1

Synthesis, Characterization, and Photopolymerization of Polyisobutylene Phenol

(Meth)Acrylate Macromers

Bin Yang, Corey M. Parada, and Robson F. Storey*

*School of Polymers and High Performance Materials, The University of Southern

Mississippi, 118 College Drive #5050, Hattiesburg, MS 39406, USA.

E-mail: robson.storey@usm.edu

Supporting Information

Page

Table S1 2

Table S2 3

Figure S1 4

Figure S2 5

Figure S3 6

Figure S4 7

Figure S5 8

Figure S6 9

Figure S7 10

Figure S8 11

Figure S9 13

Figure S10 14

2

Table S1. PIB Isopropoxybenzene- and Phenol-Terminated PIB Precursors

Entry Sample Funct. Mn

(g/mol) PDI

1 3K PIB Diisopropoxybenzene 2 2,700 1.19

2 3K PIB Diphenol 2 2,700 1.19

3 4K PIB Triisopropoxybenzene 3 4,200 1.16

4 4K PIB Triphenol 3 4,300 1.15

5 10K PIB Triisopropoxybenzene 3 10,200 1.08

6 10K PIB Triphenol 3 10,000 1.10

3

Table S2. Thermal Stability of the Starting PIB (Meth)acrylate Macromers.

Sample Decomposition

Temp (starta), °C

Decomposition

Temp (mid pointb), °C

3K PIB diphenol diacrylate 381 427

3K PIB diphenol dimethacrylate 385 424

4K PIB triphenol triacrylate

387 430

4K PIB triphenol trimethacrylate 383 429

10K PIB triphenol triacrylate 381 420

10K PIB triphenol trimethacrylate 381 418

10K aliphatic PIB triol triacrylate 380 418 a5% PIB starting macromer weight loss,

b50% PIB starting macromer weight loss.

4

Figure S1. 1H NMR (600 MHz, CD2Cl2, 23°C) spectra of 10K PIB triphenol

triacrylate and trimethacrylate, and trifunctional PIB precursors, with peak

integrations: (A) PIB triisopropoxybenzene; (B) PIB triphenol; (C) PIB triphenol

triacrylate; (D) PIB triphenol trimethacrylate.

5

10 12 14 16

Elution Time (min)

4K PIB triIPB

4K PIB triphenol

4K PIB triphenol triA

4K PIB triphenol triMA

10K PIB triIPB

10K PIB triphenol

10K PIB triphenol triA

10K PIB triphenol triMA

10K aliphatic PIB triol triA

Figure S2. GPC traces of 4K and 10K trifunctional PIBs: PIB triisopropoxybenzene

(black), PIB triphenol (red), PIB triphenol triacrylate (blue), PIB triphenol

trimethacrylate (green), and aliphatic PIB triacrylate (dotted blue).

6

1500 2000 2500 3000 3500 4000

0

20000

40000

60000

80000

100000

120000

Inte

nsi

ty

M/z

2500 2550 2600 2650 2700 2750 2800

0

5000

10000

15000

20000

25000

B)

Inte

nsi

ty

M/z

2534.88

2590.932646.97

2703.072759.16

1500 2000 2500 3000 3500 4000

0

10000

20000

30000

40000

Inte

nsi

ty

M/z

2500 2550 2600 2650 2700 2750 2800

0

2000

4000

6000

8000

10000

12000

Inte

nsi

ty

M/z

2549.00

2605.11

2661.20

2717.222773.26

A)

Figure S3. MALDI-TOF mass spectra of A) 4K PIB triphenol triacrylate, and B)

PIB triphenol trimethacrylate, prepared by the dried droplet method using DCTB as

the matrix, AgTFA as the cationizing agent, and THF as the solvent.

7

3000 4000 5000 6000 7000 8000

0

1000

2000

3000

4000

Inte

nsi

ty

M/z

4500 4550 4600 4650 4700 4750

0

1000

2000

3000

4000

B)In

ten

sity

M/z

4500.09

4556.254612.37 4668.52

4724.63

3000 4000 5000 6000 7000 8000

0

5000

10000

15000

20000

Inte

nsi

ty

M/z

4550 4600 4650 4700 4750 4800

0

2000

4000

6000

8000

10000

12000

A)

Inte

nsi

ty

M/z

4570.55

4626.704682.81

4738.874794.94

Figure S4. MALDI-TOF mass spectra of A) 10K PIB triphenol triacrylate, and B)

10K PIB triphenol trimethacrylate, prepared by the dried droplet method using DCTB

as the matrix, AgTFA as the cationizing agent, and THF as the solvent.

8

2000 3000 4000 5000 6000 7000 8000 9000

0

5000

10000

15000

20000

Inte

nsi

ty

M/z

5150 5200 5250 5300 5350 5400 5450

0

5000

10000

15000

Inte

nsi

ty

M/z

5175.815231.83 5288.00

5344.14 5400.30

A)

Figure S5. MALDI-TOF mass spectrum of 10K PIB aliphatic triol triacrylate,

prepared by the dried droplet method using DCTB as the matrix, AgTFA as the

cationizing agent, and THF as the solvent.

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Figure S6. 1H NMR (600 MHz, CD2Cl2, 23°C) spectrum of 10K aliphatic PIB triol

triacrylate.

10

0 50 100 150 200 250 300 350

0

20

40

60

80

100

4K PIB triphenol triacrylate

4K PIB triphenol trimethacrylate

10K PIB triphenol triacrylate

10K PIB triphenol trimethacrylate

Co

nv

ersi

on

(%

)

Time (s)

Figure S7. Conversion vs. time for bulk photopolymerization of 4K PIB triphenol

tri(meth)acrylate and 10K PIB triphenol tri(meth)acrylate. Samples were irradiated

at 12 mW cm-2

using 1 wt% of Darocur® 1173 photoinitiator.

11

0 100 200 300 400 5000

20

40

60

80

100

3K PIB diphenol diacrylate

3K PIB diphenol dimethacrylate

4K PIB triphenol triacrylate

4K PIB triphenol trimethacrylate

Co

nv

ersi

on

(%

)

Time (s)

Figure S8. Conversion vs. time for bulk photopolymerization of 4K PIB triphenol

tri(meth)acrylates and 3K PIB diphenol di(meth)acrylates. Samples were irradiated

at 12 mW cm-2

using 1 wt% of Darocur® 1173 photoinitiator.

12

1700 1600 1500 1400 1300

F)

Wavenumbers (cm-1)

Before curing

UV cured

1700 1600 1500 1400 1300

Wavenumbers (cm-1)

Before curing

UV cured

E)

1700 1600 1500 1400 1300

D)

Wavenumbers (cm-1)

Before curing

UV cured

13

1700 1600 1500 1400 1300

C)

Wavenumbers (cm-1)

Before curing

UV cured

1700 1600 1500 1400 1300

B)

Wavenumbers (cm-1)

Before curing

UV cured

1700 1600 1500 1400 1300

Wavenumbers (cm-1)

Before curing

UV cured

A)

Figure S9. ATR-FTIR spectra of PIB tri(meth)acrylates before and after UV curing

(15 mW cm-2

, broad-spectrum centered 365 nm, 2 wt% Darocur® 1173): A) 4K PIB

triphenol triacrylate; B) 10K PIB triphenol triacrylate; C) 10K PIB triphenol

trimethacrylate, D) 10K aliphatic PIB triol triacrylate; E) 3K PIB diphenol

diacrylate, and F) 3K PIB diphenol dimethacrylate.

14

100 200 300 400 500 600

0

20

40

60

80

100

Wei

gh

t (%

)

Temperature (oC)

3K PIB diphenol diA

3K PIB diphenol diMA

4K PIB triphenol triA

4K PIB triphenol triMA

10K PIB triphenol triA

10K PIB triphenol triMA

10K aliphatic PIB triol triA

Figure S10. TGA analysis of seven starting PIB macromers before photocuring.