to Handle Them
4 Sh
4. Shrinkage,
i k Internal
I t l Stress
St and
dHHow tto H
Handle
dl Them
Th
The cure off an UP-resin

Th UP i causes a volume
l shrinkage
hi k off 6 – 8 V
Vol.-%
l %d depending
di
on the styrene content.
• The shrinkage of pure styrene is 17 Vol.-%.

• The shrinkage of an unsaturated polyester is about 3 Vol.%.
• The shrinkage of the resin is a linear combination of both parameters
and can be calculated:
Resin shrinkage = wunsat Polyester * 3 % + wStyrene * 17 %
• UP-Resins and other styrene based resins exhibit relatively high shrinkage
values when compared to e.g. EP-Resins.
• The high
g shrinkageg values of UP-Resins should be considered
in connection with the early gel point at ~15 % turnover.
Both parameters increase the internal stress in the molded part.
R. Lorenz 26 31.03.2011
Most Important Effects of Volume Shrinkage
• Surface waviness of the molded part.

• Fiber print through (the fiber pattern can be seen on
the surface).
• IInternal
t l stress
t i th
in the part.
t
• Internal stress causes warpage or warping
(= unwanted change of geometry).
This effect is often increasing with the size of the part
and with its geometric complexity.
• Internal stress favors crack formation during service life.
R. Lorenz 27 31.03.2011
How to Reduce Volume Shrinkage

g and Internal Stress?
A. Lamination
• Part is built up layer by layer.
• Most of the shrinkage is happening perpendicular to the large surfaces.
B. Tempering
B
• Store the part 20 to 50 °C below the glass transition temperature
for a sufficient time (several hours).
• To maintain dimensional stability tempering is best done in the mold
mold.
R. Lorenz 28 31.03.2011
How to Reduce Volume Shrinkage and Internal Stress?
C. Shrink Control
Shrink control means distribution of macroscopic shrinkage to microscopic
voids or holes homogenously dispersed in the part.
Shrink Control is very often applied in SMC & BMC.
Shrink control works best when

• a highly cross linked resin is used that yields a relative brittle thermoset
(little internal stress relaxation in the network),
• a thermoplastic polymer is applied
applied,
which is soft under the curing conditions (low cohesive forces) and
which forms its own phase,
• curing is very fast
(rapid built up of internal stress necessary for maximum stress
transfer to the thermoplastic phase).
R. Lorenz 29 31.03.2011
5. SMC / BMC
5 Sheet Molding Compound and Bulk Molding Compound

5.
Both compounds are designed for (highly) automated processing
A Sheet
A. Sh t Molding
M ldi C Compound d (SMC) ffor press molding
ldi
Characteristics:
- Compound is stored between protective films.
- Very little glass fiber damage by the press molding process
B. Bulk Molding Compound (BMC) for injection molding
Characteristics:
- Lower glass fiber content and gradually higher filler load than in SMC
- Shorter fibers and more fiber damage by the screw machine.
- Lower mechanical properties than SMC
Both compounds make use of:

• Highly cross linked resins
• Shrink control technologies
• Thickening
• High filler load (≥ 150 parts)
• Fast thermal cure in hot molds ⇒ short cycle
y time
⇒ good economics for high volume production
R. Lorenz 30 31.03.2011
5. SMC / BMC
A typical SMC Recipe
60 p
parts UP-resin
40 parts Shrink control agent
(most often a polymer dissolved in styrene)
3,0 parts Mold release agent (mostly metal salts of stearic acid)
2,5 parts Thickening agent (most often based on MgO)
1,0 part Thermal initiator
200 parts Filler (mostly

( C CO3 with ~1,5
CaCO 1 µm particle-Ø)
Ø)
• Mixing these ingredients gives the so called “paste”.

• O a SMC-machine
On SMC hi ~72 72 % paste
t are b
brought
ht
together with ~28 % chopped glass fibers
(typically 1 inch long).
• After 3 - 7 days of thickening the compound
is ready for molding (leathery behavior).
R. Lorenz 31 31.03.2011
5. SMC / BMC
Thickening
Thickening is an acid-base-reaction: COOH groups of the unsaturated polyester
resin are reacting with MgO particles at the particle surface.
HO COOH
CH3
+ x MgO
HO OH
CH3
HOOC
HO COOH
CH3 - x H2O
Mg ++ Mg ++ OOC
- - - - - -
OOC
HO COO
CH3 OOC
HO COO
CH3 HO COO
CH3
- - -
HO COO
CH3 HO COO
CH3 HO COO
CH3
++ ++
HO OH
CH3
Mg HO OH
CH3
Mg HO OH
CH3
The highly
g yp polar Mg-carboxylate
g y units exhibit a low solubility
y in the resin and
precipitate:
• They form nano-clusters that act as multifunctional crosslink points in the resin.
• They increase the viscosity by roughly 3 decades.
• By shearing the material the clusters are broken up – they reform after shear.
R. Lorenz 32 31.03.2011
5. SMC / BMC
Shrink Control Technologies
3 types of formulations are most often used in practice
a. Use of LDPE-powder
LDPE powder (“Coethylene”).
( Coethylene ).
The internal stress in the part is gradually reduced.
Additionally, some thoughening of the composite is achieved and it is less

