Advancing Manufacturing through Chemistry

Mengfei Huang, Aniruddha Palsule, Guozhen Yang, John Klier, Jessica Schiffman

Sirrus Inc.

Subsidiary of Nippon Shokubai Co. Ltd.

Waterborne Symposium

New Orleans, LA

February 2018

CONFIDENTIAL2

Introduction to Sirrus Technology

CONFIDENTIAL3

Core Technology Platform

Acrylic (~20 billion Pound Market)

Sirrus Monomer – 1,1-Disubstituted Alkene

Functional group enables unique performance properties

Alkene requires energy to undergo free radical polymerization

Two additional functional groups enable physical properties such rigidity, flexibility, crystallinity,

thermal and chemical resistance

The highly reactive electron deficient alkene group promotes fast polymerization at room temperature

CONFIDENTIAL4

High Yield & Selectivity

CondensationCatalytic Cracking /

Fractional DistillationTransesterification

High molar yielding process eliminates co-product drag

OR

OR

O

O

OR

OR

O

O

OR

OR

O

OOH

OH

OR

OR'

O

O

➢ Low Raw Material Cost

➢ No Solvents

➢ Atom Economical

➢ Efficient Catalysis

➢ Minimal Waste

➢ High Yield

CONFIDENTIAL5

Polymerization Control

Initiation

Propagation

Termination

C CC C C C

CT

O O

R RR R R R

OOOO

n

C CO O

R R

C CC C

O O

R RR R

OO

n

R1

R2

O

O

INITIATOR(INIT)

+

C C

R R

OOC CO O

R R

R1

R2

O

O

+

C CC C

O O

R RR R

OO

n

C C

R R

OOCHAIN

TERMINATOR(CT)

+

INITIATION

CHAIN PROPAGATION

CHAIN TERMINATION

INIT

INIT

INIT INIT

INIT

C CC C C C

CT

O O

R RR R R R

OOOO

n

C CO O

R R

C CC C

O O

R RR R

OO

n

R1

R2

O

O

INITIATOR(INIT)

+

C C

R R

OOC CO O

R R

R1

R2

O

O

+

C CC C

O O

R RR R

OO

n

C C

R R

OOCHAIN

TERMINATOR(CT)

+

INITIATION

CHAIN PROPAGATION

CHAIN TERMINATION

INIT

INIT

INIT INIT

INIT

C CC C C C

CT

O O

R RR R R R

OOOO

n

C CO O

R R

C CC C

O O

R RR R

OO

n

R1

R2

O

O

INITIATOR(INIT)

+

C C

R R

OOC CO O

R R

R1

R2

O

O

+

C CC C

O O

R RR R

OO

n

C C

R R

OOCHAIN

TERMINATOR(CT)

+

INITIATION

CHAIN PROPAGATION

CHAIN TERMINATION

INIT

INIT

INIT INIT

INIT

CONFIDENTIAL6

Polymerization of Methylene Malonates with Various Functionalities

CONFIDENTIAL7

ChemilianTM M1000 DEMM reacts with various functional monomer salts

Fast reaction, fully polymerized in 20h

90wt% BDPE polymerized in 70h

➢ Methacrylic acid (MAA)-DEMM

➢ 2-Acrylanmido-2-methyl propanesulfonic acid (AMPS)-DEMM

0 10 20 30 40 50 60 70

0

60

70

80

90

100

VBA

MAA

AMPS

DE

MM

Co

nvers

ion

(%

)

Time (h)

Diethyl 2-Methylenemalonate (DEMM)

+ X-

X: OH-, COO-, SO3-, Anhydride etc.

Fast reaction in 5min

➢ 2-Vinylbenzoic acid (VBA)-DEMM

• Room temperature reaction

• Anionic polymerization

• Fast reaction rate

Procedure: Mix neutralized monomer salts with DEMM, conduct NMR study

CONFIDENTIAL8

Polymerization of ForzaTM B3100 BDPE with functional groups

0 1 2 3 4 5

0.01

0.1

1

10

100

1000

10000

100000

1000000

G' G

" (

Pa

)

Time (min)

G' (BDPE)

G" (BDPE)

G' (BDPE+MAA salt)

G" (BDPE+MAA salt)

Gel point

• Carboxylate group can initiate BDPE polymerization in a short period of time

➢ Experimental procedure:

(1) Neutralize Methacrylic acid pH7

(2) Blow with N2 and get dry MAA sodium salt

(3) Mix MAA salt with BDPE with weight ratio 1:2

(4) Measure the modulus with rheometer

BDPE crosslinker • Room temperature reaction• Anionic polymerization• React with water under high pH• Viscous, light yellow liquid

+ BDPE Polymer network

CONFIDENTIAL9

Crosslinking Functional Latex with ForzaTM B3100 BDPE

• Room temperature cure• Excellent Material performance• Solvent and corrosion resistant

• Matrix monomer of latex: Methyl Methacrylate and Butyl Acrylate

• Co-polymerize with functional monomers• No volatile organic Compounds

Methacrylic acid 2-Acrylanmido-2-methyl

propanesulfonic acid

Acetoacetoxyethyl

methacrylate

2-Hydroxyethyl acrylate Phosphoethyl methacrylate4-Vinylbenzoic acid Maleic anhydride

2-(Dimethylamino)ethyl

methacrylate

➢ Functional monomers that were investigated:

Functional latex

Copolymer chains with anionic groups

+

BDPE crosslinker

Crosslinked coating

-F: functional group, eg COO-, SO3-, -NH2, -OH

CONFIDENTIAL10

Crosslinking of Model Latexes

CONFIDENTIAL11

Functional Latex by Emulsion Polymerization

1. Nucleation 2. Growth 3. Consumption

• Emulsion polymerization can synthesize stable latex with narrow particle size distribution

• A widely used approach in industry due to its convenience

Sample: 5wt% MAA latex

Number average size: 197.5 nm

PDI: 0.053 Tg: 12.5℃

CONFIDENTIAL12

Side Reactions with Water

• BDPE reacts with H2O

BDPE can react with water, but this side reaction can be suppressed by the control over pH.

