＜ADDRESS＞ ＡＤＥＫＡ CORPORATION 7-2-35, HIGASHI OGU, ARAKAWA-KU TOKYO 116-8554 JAPAN SALES TEL +81-3-4455-2833 FAX +81-3-3809-8232 R&D TEL +81-50-5518-4336 FAX +81-3-3809-8284

Date of issue: May/31/2010 Date revised:Septemer/30/2011

ADEKA REASOAP ER/ＳＲ Series (2) Many kinds of surfactants are used for emulsion polymerization. Although surfactant is very useful material, it is known that surfactants cause various drawbacks on the emulsions and the films. Reactive surfactant is one of the most effective means to resolve the drawbacks. It copolymerizes with monomers during emulsion polymerization so that it shows different behavior compared to conventional surfactants. For instance, it might cause coagulation and poor water resistance. However, optimized formulation can improve these issues; here we will introduce the usage instructions.

【Chemical Structure】

C H 2 = C H -C H 2 -O -C H 2

R= Alkyl group X= H ： ER series SO3NH4、SO3Na ： SR series

R -O -C H 2 - C H (O C H 2 C H 2 ) n O X

【Physical properties of ADEKA REASOAP series】 NONION

ANION

ER-10

ER-20

ER-30

ER-40

SR-10

SR-20

SR-1025

SR-3025

20 75 ―

30 65 ―

40 60 ―

10 100

20 100

10 25

30 25

Counter ion

10 100 ―

NH4+

NH4+

NH4+

NH4+

Solvent Color （APHA） PH （2,5%aq） Viscosity (mPa･s,25℃)

― 100 7 120

water 100 7 400

water 100 7 800

water 100 7 1400

― 5(G) 7 7000

― 5(G) 7 10000

water 2(G) 7 20

water 2(G) 7 20

EO mol Solid content (%)

（1/13）

品名 ： ADEKA REASOAP ER/ＳＲ Series

Page

Contents 1. Emulsion polymerization

3

1-1. Usage instruction 1-2. Emulsion polymerization process 1-3. Evaluation method

3 4 4

2.Acrylic type emulsion polymerization【monomer：BA/MMA/AA(49/49/2 wt%)】 2-1. Dosage effect 2-2. Influence of initial monomer and surfactant ratio 2-3. Recommended formulation 3.Acrylic styrene type emulsion polymerization【monomer：BA/St/AA(49/49/2 wt%)】 3-1. Dosage effect 3-2. Influence of initial monomer and surfactant ratio 3-3. Recommended formulation

（2/13）

5 5 6 9 10 10 11 13

品名 ： ADEKA REASOAP ER/ＳＲ Series

１．Emulsion polymerization 1-1. Usage instruction 1) Dosage of reactive surfactant ■ Over 1.5wt% on monomer (recommendation 2.0-3.0wt%) Emulsion surface with reactive surfactant becomes more hydrophobic so that dosage of reactive surfactant should be increased than that of conventional surfactants to prevent coagulation. Combination with non reactive surfactant is available. 2) Initial polymerization condition (monomer + surfactant + water + initiator) ■ Time：15min, Temperature：75oC Enough initial polymerization (nucleation) is necessary to decrease coagulation and achieve narrow range particle distribution. Recommended formulation of initial polymerization Monomer (wt%) Initial polymerization (flask) Surfactant on monomer (wt%) Flask (wt%) Surfactant ratio Feed (wt%)

5 1-5 2-10 90-98

10 2.5-5.0 10-20 80-90

Polymerization rate of ADEKA REASOAP SR/ER can improve in emulsion polymerization and co-existence with acrylic monomers so that initial polymerization ratio of monomer to ADEKA REASOAP is very important. Initial excess surfactants might cause polymerization of only acrylic monomer (with less SR/ER), and consequently unreacted SR/ER remain. On the contrary, initial lack of surfactants might cause bigger particle size in some monomer composition. 3) Standard polymerization condition ■ Temperature：75oC, Feed time: 3hrs, Aging: 2hrs Enhanced condition such as high temperature and short feeding time might cause coagulation or generation of oligomer. 4) In the case of using styrene monomer ■ Optimized condition corresponded to the characteristic of styrene Styrene has the following characteristics, 1) Hydrophobic and low emulsified stability 2) Low reactivity compared to acrylic monomer due to its conjugation 3) Low reactivity with allyl group of SR (ex. Ally alcohol=-1.48, Q=0.005) due to electron donor (e=-0.8) and conjugated (Q=1.0) monomer Accordingly in the case of over 40 wt% of styrene in the compositions, the following optimized condition is necessary in order to improve the conversion of SR. 1) Make polymerization rate similar by adjusting of initial surfactant and monomer ratio. 2) Post polymerization (chaser)

