Tietze Huntsman Presentation

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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Huntsman Advanced Materials

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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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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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

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Tietze Huntsman Presentation