BDPEIncreasing pH

CONFIDENTIAL13

Performance after Crosslinking

CONFIDENTIAL14

MEK Double Rub Test Procedure (ASTM D4752)

Drawdown the latex Curing with water evaporation MEK double rub test

Rubbing procedure

CONFIDENTIAL15

MEK Rub-Resistance with ForzaTM B3100 BDPE Addition

Preparation： Add BDPE directly to latex (pH 7), mix for 2h, drawdown and cure at room temperature for 3 days before rub test.

MAA latex AMPS latex

• Rub-resistant performance is improved by increasing the content of functional monomers and BDPE crosslinker

• In this experiment, AMPS might be less protonated than MAA, resulting in higher activity

1% 3% 5%0

20

40

60

80

100

120

140

Ru

b C

ycle

MAA Content (wt%)

BDPE 0wt%

BDPE 2wt%

BDPE 8wt%

BDPE 15wt%

1% 3% 4%0

100

200

300

400

500

600

700

800

Ru

b C

yc

leAMPS Content (wt%)

BDPE 0wt%

BDPE 2wt%

BDPE 8wt%

BDPE 15wt%

Improvement

289%Improvement

360%

CONFIDENTIAL16

MAA latex AMPS latex

Curing Time Dependence

• The performance of MAA and AMPS latex crosslinked by BDPE is greatly improved with longer curing time.

Preparation： Add BDPE directly to latex, mix for 2h, drawdown and cure at room temperature for various curing time then conduct rub test.

0wt% 2wt% 8wt% 15wt%0

20

40

60

80

100

120

140

Ru

b C

yc

le

BDPE Content with MAA 5wt%

20h

40h

70h

0wt% 2wt% 8wt% 15wt%0

100

200

300

400

500

600

700

800

Ru

b C

yc

leBDPE Content with AMPS 4wt%

20h

40h

70h

Improvement

327%

Improvement

353%

CONFIDENTIAL17

1% 3% 5%0

100

200

300

400

500

Ru

b C

yc

le

MAA Content (wt%)

BDPE 0wt%

BDPE 2wt%

BDPE 8wt%

BDPE 15wt%

1% 3% 5%0

100

200

300

400

500

Ru

b C

yc

le

MAA Content (wt%)

BDPE 0wt%

BDPE 2wt%

BDPE 8wt%

BDPE 15wt%

1% 3% 5%0

100

200

300

400

500

Ru

b C

yc

le

MAA Content (wt%)

BDPE 0wt%

BDPE 2wt%

BDPE 8wt%

BDPE 15wt%

➢ Three other methods applied for MAA latex

Pre-emulsified BDPE in surfactant in water first

Dissolve BDPE in Chloroform then apply to dry film

Add BDPE directly

Comparison of Different Sample Preparation Techniques

• The introduction of surfactant molecular might wrap BDPE into micelles• Organic solvent allows penetration of BDPE across the coating layer

BDPE crosslinker

Improvement

1328%

Improvement

289%

Improvement

80%

CONFIDENTIAL18

➢ Film formation of 5wt% MAA latex with BDPE

Improvements in Film Formation

➢ Contact angle experiment

• Addition of BDPE improves film forming capabilities• Addition of BDPE results in higher hydrophobicity

Preparation： Drop 4ul water onto 5wt% MAA latex film with and without BDPE.

CONFIDENTIAL19

Stain-Resistance and Gel Content of ForzaTM B3100 BDPE-Containing latex

➢ Apple juice test➢ Gel content experiment

0 wt% 8 wt% 15 wt%

0

10

20

30

40

50

60

70

80

MAA

AMPS

Gel C

on

ten

t (w

t%)

BDPE Content (wt%)

Procedure: 1. BDPE and functional latex react for 2h, get solid product2. Dissolve solid latex in dimethylformamide for two days3. Dry the mixture again, and measure gel content

• The addition of BDPE causes gelation, indicating the formation of network• BDPE increased the hydrophobicity of the latex film

CONFIDENTIAL20

Conclusions

• ChemilianTM M1000 (DEMM) and ForzaTM B3100 (BDPE) exhibit rapid reaction rate with anionic groups on polymer latexes at room temperature reaction

• pH impacts the anionic initiation through neutralization of acid functionality

• Evidence of crosslinking is based on • Improved resistance to solvent, rub and stain• Good film formation

• Multifunctional methylene malonates can provide a new crosslinking technology for latexes

CONFIDENTIAL21

Advisor:

Dr. Jessica Schiffman

Dr. John Klier

Postdoc:

Dr. Guozhen Yang

Dr. Yuan Liu

PhD Candidates:

Kerianne Dobosz Kelsi Skeens

Kris Kolewe Shane Taylor

Irene Kurtz Nicholas Hight-Huf

Xiangxi Meng Yen Tran

Juanfeng Sun Lei Zheng

Samuel Trevenen

Acknowledgements

• Contact: schiffman@ecs.umass.edu

• Contact: klier@umass.edu

Schiffman Group, Fall 2017

Klier Group, Spring 2018