tietze huntsman presentation
TRANSCRIPT
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7/25/2019 Tietze Huntsman Presentation
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Polyurethanes & Specialties
Polybenzoxazines : New ChemistryPolybenzoxazines : New Chemistry
Roger TietzeRoger TietzeRobert KultzowRobert Kultzow
Tim TruongTim Truong
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PresentationPresentation
IntroductionIntroduction
ChemistryChemistry
Material PropertiesMaterial Properties
Bisphenol A benzoxazineBisphenol A benzoxazine
ConclusionConclusion
Future DevelopmentsFuture Developments
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IntroductionIntroduction
Technology Origin:Technolo
gy Origin:
Chemistry discovered in the 1!"#sChemistry discovered in the 1!"#s
Patent technolo$y %as ac&uired 'rom a (%issPatent technolo$y %as ac&uired 'rom a (%iss
)esearch or$anization in the early 1"#s)esearch or$anization in the early 1"#s
*untsman has modi'ied and enhanced the scope o'*untsman has modi'ied and enhanced the scope o'
benzoxazine technolo$ybenzoxazine technolo$y
+echnolo$y has been commercialized+echnolo$y has been commercialized
*untsman trade name , Azyrals*untsman trade name , Azyrals
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ChemistryChemistry
Benzoxazines are a uni&ue non-halo$en thermosetBenzoxazines are a uni&ue non-halo$en thermoset
resin chemistryresin chemistry
+hese compounds can be synthesized 'rom phenols.+hese compounds can be synthesized 'rom phenols.
'ormaldehyde. and amines/'ormaldehyde. and amines/ 0o halo$en based precursors0o halo$en based precursors
Benzoxazines can homopolymerize to 'orm aBenzoxazines can homopolymerize to 'orm a
polybenzoxazine thermoset net%orspolybenzoxazine thermoset net%ors
Benzoxazines also co-cure %ith epoxiesBenzoxazines also co-cure %ith epoxies
2lectronics P3B maret has a need 'or a non-2lectronics P3B maret has a need 'or a non-
halo$en resin chemistry/halo$en resin chemistry/
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Huntsman Advanced Materials
Polybenzoxazine ChemistryPolybenzoxazine Chemistry
AdvantagesAdvantages
Potential lo% cost hi$h per'ormance thermosetPotential lo% cost hi$h per'ormance thermoset
*i$h purity resin system*i$h purity resin system
*i$h $lass transition temperature*i$h $lass transition temperature 4o% shrina$e4o% shrina$e
4o% coe''icient o' thermal expansion4o% coe''icient o' thermal expansion
Better moisture resistance/Better moisture resistance/
Better 'lammability resistance than epoxies and otherBetter 'lammability resistance than epoxies and otherthermosetsthermosets
2xcellent electrical properties2xcellent electrical properties
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Benzoxazine Synthesis
5*)!
)6
)1
* *
5
0*6
)7
0
5
)7
)!
)6
)1
-6*65
6 x8 8
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XU!"# $enzoxazine :XU!"# $enzoxazine :
$is%henol & benzoxazine$is%henol & benzoxazine
C*!
C*!
5 5
00
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$enzoxazine Polymerization$enzoxazine Polymerization
0
55
0
5
5
*
*
)1
)1
5
5
*
*
0
5
5
*
*
0
0 0
)1
)1
*eat
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Huntsman Advanced Materials
5
5
)6
95
5
0
55
0
5
55
)69
5
5
55
)69
5
5*
)1
)1
5
5
*
0
5*
0
0 0
)1
)1
55
)69
5
* * *
Catalyst
*eat
8
2poxy
$enzoxazine'(%oxy$enzoxazine'(%oxy
PolymerizationPolymerization
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Benzoxazine: Neat Resin Sample
Preparation
+o test the properties o' benzoxazines and other
thermosets. neat resin samples %ere prepared by the