Additionally
sensitive to crack formation.
b Use of PS
b. PS, HIPS
HIPS, PMMA or rubbers dissolved in styrene (medium effect)
These recipes are called Low Shrink (LS) Formulations.
LS-formulations
LS f l i are used d when
h a di dimensionally
i ll stable
bl part
with a low level of internal stress is required.
R. Lorenz 33 31.03.2011
5. SMC / BMC
c. Use of PVAc and saturated polyesters dissolved in styrene.
Both types of polymers can be broadly modified and combined.
They allow a very high degree of shrink control (zero shrink!)

and are named Low Profile (LP-) Formulations.
The very best

Th b LP
LP-Formulations
F l i give
i so called
ll d Cl
Class A surfaces
f
that match the surface performance of automotive sheet steel.
Class A systems can be painted without a mechanical surface treatment.
R. Lorenz 34 31.03.2011
5. SMC / BMC
Mechanism of Low Profile Recipes

p
Before cure
1-phase mixture of UP-resin and
PVAc-solution in styrene
Initial phase of cure

Cross linked particles
precipitate. They are more or
less spherical.
After cure.
Void formation (= gas bubbles) in
the thermoplastic phase
The spherical thermoset particles
grow together and form 3-
dimensional continuous frame
work. The thermoset morphology after cure
is called “pearl structure”. The pearls
are ~1 µm in diameter and can be
seen in the REM picture (after the
th
thermoplastic
l ti phase
h was removed d
with a solvent).
R. Lorenz 35 31.03.2011
6 Current Developments
6.
R&D on UP
UP-Resins
R i andd Related
R l t d Products
P d t
• St
Strong activities
ti iti and
d a llott off b
basic
i work
k iin th
the 1950
1950s tto 1980
1980s.
• Continuously declining research activities in the following 2 decades.
• B t There
But: Th is
i ongoing
i product
d t development
d l t and
d process optimisation
ti i ti
for the large applications.
• A a consequence off the
As th declining
d li i research
h efforts
ff t ththe
“tool box for UP-Chemistry, UP–Technology and UP-Applications”
did not grow any more in the last 15 years!
Our knowledge and understanding are stagnating!
R. Lorenz 36 31.03.2011
A
A. Flame Retardant UP-Formulations
1. Regulations and standardisation became increasingly strict.
2
2. More and more detail requirements are defined and must be
measured and fulfilled by the composite:
- Smoke density (avoid black smoke)
- Toxicity of the flame gases (minimize HCN, HBr, HCl, NOx, CO, …)
- Heat generation
- Spread of Flame (avoid a flash over!)
3
3. Many new resin systems becoming commercially available are based
on Al(OH)3 or Nitrogen- and Phosphor-containing compounds.
4
4. Pivotal point: Achieve the required flame protection in all its details
without sacrificing the process and material properties.
R. Lorenz 37 31.03.2011
B. VOC Emissions (Volatile Organic Compounds)
1. UP-, VE- and VU-Resins with film forming agents reduce the styrene
emission during lamination and cure
cure.
2. VOC after cure
For automotive Class A SMC parts the VOC emission (initiator
fragments, solvents, impurities, residual glycols, residual styrene, …)
were reduced from >1000 ppm to <150 ppm between 1998 und 2008
2008.
A commercial example is Palapreg Premium!
Background information:
Demanding requirements for cars introduced in California (CARB)!
R. Lorenz 38 31.03.2011
C. Odourless UP-Resins and UP-Networks
1. Styrene is a cost-efficient reactive thinner that contributes much to the

high reactivity of the UP-, VE- or VU-resins and to the technological
properties of their networks.
2. But styrene (and residual styrene in the network) is smelling
intensively. This caused problems in certain fields of application:
roof repair, relining, chemical anchoring, gelcoats, ...
3. The most successful substitution of styrene-based UP-resins took
place in chemical anchoring. Almost all product were converted.
4. The newest styrene-free resin for relining:
Atlac Premium, DSM Composite Resins
R. Lorenz 39 31.03.2011
D. Further Activities related to Human Health and Well Being
1. Remove all substances with a potential CMR risk (carcinogenic,

