The Journal of Adhesion

ISSN: 0021-8464 (Print) 1545-5823 (Online) Journal homepage: https://www.tandfonline.com/loi/gadh20

Preparation and properties of polyisobutene/

organic montmorillonite hot melt pressure-
sensitive adhesive (HMPSA)

Xing Peng, Yu Wang, Hui Chen, Jie Ying & Jikui Wang

To cite this article: Xing Peng, Yu Wang, Hui Chen, Jie Ying & Jikui Wang (2019): Preparation and
properties of polyisobutene/organic montmorillonite hot melt pressure-sensitive adhesive (HMPSA),
The Journal of Adhesion, DOI: 10.1080/00218464.2018.1476145

To link to this article: https://doi.org/10.1080/00218464.2018.1476145

Published online: 06 Mar 2019.

Submit your article to this journal

Article views: 7

View Crossmark data

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=gadh20
THE JOURNAL OF ADHESION
https://doi.org/10.1080/00218464.2018.1476145

Preparation and properties of polyisobutene/organic

montmorillonite hot melt pressure-sensitive adhesive
(HMPSA)
Xing Penga, Yu Wanga, Hui Chenb, Jie Yinga, and Jikui Wanga
a
Key Laboratory for Preparation and Application of Ultrafine Materials of Ministry of Education, School
of Material Science and Engineering, East China University of Science and Technology, Shanghai,
China; bZhejiang Good Adhesive Co., Ltd, Tongxiang, Zhejiang, China

ABSTRACT ARTICLE HISTORY

To enhance the interfacial adhesion between Na-montmorillonite Received 13 March 2018
(Na-MMT) and polyisobutene (PIB) matrix, it is necessary to modify Accepted 9 May 2018
Na-MMT in organic way. Organic montmorillonite (OMMT) was KEYWORDS
successfully modified by Na-MMT with cetyltrimethyl ammonium Adhesion property; hot melt
bromide (CTAB) intercalation reagent. The X-ray diffraction (XRD) pressure-sensitive adhesives;
result showed that the d-spacing of Na-MMT was increased from organic montmorillonite;
1.424 to 2.480 nm after organic modification. PIB/OMMT hot melt polyisobutylene; system
pressure-sensitive adhesive (HMPSA) samples were prepared by stability
melt-intercalation process. The amount of OMMT was optimized
according to the system stability and adhesion performance. The
effects of OMMT content on rheological, adhesion and thermal
properties of PIB HMPSA were investigated. Adhesion performance
and system stability of PIB HMPSA were greatly improved by
adding moderate amounts of OMMT. In addition, the sample
containing 1 wt% OMMT exhibited optimal adhesion property
and excellent stability, meanwhile, its 180° peel strength was 1.19
times greater than pristine sample.

1. Introduction
Hot melt pressure sensitive adhesive (HMPSA) is a class of solvent-free
pressure sensitive adhesive (PSA) that adhere to surfaces under light contact
pressure and short contact time, which is considered eco-friendly due to the
absence of organic solvent. Base polymers, tackifier resins, plasticizers, and
fillers are the primary components of HMPSA. Nowadays, base polymers
have received extensive attention due to their large influences on main
performance of PSAs. There are variety of base polymers such as polyisobu-
tene (PIB), acrylic and styrenic. [1,2]
As a polymer matrix of HMPSA, PIB has many unique merits such as anti-
aging, high tack, and excellent chemical resistance [2] but creep behavior

CONTACT Jikui Wang wang326@ecust.edu.cn Key Laboratory for Preparation and Application of Ultrafine
Materials of Ministry of Education, School of Material Science and Engineering, East China University of Science and
Technology, Shanghai 200237, China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gadh.
© 2018 Taylor & Francis
2 X. PENG ET AL.