'ollo%in$ procedure,
)esins and hardeners are melted
De$assed
Poured into a mold
Cured %ith the appropriate cure cycle
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Neat Resin Castings
ResinResin TypeType CureCure
LZ8001LZ8001 FR4 bis A epoxyFR4 bis A epoxy 1 hour @ 177C1 hour @ 177C
MY720/DDSMY720/DDS i!h "! epoxyi!h "! epoxy 4 hour @ 200C4 hour @ 200C
Aro#y $40Aro#y $40 Cy%&%'e (s'erCy%&%'e (s'er 4 hours @ 218C4 hours @ 218C
$M)/DA$A$M)/DA$A *o+yi,i-e*o+yi,i-e 4 hours @ 218C4 hours @ 218C
*o+ybe&.ox%.i&e A*o+ybe&.ox%.i&e A $e&.ox%.i&e$e&.ox%.i&e 2 hours @ 200C2 hours @ 200C
*o+ybe&.ox%.i&e $*o+ybe&.ox%.i&e $ $e&.ox%.i&e$e&.ox%.i&e 2 hours @ 200C2 hours @ 200C*o+ybe&.ox%.i&e C*o+ybe&.ox%.i&e C $e&.ox%.i&e$e&.ox%.i&e 2 hours @ 200C2 hours @ 200C
*o+ybe&.ox%.i&e D*o+ybe&.ox%.i&e D $e&.ox%.i&e$e&.ox%.i&e 2 hours @ 200C2 hours @ 200C
*o+ybe&.ox%.i&e (*o+ybe&.ox%.i&e ( $e&.ox%.i&e$e&.ox%.i&e 2 hours @ 200C2 hours @ 200C
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Neat Resin CastingsNeat Resin Castings
ResinResin lass Transition Temperatures! "Class Transition Temperatures! "C
LZ8001 epoxy / Di#yLZ8001 epoxy / Di#y 10C 140C10C 140C
MY720 / DDSMY720 / DDS 200C200C
Aro#y $40Aro#y $40 240C240C
$M) Resi&/DA$A$M) Resi&/DA$A 240C240C
*o+ybe&.ox%.i&e A*o+ybe&.ox%.i&e A 10C10C
*o+ybe&.ox%.i&e $*o+ybe&.ox%.i&e $
1C1C
*o+ybe&.ox%.i&e C*o+ybe&.ox%.i&e C 20C20C
*o+ybe&.ox%.i&e D*o+ybe&.ox%.i&e D 170C170C
*o+ybe&.ox%.i&e (*o+ybe&.ox%.i&e ( 200C200C
3"MA A&%+ysis
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U)*+ Testing : Neat ResinU)*+ Testing : Neat Resin
ResinResin 11ststBurnBurn ##ndndBurnBurn $ength$ength RatingRating
LZ8001 / Di#yLZ8001 / Di#y 8080 5/%5/% $ur& 'o #+%,p$ur& 'o #+%,p $$
MY720 / DDSMY720 / DDS 4040 5/%5/% $ur& 'o #+%,p$ur& 'o #+%,p $$
Aro#y $40Aro#y $40 11 7878 22 6161
$M) Resi&/DA$A$M) Resi&/DA$A 1010 5/%5/% $ur& 'o #+%,p$ur& 'o #+%,p $$
*o+ybe&.ox%.i&e A*o+ybe&.ox%.i&e A 1010 1212 4242 $$
*o+ybe&.ox%.i&e $*o+ybe&.ox%.i&e $ 280280 7272 2828 $$
*o+ybe&.ox%.i&e C*o+ybe&.ox%.i&e C 44 2020 00 6060
*o+ybe&.ox%.i&e D*o+ybe&.ox%.i&e D 2020 6161
*o+ybe&.ox%.i&e (*o+ybe&.ox%.i&e ( 22 2424 1111 6060
5o'e Lo&!es' bur& 'i,e re#or-e-
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$enzoxazine: (lectrical Testing$enzoxazine: (lectrical Testing
0eat resin specimens , "/:; x "/:;0eat resin specimens , "/:; x "/:;
0eat resin specimen thicness , 6/" mm < 6/: mm0eat resin specimen thicness , 6/" mm < 6/: mm
*P761A )F Impedance=Material Analyzer*P761A )F Impedance=Material Analyzer
4ined to *P 1>7:!A Dielectric Material +est4ined to *P 1>7:!A Dielectric Material +est
Fixture %ith a *i$h Impedance +est *eadFixture %ith a *i$h Impedance +est *ead
Calibration included the *P lo% loss capacitorCalibration included the *P lo% loss capacitor
Fre&uency ran$e , 1 M*z to 1/? @*Fre&uency ran$e , 1 M*z to 1/? @*
)eported data ran$e , 1" M*z < 1/: @*)eported data ran$e , 1" M*z < 1/: @*
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$enzoxazine: (lectrical Pro%erties$enzoxazine: (lectrical Pro%erties
o, Neat Resinso, Neat Resins
Neat Resin SampleNeat Resin Sample DK RangeDK Range Df RangeDf Range
LZ8001LZ8001 7 7 0020 000020 00
A(R4100A(R4100 7 7 0020 000020 00
Aro#y $40Aro#y $40 280 27280 27 0000 00000000 0000
*o+ybe&.ox%.i&e A*o+ybe&.ox%.i&e A 00 100 1 0000 001000000 00100
*o+ybe&.ox%.i&e $*o+ybe&.ox%.i&e $ 1 01 0 00070 0011000070 00110
*o+ybe&.ox%.i&e C*o+ybe&.ox%.i&e C 4 04 0 00070 000000070 0000
*o+ybe&.ox%.i&e D*o+ybe&.ox%.i&e D 40 440 4 000 0008000 0008
Fre9uey : 10 MZ 1 ;.
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Benzoxazines more 'lame resistant than epoxiesBenzoxazines more 'lame resistant than epoxies
@ood electrical properties@ood electrical properties
*i$h $lass transition temperatures*i$h $lass transition temperatures
Neat Resin ResultsNeat Resin Results
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Ty%ical Pro%erties XU!"#Ty%ical Pro%erties XU!"#
isual appearanceisual appearance ello% chunsello% chuns
Meltin$ point. CMeltin$ point. C ?"-?:?"-?:
iscosity E 16:iscosity E 16:C. cpsC. cps 1?:1?:
olatile. olatile. G6G6
D(C uncuredD(C uncured
Initiation +emperature +o.Initiation +emperature +o. CC 6!16!1 Pea +emperature +$.Pea +emperature +$. CC 671671
*. H=$*. H=$ 6!?6!?
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-echanical Pro%erties-echanical Pro%erties
%&'()*
Curin$ Cycle 6hr=1?"C 8 6hr=6""C
+$CJ D(C 1K1
+$CJ DMA 1>!
+$CJDMA 3etL 1:"
+lex Properties ,ry - RT
Modulus. si. MPaJ >>K 7>"6J(tren$th. si. MPaJ 1/1 1!6JTensile Properties ,ry - RTModulus. si. MPaJ KK! :!!7J(tren$th. si. MPaJ 7/: !1J2lon$ation. 1/6Compression Properties ,ry - RTModulus. si. MPaJ :"? !:":J(tren$th. si. MPaJ !! 66?J2lon$ation. ?/!Toughness Properties ,ry - RT
Ic. lbin=in6. MPamJ ?77 "/7J
@Ic. in-lb=in6. H=m
6J "/> 1>?J
L7?hrs boilin$ %ater
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.ormulations ,or XU!"#.ormulations ,or XU!"#
. # '
/01./. 0( 0* 0*
C2 .0/ #( '* '*
3ycar CTBN.'**x.' 111 .*
%B )*0/ '4(* '4(*
Benzopinacol .4*( .4*(
Curin$ Cycle 6hr=1?"C 8
6hr=6""C
1hr=16"C 8
7hr=1?"C
1hr=16"C 8
7hr=1?"C
+$CJ D(C 61 6"7 0+
+$CJ DMA. 2# 66K 1? 6""
+$CJDMA. 2# 3etL 1?1 1>7 1:?
+lex Properties ,ry - RTModulus. si. MPaJ >76 K76 :6K
(tren$th. si. MPaJ 1>/K 1/! 1/6Tensile Properties ,ry - RTModulus. si. MPaJ >6> K66 :>7(tren$th. si. MPaJ K/> K/7 16/>2lon$ation. 1/> 1/" 6/?Toughness Properties ,ry - RT
Ic. lbin=in6. MPamJ :?1 0+ ?:"
@Ic. in-lb=in6. H=m
6J "/7K 0+ 1/6!
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No/el 0igh er,ormance
o/el 0igh er,ormance
1ystems
ystems
Conclusions ,Conclusions ,
3e have developed uni&ue benzoxazine resins %ith commercially3e have developed uni&ue benzoxazine resins %ith commercially
viable manu'acturin$ processes/viable manu'acturin$ processes/
+hese resins a''ord %ide 'ormulation latitude and can be+hese resins a''ord %ide 'ormulation latitude and can be
'ormulated %ith epoxies. thermoplastics and catalysts to suit'ormulated %ith epoxies. thermoplastics and catalysts to suit
various applications and 'abrication processes/various applications and 'abrication processes/
+hese resins are ideal 'or hi$h per'ormance composite. structural+hese resins are ideal 'or hi$h per'ormance composite. structural
adhesive and printin$ %irin$ board P3BJ applications/adhesive and printin$ %irin$ board P3BJ applications/
+he benzoxazine=epoxy systems have hi$h +$+he benzoxazine=epoxy systems have hi$h +$CC. $ood thermal. $ood thermal
oxidation stability. lo% %ater pic-up. reduced shrina$e. $oodoxidation stability. lo% %ater pic-up. reduced shrina$e. $ood
electrical. and are room temperature stable/electrical. and are room temperature stable/
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$enzoxazine Technology$enzoxazine Technology
Current StatusCurrent Status +echnolo$y development %or continues+echnolo$y development %or continues 0e% candidate products have been introduced 'or0e% candidate products have been introduced 'or
< Aerospace composite maretsAerospace composite marets
< *i$h per'ormance laminatin$ marets*i$h per'ormance laminatin$ marets 3e have cooperative developments pro$rams %ith ey3e have cooperative developments pro$rams %ith ey
customerscustomers Nuali'ications in pro$ress at maOor customers in both 2lectronicNuali'ications in pro$ress at maOor customers in both 2lectronic
and Aerospace se$mentsand Aerospace se$ments Industrial applications are bein$ exploredIndustrial applications are bein$ explored
Manu'acturin$ in place in 0orth America and 2urope/Manu'acturin$ in place in 0orth America and 2urope/ Process development %or to install manu'acturin$ capability inProcess development %or to install manu'acturin$ capability in
Asia in the near 'uture/Asia in the near 'uture/
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+han ou+han ou
NuestionsNuestions