mutagenic or reprotoxic) from the recipes.
One example for such a material may be p-benzoquinone
– a traditionally used inhibitor with a typical concentration range of
50 to 200 ppm (equals 50 to 200 mg per kg resin).
2. Substitution of cobalt based accelerators by suitable salts of
manganese, copper or iron.
New accelerators are commercially available (e.g. from AKZO).
R. Lorenz 40 31.03.2011
E. Rotor Blades for Wind Energy Generation
• Present situation: ~70 % of the rotor blades are made from EP-resins
because of their excellent fatigue and bonding properties!
Aim: Expand the share of UP- and VU-resins to more than 30 %!
• A lot of research is done on UP- and VU-Resins that combine fast
cure with more epoxy-like material properties.
R. Lorenz 41 31.03.2011
F. SMC- and BMC-Resins with improved Thermal Properties
1. Aim: Increase the glass transitions temperature and the thermo-

mechanical properties beyond the level of today´s pure maleic resins
(based on 1,2-Propylenglycol).
2. This research is still in an early stage – no commercial
products are available so far.
R. Lorenz 42 31.03.2011
G. Raw Materials from Renewable Sources
1. Look for suitable dicarbonic acids, glycols and reactive thinners that
can be made from a renewable source directly or by a subsequent
chemical or biotechnological step.
2. Create new resins that combine these renewable raw materials with
conventional ones based on steam cracking.
3. Give a clear indication to the market that the percentage of renewable
raw materials in our resins can be increased continuously in the years
ahead – if there is a growing demand and if the cost difference to
conventional raw materials is accepted.
4. First products are commercially available.
R. Lorenz 43 31.03.2011
7. Expression of Thanks / Remarks
7 Expression of Thanks / Remarks

7.
Dr. Dale Gerth, DSM Composite Resins
Peter Hilzendegen, DSM Composite Resins
Dr. Erik Reuther, DSM Composite Resins
Dr. Joachim Zwecker, BASF SE
Dirk Punke, BÜFA
Sven Glaser, BÜFA
Tobias Kiepe, BÜFA
Lothar Kempf, BÜFA
Jörg Bünker, Saertex
Dr. Bernd Jaschinski, Lorenz Kunststofftechnik
Thomas Lorenz, Lorenz Kunststofftechnik
Dr. Thomas Folda, AOC
R. Lorenz 44 31.03.2011
7. Expression of Thanks / Remarks
This presentation is available on CD
via
muchow@fh-muenster.de
R. Lorenz 45 31.03.2011

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Chemistry and Chemical Technology of Unsaturated Polyester Resins and Related Resins

(Radically Curing Resins

1. Chronology and Introduction

1 Chronology and Introduction

2 Basic Chemistry of UP-,

Condensation of an Unsaturated Polyester

• Simple melt condensation of dicarbonic acids and glycols in a batch process.

Condensation of an Unsaturated Polyester Resin (UP-Resin)

• Condensation time: 8 - 30 hours.

Raw Materials for UP

A Unsaturated Dicarbonic Acids to Achieve Cross Linking with

B Saturated Dicarbonic Acids to Control Cross Link Density and

Phthalic acid anhydride Isophthalic acid Terephthalic acid

highly cost efficient, increases chemical increases toughness

good overall performance best weathering

1,2 Propylenglycol Dipropylenglycol Diethylenglycol

cost efficient cost efficient highly cost efficient

working horse in increases toughness increases toughness

enhances isomerisation decreases the decreases the

D Acids and Glycols Contributing Special Effects (Part 1)

D Acids and Glycols Contributing Special Effects (Part 2)

Group 4 according to DIN 18820 or

Group 6 according to DIN 18820 and EN 13121

D Acids and Glycols Contributing Special Effects (Part 3)

O This chemistry is used in so called “DCPD”-

Most important is the solubility of the unsaturated polyester

Half ester formation:

Unsaturated Polyesters Exhibit 2 further Important Reactions

The trans fumaric structure is more reactive during

Michael Addition during Condensation Reaction

Dissolution of the oligomer mixture in styrene yields the VE-Resin

• Generally higher chemical resistance than UP-networks ⇒ group 7A in EN 13121

Scheme of Synthesis for a VU

Advantageous Profile of VU-Resins

• This chemistry gives access to a broad range of material properties

• Excellent adhesion to glass fibers and other substrates.

• Commercial methacrylate monomers allow easy substitution of styrene!

After curing with a thermal initiator (or an light initiator) 3-dimensional

The Characteristics of Curing (or Crosslinking)

• Radical copolymerization of fumaric double bonds and styrene is

The Characteristics of Curing (Part 2)

• Depending on the crosslink density and the cure conditions roughly

DMA Measurement of a Cured UP-Resin

DMA Measurement of a Cured UP-Resin

The best way to measure the glass transition temperature (TG)

The most important parameters influencing TG of an UP-network

State of the Art

The cure off an UP-resin

• The shrinkage of pure styrene is 17 Vol.-%.

Most Important Effects of Volume Shrinkage

• Surface waviness of the molded part.

How to Reduce Volume Shrinkage

How to Reduce Volume Shrinkage and Internal Stress?

Shrink Control is very often applied in SMC & BMC.

Shrink control works best when

5 Sheet Molding Compound and Bulk Molding Compound

Both compounds make use of: