October,  2016 RAMSPEC 1

Optimizing  Epoxy  Toughness  with  Greater  Formulation  Latitude  Using  Reactive  Liquid  Polymers

Presented  by:  Erwin  Wild

CVC  Thermoset  Specialties,  An  Emerald  Performance  Materials  CompanyOctober,  2016

October,  2016 RAMSPEC 2

Contents

• Epoxy  Toughening  

• Epoxy  Adduct  Synthesis

• Glycidyl  Ester  Synthesis

• Adhesive  Result  Comparisons

• Conclusions

October,  2016 RAMSPEC 3

Epoxy  Applications

• Coatings • Composites

• Adhesives • Electrical  Encapsulation

October,  2016 RAMSPEC 4

Epoxy  Properties

• High  modulus

• High  dimensional  stability

• Good  elevated  temperature  performance

• Chemical  resistance

• Low  creep

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October,  2016 RAMSPEC 6

How  Reactive  Liquid  Polymers  Work

• Copolymer  is  initially  soluble   in  epoxy  resin

• End  group  chemistry  is  chosen  to  react  into  matrix

• MW  grows,  RLP  phase  separates  into  micron  sized  domains

RLP  MODIFIED

UNMODIFIED

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October,  2016 RAMSPEC 8

Epoxy  Adduct  Synthesis

October,  2016 RAMSPEC 9

Disadvantages  of  Epoxy  Adducts• Increase  in  viscosity

• Unreacted  epoxy

050000100000150000200000250000

0 5 10 15 20

Viscosity

 @  27°C  (cp)

phr  RA1340

Viscosity  of  One  Part  Adhesivew/  26%  Acrylonitrile  CTBN-­‐Epoxy  Adduct

October,  2016 RAMSPEC 10

Glycidyl  Ester  Synthesis

October,  2016 RAMSPEC 11

Epoxy  Adhesive  Formulations

• 100  parts  epoxy  (diglycidyl  ether  of  bisphenol  A  – DGEBA)

• 5  parts  dicyandiamide  curative

• 2  parts  urea  accelerator

• 3  parts  fumed  silica

• Cured  for  30  minutes  at  177°C

• T-­‐Peel  and  lap  shear  tested  on  electrogalvanized  steel

• DSC  tested  at  10°C/min  heated  rate,  Tg  taken  as  midpoint

October,  2016 RAMSPEC 12

Advantages  of  Glycidyl  Esters• Minimal  viscosity  increase:

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18%  Acrylonitrile  ETBN 26%  Acrylonitrile  ETBN

Viscosity

 @  27°C  (cp)

Adhesives  Containing  15  phr  ETBN

Glycidyl  Ester

Adduct

Control  w/o  ETBN

October,  2016 RAMSPEC 13

Adduct  Chain  Extension

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October,  2016 RAMSPEC 21

Glycidyl  Ester  of  CTB

• Produces  epoxy  terminated  polybutadiene  without  free  epoxy,  previously  unachievable  with  traditional  adduct  synthesis

October,  2016 RAMSPEC 22

Conclusions

• Glycidyl  Esters  of  CTBNs  are  epoxy  terminated  RLP• With  no  free  epoxy• With  minimal  viscosity  impact  to  the  formulation

• 18%  Acrylonitrile  Glycidyl  ester  performance  • T-­‐Peel  equivalent  to  adduct  at  <  10  phr• Improved  lap  shear  at  <  15  phr• Less  Tg decrease  at  10-­‐20  phr

October,  2016 RAMSPEC 23

Conclusions  Continued

• 26%  Acrylonitrile  Glycidyl  ester  performance  • T-­‐Peel  slightly  less  than  adduct,  but  still  excellent  toughening• Improved  lap  shear  at  all  concentrations• Near  equivalent  Tg to  adduct  at  all  concentrations

• Polybutadiene  glycidyl  ester• Produces  epoxy  terminated  polybutadiene  directly• Application  in  systems  compatible  with  polybutadiene

October,  2016 RAMSPEC 24

Questions?