（3/13）

品名 ： ADEKA REASOAP ER/ＳＲ Series

1-2. Emulsion polymerization process

Feed

1. Pre emulsification (flask)

Water（48%） Monomer Surfactant Initiator

2. Heat (75 oC)

Flask

3. Initiator

Water（52%） Monomer Surfactant

Post polymerization

Standard

Initial polymerization for 15min [Nucleation]

4. Feed

Ｎ２

250rpm

Emulsion※ feeding for 3hrs ※ water, monomer, surfactant, initiator

5. Aging

Aging for 1-3hr (75 oC)

6. Post polymerization 7. Aging 8. Neutralization

9. Filtration

Post polymerization + initiator, (monomer) Aging for 1-3hrs (75 oC)

Neutralization by 28% ammonia

#200 mesh filtration

1-3. Evaluation method Item Solid (%) Monomer conversion (%) Coagulation (%) Particle size(nm)

Method The dispersion is filtrated by 200mesh and heated at 105 oC until dried Calculation from Solid (%) Residue after filtration of the dispersion by 200 mesh. Dynamic light scattering method (25 oC)

Viscosity （mP・s）

Brookfield viscometer, at 25 oC by 10rpm.

SR conversion (%)

SR conversion is calculated from standard curve of HPLC The dispersion is applied on the glass plate by 51μm. Dry it up for 3days and put the glass into 50℃ water. Measured the time until 8-point letters is NOT readable. Texanol is added to emulsion (3% on emulsion) and measureｄ as above

Water resistance (1) (ｈｒ) Water resistance (2) (ｈｒ)

（4/13）

品名 ： ADEKA REASOAP ER/ＳＲ Series

2. Acrylic system emulsion polymerization 2-1. Dosage effect There are optimized dosages in order to emulsify monomer. It shows physical properties of the emulsion and the film with different dosage of surfactants. Monomer：BA/MMA/AA(49/49/2 wt%) Surfactant Polymerization prescription Dosage of surfactant on monomer (wt%) Initial monomer (wt %) Initial surfactant (wt %) Monomer (g) Flask Water (g) SR-10 (g) Initiator (g) APS Monomer (g) Water (g) Feed SR-10 (g) Initiator (g) APS Total (g) Solid (%) Coagulation (%) Particle size (nm) Viscosity (mPa.s/25 oC ,10rpm) SR conversion (%) Water resistance (1) (hrs) Water resistance (2) (hrs)

0.75 5 10 4.5 56.80 0.068 0.1 85.5 52.40 1.282 0.1 199.3 45.6 1＜ 160 50 95 1 2

1.5 5 5 4.5 57.20 0.068 0.1 85.5 52.75 2.182 0.1 200.8 45.6 0.08 234 100 95 144 216

2.5 5 3 4.5 58.8 0.135 0.1 85.5 54.2 4.365 0.1 202.4 45.6 0.05 180 180 95 168 340

5.0 5 3 4.5 58.8 0.135 0.1 85.5 54.2 4.365 0.1 207.7 45.6 0.03 140 250 50 650 1000

In the case of lower dosage of SR-10, it tends to cause coagulation and poorer water resistance. Much dosage of SR-10 shows better water resistance. 2-3 wt % of SR-10 is recommended as standard dosage.

Water resistance

Surfactant amount on momer (%)

● ●

SR-10 Standard

650

5.00

1000 168

2.50

340 144 216

1.50

0.75 0

water resistance ① water resistance ②

1 2

250

500

time (hr) （5/13）

750

1000

品名 ： ADEKA REASOAP ER/ＳＲ Series

2-2.Influence of initial polymerization formulation Even if in the same dosage of surfactants, it might cause coagulation and poor water resistance if the formulation is not optimized. It shows physical properties of emulsions and water resistance of films by changing of the ratio of initial monomers to surfactants. z Surfactant on monomer= 1.5%, 2.5%

Monomer：BA/MMA/AA(49/49/2 wt%)

Surfactant type Polymerization prescription

SR-10 Standard 1.5

Dosage of surfactant on monomer (wt %)

2.5

Initial monomer (wt %) 5 5 5 10 5 5 5 10 Initial surfactant (wt %) 1 5 10 10 1 5 10 10 Monomer (g) 4.5 4.5 4.5 9.0 4.5 4.5 4.5 9.0 Flask Water (g) 56.79 56.80 56.81 56.81 57.38 57.4 57.38 57.28 SR-10 (g) 0.014 0.068 0.135 0.135 0.023 0.068 0.225 0.225 Initiator (g) APS 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Monomer (g) 85.5 85.5 85.5 81.0 85.5 85.5 85.5 81.0 Water (g) 52.41 52.40 52.40 52.40 52.88 52.85 52.88 52.98 Feed SR-10 (g) 1.336 1.282 1.215 1.215 2.227 2.182 2.025 2.025 Initiator (g) APS 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 202.4 202.4 202.4 202.4 Total (g) 200.8 200.8 200.8 200.8 Solid (%) 45.4 45.6 45.6 45.5 45.5 45.6 45.6 45.4 Coagulation (%) 0.05 0.08 0.1 0.3＜ 0.05 0.05 0.05 0.1 Particle size (nm) 308 234 143 185 280 180 145 145 Viscosity (mPa.s/25 oC ,10rpm) 50 100 120 100 100 180 200 200 SR conversion (%) 95 95 95 95 95 95 95 95 Water resistance (1) (hrs) 144 144 96 96 168 168 144 144 Water resistance (2) (hrs) 336 216 96 96 504 340 196 216 ● Film with 2.5% of SR-10 shows better water resistance than that with 1.5% of SR-10. However, in the case of 1.5% of SR-10, water resistance can be improved by optimized formulation. (Particle size might be bigger in some cases such as hydrophilic monomer.)

96 96

10/10

water resistance ① water resistance ②

96

5/10

96 144

5/5

216 144

5/1 0

Water resistance Initial monomer/surfactant(%)

Initial monomer/surfactant (%)

Water resistance

336 100

200

300

400

500

600

216

water resistance ① water resistance ②

144 196 168

5/10 5/5

340 168

5/1 0

time (hr)

144

10/10

504 100

200

300

400

500

time (hr)

Surfactant on monomer =1.5%

Surfactant on monomer =2.5%

（6/13）

600

品名 ： ADEKA REASOAP ER/ＳＲ Series

Randomness of monomer and SR-10 in copolymer ¾

¾

Randomness of monomer and SR-10 is changed by the polymerization rate polymerization rate depend on 1) dosage of surfactants, 2) dosage of initiator, 3) temperature. Here, it shows control of polymerization by dosage of SR-10. Polymerization place (micelle) decrease in the case of lower dosage of the surfactants, and polymerization rates of monomer and SR-10 come closer by suppressing polymerization rate of monomer. As a result, randomness of monomer and SR-10 become high (the left figure). However, in the case of lower randomness, SR-10 is localized in the polymer and form water adsorption pocket causing poor water resistance. Initial polymerization Monomer/SR-10 = 5/10 wt% (SR-10=2.5ｗｔ%(on monomer))

100

100

75

75

Conversion (%)

Conversion (%)

Initial polymerization Monomer/SR-10 = 5/1 wt% (SR-10=2.5ｗｔ%(on monomer))

50 SR-10 monomer

25 0

50 SR-10 monomer

25 0

0

2

4

6

0

time (hr)

2

4 time (hr)

Polymer chain

Coalescing process (Particle inter diffusion)

Film Water resistance

SR copolymerized randomly

SR is localized

SR homogeneous distribution

Localized SR assemble

Without water adsorption pocket

Water adsorption pocket is formed

Air

Air

Adherend

Adherend

Excellent

Poor

（7/13）

6

品名 ： ADEKA REASOAP ER/ＳＲ Series ＊SR-10 = 5wt% on Monomer Much dosage of SR-10 shows better water resistance, however in the case of 5% of SR-10, unreacted SR-10 remains. Here, it shows the example of the improvement of conversion of SR-10 by post polymerization (chaser).

Surfactant type Polymerization prescription Dosage of surfactant on monomer (wt %) Initial monomer (wt %) Initial surfactant (wt %) Monomer (g) Flask Water (g) SR-10 (g) Initiator (g) APS Monomer (g) Water (g) Feed SR-10 (g) Initiator (g) APS Add APS (g) Post Add monomer (ppm) polymerization Aging temperature (℃) Aging time (hr) Total (g) Solid (%) Coagulation (%) Particle size (nm) Viscosity (mPa.s/25 oC ,10rpm) SR conversion (%) Water resistance (1) (hrs) Water resistance (2) (hrs)

SR-10 Post polymerization 5.0 5 3 4.5 4.5 58.80 58.73 0.135 0.135 0.100 0.025 85.5 85.5 54.20 54.27 4.365 4.365 0.100 0.175 0.2(0.1+0.1) 0.2(0.1+0.1) 1000(500+500) 75 75 3 1.5 207.7 207.7 45.8 45.8 0.03 0.03 145 145 250 250 95 95 312 312 650 650

Standard

4.5 58.80 0.135 0.100 85.5 54.20 4.365 0.100 207.7 45.6 0.03 142 250 50 650 1000

● Here, as a reason for decreased water resistance, it is considered that the formation of hydrophilic oligomer and localized SR-10 in the polymer absorb water. It means that only post polymerization is not enough and it needs optimized formulation by approximation of polymerization rate of monomer and SR-10.

Conversion (%)

100 80 Add monomer (500ppm)

60

Add APS 0.1g

40

ﾓﾉﾏｰ APS=0.1/0.1 APS=0.025/0.175 APS=0.025/0.175 with monomer

20 0 0

2

4

6 time (hr) （8/13）

8

10

12

品名 ： ADEKA REASOAP ER/ＳＲ Series

2-3. Recommended formulation in each dosage It shows recommended formulation with using SR-10. Monomer：BA/MMA/AA(49/49/2 wt%) Surfactant type Polymerization prescription Surfactant dosage on monomer (wt%) Initial monomer (wt %) Initial surfactant (wt %) Monomer (g) Water (g) Flask SR-10 (g) TNS-100 (g) Initiator (g) APS Monomer (g) Water (g) Feed SR-10 (g) TNS-100 (g) Initiator (g) APS Total (g) Solid (%) Coagulation (%) Particle size (nm) Viscosity (mPa.s/25 oC ,10rpm) SR conversion (%) Water resistance (1) (hrs) Water resistance (2) (hrs)

TNS-100※

SR-10 Standard 1.5

2.5

5

5 5 4.5 56.80 0.068 0.1 85.5 52.40 1.282 0.1 200.8 45.6 0.08 230 100 95 144 216

5 3 4.5 57.20 0.068 0.1 85.5 52.75 2.182 0.1 202.4 45.6 0.05 180 180 95 168 336

5 3 4.5 58.80 0.135 0.1 85.5 54.20 4.365 0.1 207.7 45.6 0.03 142 250 50 650 1000

1.5 5 5 4.5 56.80 0.068 0.1 85.5 52.40 1.282 0.1 200.8 45.5 0.06 145 130 36 36

2.5

5

5 3 4.5 57.20 0.068 0.1 85.5 52.75 2.182 0.1 202.4 45.5 0.05 153 150 50 50

5 3 4.5 58.80 0.135 0.1 85.5 54.20 4.365 0.1 207.7 45.5 0.01 135 280 24 24

※TNS-100：C13-10EO-SO3NH4 (Conventional surfactant)

● All formulation with SR-10 show better water resistance than that with conventional surfactants.

Water resistance

TNS-100

50 50

168

SR-10 0

water resistance ① water resistance ②

336 100

200 time (hr)

（9/13）

300

400

Surfactant on monomer=2.5%

品名 ： ADEKA REASOAP ER/ＳＲ Series

3. Ac/St system emulsion polymerization 3-1. Dosage effect In the case of styrene monomer, it is a little difficult to use SR-10 compared to acrylic monomer due to its characteristic of styrene. Here, it shows physical properties of the emulsion and the film with different dosage of surfactants. Monomer：BA/St/AA(49/49/2 wt%) Surfactant type Polymerization prescription Surfactant content on monomer (wt%) Initial monomer (wt %) Initial Surfactant (wt %) Monomer (g) Flask Water (g) SR-10 (g) Initiator (g) APS Monomer (g) Water (g) Feed SR-10 (g) Initiator (g) APS Total (g) Solid (%) Coagulation (%) Particle size (nm) Viscosity (mPa.s/25 oC ,10rpm) SR conversion (%) Water resistance (2) (hrs)

SR-10 Standard 0.75 1.5 5 5 10 5 4.5 4.5 56.40 56.80 0.068 0.068 0.1 0.1 85.5 85.5 52.02 52.40 0.608 1.282 0.1 0.1 199.3 200.8 45.5 45.5 1＜ 0.08 170 140 140 80 54 60 3 36

●Much dosage of SR-10 shows better water resistance.

Surfactant on monomer (%)

Water resistance

2.5

1.5

water resistance②

0.75 0

50

100 time (hr)

（10/13）

150

200

2.5 5 3 4.5 57.35 0.068 0.1 85.5 52.90 2.182 0.1 202.7 45.0 0.05 130 100 90 144

品名 ： ADEKA REASOAP ER/ＳＲ Series

3-2. Improvement of the conversion of SR-10 In the case of styrene showing lower emulsion stability, possible formulation is limited. Here, it shows that 1) initial polymerization ratio of monomer to SR-10 2) optimized formulation by post polymerization. ＊ SR-10=2.5 wt% on monomer Surfactant type Polymerization prescription Surfactant content on monomer (wt%) Initial monomer (wt %) Initial surfactant (wt %) Monomer (g) Water (g) Flask SR-10 (g) ER-30 (g) Initiator (g) APS Monomer (g) Water (g) Feed SR-10 (g) ER-30 (g) Initiator (g) APS Add APS (g) NaHSO3 (g) Post polymerization

Aging temperature (℃)

Aging time (hr) Total (g) Solid (%) Coagulation (%) Particle size (nm) Viscosity (mPa.s/25 oC ,10rpm) SR conversion (%) Water resistance (2) (hrs)

Monomer：BA/St/AA(49/49/2 wt%)

2.5 10 10 9.0 57.33 0.225 0.1 81.0 52.93 2.025 0.1 202.7 45.2 0.18 110 150 50 48

SR-10 Standard 2.5 2.5 5 5 5 3 4.5 4.5 57.34 57.35 0.113 0.068 0.1 0.1 85.5 85.5 52.91 52.90 2.138 2.182 0.1 0.1 202.7 202.7 45.2 45.0 0.09 0.05 120 130 150 150 70 90 72 144

SR-10/ER-30 Post polymerization 3.75(SR-10:2.5%,ER-30:1.25%) 10 20 9.0 57.20 0.450 0.225 0.1 81.0 52.8 1.800 0.900 0.1 0.2 75 1 203.8 45.5 0.05 110 200 90 96

● Generally St shows lower reactivity with SR-10 so that it might cause unreacted SR-10. In this case, optimized initial ratio of monomer to SR-10 can achieve closeness of polymerization rate and higher conversion without coagulation. Initial polymerization Mnomer/SR-10=5/3wt% (SR-10=2.5wt%(on monomer))

100

100

75

75

Conversion (%)

Conversion (%)

Initial polymerization Mnomer/SR-10=10/10wt% (SR-10=2.5wt%(on monomer))

50 25

SR-10

monomer

50 25 monomer

0 0

2

4

SR-10

0

6

0

time (hr)

2

4 time (hr)

（11/13）

6

品名 ： ADEKA REASOAP ER/ＳＲ Series

＊SR-10=1.5wt% on monomer

Monomer：BA/St/AA(49/49/2 wt%) Surfactant type Polymerization prescription Surfactant content on monomer (wt%) Initial monomer (wt %) Initial surfactant (wt %) Monomer (g) Flask Water (g) SR-10 (g) Initiator (g) APS Monomer (g) Water (g) Feed SR-10 (g) Initiator (g) APS Add APS (g) NaHSO3 (g) Post Aging temperature polymerization (℃) Aging time (hr) Total (g) Solid (%) Coagulation (%) Particle size (nm) Viscosity (mPa.s/25 oC ,10rpm) SR conversion (%) Water resistance (2) (hrs)

SR-10 Standard

Post polymerization 1.5

10 10 9.0 56.6 0.135 0.1 81.0 52.25 1.215 0.1 -

5 5 4.5 56.8 0.068 0.1 85.5 52.40 1.282 0.1 -

5 5 4.5 56.8 0.068 0.1 85.5 52.31 1.282 0.1 0.1 -

5 5 4.5 56.8 0.068 0.1 85.5 52.31 1.282 0.1 0.05 0.05

-

-

75

60

200.8 45.2 0.25 130 80 50 36

200.8 45.5 0.08 140 80 60 36

3 200.9 45.0 1＜ 160 100 90 96

3 200.9 45.0 0.1 150 100 90 96

● In the case of 1.5wt% of SR-10, possible formulation is limited and the post polymerization is effective.

Post polymerization with redox chaser (initiator) with lower temperature can improve conversion of SR-10 without coagulation. Improvement of conversion(SR-10) Initial polymerization monomer/SR-10=5/5wt%

Conversion of SR-10

100 75 APS 0.05g, NaHSO3 0.05g Aging temperture：75℃⇒60℃

50 25

post polymerization post polymerization none

0 0

2

4

6

time (hr)

（12/13）

8

10

品名 ： ADEKA REASOAP ER/ＳＲ Series

3-3. Recommended formulation example in each dosage It shows recommended formulation with SR-10.

Monomer：BA/St/AA(49/49/2 wt%) Surfactant

SR-10

Polymerization type

※

SR-10/ER-30 mix

TNS-100

Post polymerization

Standard

Post polymerization

1.5

2.5

3.75 (SR-10:2.5%,ER-30:1.25%)

1.5

2.5

5

5

10

5

5

5

3

20

5

3

4.5 56.8 0.068 0.1 85.5 52.40 1.282 0.1 200.8 45.5 0.03 130 120 3

4.5 57.35 0.068 0.1 85.5 52.90 2.182 0.1 202.7 45.6 0.04 140 160 6

Surfactant content on monomer (wt%) Monomer content of pure emulsification (wt %) Surfactant content of pure emulsification (wt %) Monomer (g) Water (g) Flask SR-10 (g) ER-30 (g) TNS-100 (g) Initiator (g) APS Monomer (g) Water (g) SR-10 (g) Feed ER-30 (g) TNS-100 (g) Initiator (g) APS Add APS (g) Post NaHSO3 (g) polymerization Aging temperature ( oC ) Aging time (hrs) Total (g) Solid (%) Coagulation (%) Particle size (nm) Viscosity(mPa.s/25 oC ,10rpm) Conversion (%) Water resistance(2) (hrs)

4.5 56.8 0.068 0.1 85.5 52.40 1.282 0.1 0.05 0.05 60 3 200.9 45.0 0.08 150 100 90 96

4.5 57.35 0.068 0.1 85.5 52.90 2.182 0.1 202.7 45.4 0.05 170 100 90 144

9 57.2 0.45 0.225 0.1 81 52.8 1.8 0.9 0.1 0.2 75 1 203.8 45.2 0.05 110 150 90 96

Standard

※

TNS-100：C13-10EO-SO3NH4(Conventional surfactant)

● The film with SR-10 shows better water resistance than that with conventional surfactant in styrene system as the same as acrylic system. Water resistance water resistance (2) TNS-100

SR-10 0

50

100

150

200

Time (hr)

（13/13）

Surfactant on monomer =2.5wt%