limits its application. Owing to the wide molecular weight distribution,

viscosity and adhesion properties could be adjusted by changing the ratio
of low- and high-molecular-weight PIBs. However, PIB adhesives have low
shear resistance as other non-cross-linked PSAs [3,4] even with high propor-
tions of high-molecular-weight PIB because of the low cohesive strength. [1]
Moreover, high viscosity may make processing difficult after increasing
molecular weight. Thus, introduction of dispersed fillers for further improve-
ment in the shear resistance of PSAs could be considered. Geiss and
Brockmann [4] introduced glass beads to styrene–isoprene–styrene (SIS)
PSAs, samples loaded with the filler indicated higher holding time and
lower creep compared with pristine PSAs. The filler geometry is crucial in
such applications, fillers with large surfaces such as fibers and flakes are
superior to spherical particles owing to higher reinforcing effect at equal
loading. Sehgal et al. [5] improved the creep behavior and mechanical
strength of SIS PSAs successfully by using clay nanoparticles.
The layered silicate nanoclay, particularly 2:1 smectic silicates such as
montmorillonite (MMT), represents the most reasonable and practical
route to polymer nanocomposites. [6] MMT is compatible with hydrophilic
polymers, such as poly(ethylene oxide) [7] and poly(vinylalcohol).[8] In
order to be miscible with non-polar polymers like PIB, MMT must be
modified in organic way. Lopez et al. [9] promoted the dispersion in poly-
amide matrix and accordingly enhancing the improvement in thermal and
mechanical properties of the corresponding nanocomposites using octadecy-
lamine modified MMT. Sadhu and Bhowmick [10] prepared SBR/MMT
nanocomposites using organic amine of different chain lengths. Hexadecyl
amine, stearyl amine, decyl amine and dodecyl amine were the amines used.
Thermal and mechanical properties of the nanocomposites is notably higher
for longer chain amine modified MMT contrasted to shorter chain amine
modified MMT.
Recently, some investigations regarding to introducing nanoclays into
PSAs have been done. Mičušik M et al. [11] prepared clay-PSAs by introdu-
cing macroinitiator modified MMT into the process of in-situ methyl acry-
late/butyl acrylate miniemulsion polymerization. They found that initiator
grafted Na-MMT provided good compatibility with the acrylic matrix and
even exist chemical interaction with the matrix during polymerization, as a
result, the tack of PSA increased significantly. Pang et al. [12] obtained a
formulation with enhanced thermal stability using silica nanoparticles mod-
ified with 3-methacryloxypropyltrimethoxysilane in the acrylic PSA, how-
ever, the peel and tack properties of the filled PSA were lower than pristine
unfilled system.
Although the active research carried out in the field of adhesion properties
of filled PSAs, non-crosslinked PSAs are rare candidates for such investiga-
tion. Kostyuk et al. [13] suppressed cold flow of PIB adhesives using fumed
 JOURNAL OF AMERICAN COLLEGE HEALTH 3

silica (up to 20 wt%) and halloysite nanotubes (up to 40 wt%). The results
revealed that the three-dimensional network was formed in the bulk of the
matrix of PIB-halloysite system and the shear adhesion properties of PIB-
silica system were highly increased. However, high concentration of clay will
largely increase the viscosity of PSA which is not conducive to the fabrication
and application of PSA. Some researchers [13–15] found that shear strength,
peel strength and tack of PSAs are generally antagonistic properties, specifi-
cally, the variation trend of peel strength is converse with tack while peel and
shear strength have the same varying trend.
In this research, organic montmorillonite (OMMT) was obtained by
modifying Na-MMT with cetyltrimethyl ammonium bromide (CTAB) and
the PIB/OMMT HMPSA was fabricated by melt-intercalation. The main
purpose of this research was to explore the effects of dispersed OMMT on
system stability and adhesion property of PIB HMPSA.

2. Experimental
2.1. Materials
Oppanol B50 (Mw = 400,000), as the PIB matrix was purchased from BASF
China Co., Ltd. (Shanghai, China). PB 1300 (Mw = 1300) was supplied by Daelim
Corporation of South Korea (Seoul, South Korea). The tackifying resin C5 1304
was obtained from Shanghai Jinsen Petroleum Resin Co., Ltd. (Shanghai, China).
Cetyltrimethyl Ammonium Bromide (CTAB) was provided by Shanghai Titan
Scientific Co., Ltd. (Shanghai, China). PGW Na-montmorillonite (Na-MMT) was
purchased from Nanocor Inc. of America (Chicago, America).

2.2. Preparation of OMMT

200 mL DI water was poured into a 500 mL three-necked flask with 10 g Na-
MMT, stirred magnetically to form homogeneous solution at room tempera-
ture for 12h. Meanwhile, 4 g CTAB was added into a 250 mL beaker with
100 mL DI water, stirred until a homogeneous organic intercalation reagent was
prepared. The flask with dispersed Na-MMT suspension was put in the ultra-
sonic water-bath and the suspension was mixed by mechanical stirring at 60°C.
The organic intercalation reagent was dropped into Na-MMT suspension
within 30 min and the reaction time was 6 h. The reaction product was vacuum
filtrated and washed with DI water several times to remove any remaining
organic intercalation reagent. After drying at 80°C for 24 h, the reaction
product was ground to fine powder which denoted as OMMT.
4 X. PENG ET AL.

2.3. Preparation of PIB/OMMT HMPSA

The filled PIB HMPSAs were prepared by melt compounding in Haake
torque rheometer (160Nm Polylab QC) equipped with roller-blade rotors.
First of all, PIB Oppanol B50, PB 1300, tackifying resin C5 1304 and OMMT
were added into the mixing chamber of Haake torque rheometer at 140°C.
The weight ratio was as follows: PIB Oppanol B50: PB 1300: tackifying resin
C5 1304 = 1: 4: 5, the content of OMMT added in the polymer matrix was 0,
0.5, 1.0, 1.5 and 2.0 wt% respectively. As a result, samples were named M0,
M0.5, M1, M1.5 and M2 accordingly.

2.4. Characterization
2.4.1. Fourier transform infrared (FT-IR) spectroscopy
The FT-IR spectra were recorded at room temperature using a Nicolet 6700
FT-IR spectrometer in the range of 4000–400 cm−1 with the scanning rate of
20 min−1 and a resolution of 4 cm−1.

2.4.2. X-ray diffraction (XRD)

The XRD analysis of Na-MMT and OMMT were obtained in a D/max2550V
X-ray diffractometer at ambient temperature. The range of the diffraction
angle (2θ) is from 0.5° to 15°. The d-spacing of Na-MMT and OMMT (d)
was calculated using the Bragg equation: nλ = 2dsinθ, where λ is the
wavelength of the X-ray and θ is the scattering half angle.

2.4.3. Contact angle measurement

The surface wettability of Na-MMT and OMMT were determined by contact
angle measurement instrument (JC2000D2, China). Samples were prepared
by using powder pressed method.

2.4.4. Microscopy
Diffusion of different amounts of OMMT in PIB matrix were observed in
room temperature by a inverted biological microscope (37XF, China).
Specimens were obtained by coating the HMPSAs onto glass slides.

2.4.5. Rheological testing

Rheological studies were performed using a rotational rheometer (Thermo
Haake RS600, America). A parallel-plate geometry was used (the diameter of
plate was 20 mm). The tests were carried out in dynamic frequency sweep
modes (selected strain: γ = 0.1%), which were conducted at 25°C over a
angular frequency range from 0.01 to 100 rad·s−1 oscillations per second in
shear mode. The diameter and thickness of flake-like specimen were 20 mm
and 1 mm respectively.
 JOURNAL OF AMERICAN COLLEGE HEALTH 5

2.4.6. Adhesive measurement

180° peel strength was measured using a universal tensile testing machine
(2KW CMT 2203, China). The samples were prepared by following GB/T
2792–1998. The adhesives were coated onto the polyester film (dimension
25 mm × 200 mm), and the coating thickness was about 0.2 mm. Then, the
film attached to stainless steel substrate and a 2 kg rubber roller was passed
twice to press onto the stainless steel substrate afterwards. The measurements
were carried out at an angle of 180° between the substrate and PSA specimen
with a peeling rate of 300 mm/min at room temperature. The peel strength
values were averaged for five specimens and expressed in N/m.

2.4.7. Thermogravimetric analysis (TGA)

The thermal stability of samples was detected using thermogravimetric ana-
lysis (HCT-3, China). The samples were heated from 80 to 650°C at a heating
rate of 10 °C·min−1 under nitrogen atmosphere.

3. Results and discussion

3.1. Organic modification of Na-MMT
FTIR spectra of Na-MMT, OMMT and CTAB are shown in Figure 1. Peaks
at 2918 and 2848 cm−1 belong to two different CH bonds vibration of the
-CH2 group in CTAB. [16] Absorption intensities of these two peaks in
OMMT are obviously stronger than those in Na-MMT, which indicates the
CTAB chains have inserted into Na-MMT layers. Besides, there appears a

Figure 1. FTIR spectra of Na-MMT, OMMT, and CTAB.

6 X. PENG ET AL.

new peak in OMMT at 720 cm−1 which is assigned to Br− of terminal group
in CTAB, [16] this further confirms that CTAB chains have intercalated into
the layers of Na-MMT.
Layer spacing of Na-MMT and OMMT which are listed in Table 1 can be
calculated from Bragg formula at peak positions of XRD curves in Figure 2.
The (001) crystal plane diffraction peak of Na-MMT appears at 2θ = 6.2º and
the peak of OMMT is in the range of 3.56º. It is clear that the interlayer space
of Na-MMT increased from 1.424 to 2.48 nm after the organic modification
process.
The hydrophilic and hydrophobic performance of Na-MMT and OMMT
surface can be reflected by water contact angle patterns which are shown in

Table 1. XRD results of Na-MMT and OMMT.

Samples 2θ (º) d001 (nm)
Na-MMT 6.200 1.424
OMMT 3.560 2.480

Figure 2. XRD pattern of Na-MMT and OMMT.

Figure 3. Water contact angles on the surfaces of (a) Na-MMT and (b) OMMT.
 JOURNAL OF AMERICAN COLLEGE HEALTH 7

Figure 3(a) and (b). The water contact angle of OMMT surface (74.5º) is
much bigger than Na-MMT surface (47º), hence OMMT is more hydropho-
bic than Na-MMT. As PIB matrix is nonpolar, OMMT is more compatible
with matrix compared to Na-MMT.

3.2. Dispersion of OMMT in the PIB matrix

In order to study the dispersion of different amounts of OMMT in PIB
matrix, HMPSAs were observed using optical microscope.
As shown in Figure 4, OMMT particles in M0.5 and M1 are small and
uniformly distributing. However, in M1.5 and M2, OMMT particles appear
some large aggregates obviously. This is attributed to high surface energy of
OMMT layers in PIB matrix, as a result, small OMMT particles will tend to
pack together to decrease surface energy while their distribution density in
PIB matrix is too large (above 1.0 wt%).

3.3. Rheological properties of PIB/OMMT HMPSAs

The dynamic frequency test is widely used in characterization of viscoelastic
performance of PSAs. In low frequency domain, storage modulus (G’)
reflects the bonding process while loss modulus (G’’) represents the debond-
ing process in high frequency domain. [17,18]

Figure 4. Optical microscope images of samples with different OMMT concentration.

8 X. PENG ET AL.

Figure 5. Dynamic frequency curves of storage modulus (G’), loss modulus (G’’), and complex
viscosity (η*) as a function of OMMT concentration in PIB HMPSAs.

The frequency sweep curves for G’, G’’ and complex viscosity (η*) of
samples tested by rotational rheometer at ambient temperature are included
in Figure 5. As it can be seen in Figure 5(a,b), in low frequency region, G’
and G” increase with angular frequency. The increase in G’ is because with
the action time of shear force is getting shorter and the direction of shear
force changes rapidly, polymer chains become stiff as they are not ready for
deforming. The increase in G” is because with the increased frequency of
polymer chain friction, work expended in unit time is getting higher.
Moreover, G’ and η* decrease with the addition of OMMT to the PIB
HMPSA. This is largely owing to some polymer chains intercalated into
the galleries of OMMT during melt blending process, as a result, there
exist local-ordering structure in PIB matrix, so the moving resistance
between molecular chains gets smaller, the G’ and η* are tend to decrease
after adding OMMT.
As can be seen from Figure 5(c), M0 is the first one which exhibited a
behavior of shear thinning in high frequency region. It shows that OMMT
enhance the stability of PIB HMPSAs under high shear frequency because
there are polymer chains intercalated into the galleries of OMMT and the
OMMT layers which absorbed polymer chains serve as physical crossing
points, such interaction between OMMT layers and polymer chains lead to
 JOURNAL OF AMERICAN COLLEGE HEALTH 9

formation of physical crosslinked network in polymer matrix. The system of

PIB HMPSA will be more stable when the additive amounts of OMMT reach
1.0 wt% or 1.5 wt%.

3.4. Adhesion performance of PIB/OMMT HMPSAs

Commonly used classification of PSAs according to the value of peel strength
is presented in Table 2, [19] which can be used as a reference for application
of PSAs.
The addition of OMMT can greatly influence 180° peel strength of PIB
HMPSAs, as shown in Figure 6. 180° peel strength reach to the maximum
when OMMT content is 1.0 wt%. This is mainly attributed to the hydro-
phobic character and the augment in d-spacing of OMMT. Due to the strong
interfacial adhesion between OMMT and PIB matrix, some PIB chains are
absorbed on OMMT layers so that there exist physical crosslinked network in
the matrix. As a result, the stability of PIB-system is improved. However,
when OMMT content is over a critical value, 1.0 wt%, peel strength will
decrease. Because OMMT particles tend to form large aggregates easily due

Table 2. Classification of pressure-sensitive adhesives versus peel resis-

tance and removability. [19]
PSA Grade 180° Peel Resistance (N/mm)
Excellent permanent >0.56
Permanent 0.4 ~ 0.56
Semiremovable 0.24 ~ 0.32
Removable and repositionable 0.08 ~ 0.16
Excellent removable <0.04

Figure 6. 180° peel strength values of PIB HMPSAs with 0, 0.5, 1, 1.5, and 2 wt% OMMT.
10 X. PENG ET AL.

Figure 7. TGA curves of PIB HMPSAs with 0, 0.5, 1.0, 1.5, and 2 wt% OMMT.

to their high surface energy while their concentration in the matrix is too
large (above 1.0 wt%), as demonstrated in Figure 4, and these large aggre-
gates which presented in bonding interface will adversely affect the peel
strength. Combining Table 2 and Figure 6, PIB/OMMT HMPSA is a type
of excellent permanent PSA.

3.5. Thermal stability of PIB/OMMT HMPSAs

The thermal stability of PIB/OMMT HMPSAs was evaluated by TGA under
nitrogen atmosphere. Figure 7 presents the TGA curves of adhesives with
different contents of OMMT (0, 0.5, 1.0, 1.5 and 2 wt%), and the tempera-
tures at 1.5, 10, 50 and 95% weight losses (T1.5%, T10%, T50% and T95%) are
summarized in Table 3. From both Figure 7 and Table 3, it is observed that
the five samples are stable up to about 210°C while the weight loss less than
1.5%. The thermal stability of HMPSAs improves significantly with the
amount of OMMT increasing when the OMMT content is below 1.0 wt%.
Moreover, the sample M1 which contains 1.0% OMMT has best thermal
stability. Besides the reason that OMMT particles block the thermal motion

Table 3. TGA results of samples with 0, 0.5, 1.0, 1.5 and 2 wt% OMMT.
Samples T1.5%(°C) T10%(°C) T50%(°C) T95%(°C)
M0 212 317 398 438
M0.5 261 351 407 441
M1 274 357 409 445
M1.5 235 338 400 437
M2 255 345 405 440
 JOURNAL OF AMERICAN COLLEGE HEALTH 11

of polymer chains, it is also attributed to the physical crosslinked networks in

the matrix which are formed between OMMT layers and PIB chains.

4. Conclusion
A series of PIB HMPSAs modified with different amounts of OMMT were
successfully prepared by melt-intercalation, the OMMT used was obtained by
modifying Na-MMT with CTAB. The addition of OMMT is beneficial to
improve the system stability of PIB HMPSA. Besides, the thermostability and
180° peel strength are also increased. Combining the results of dynamic
frequency test, adhesion property measurements and thermogravimetric
analysis, the optimum additive amount of OMMT is 1.0 wt%. PIB/OMMT
HMPSA is a type of excellent permanent PSA, due to its high adhesion
performance and stable system, there will be more potential applications of
PIB/OMMT HMPSA in many fields such as label, packaging, medical and
hygienic products.

Acknowledgements
The authors sincerely acknowledge Zhejiang Good Adhesive Co., Ltd. for providing assis-
tance and funding.

Funding
This work was supported by the Zhejiang Good Adhesive Co., Ltd.

References
[1] Willenbacher, N., and Lebedeva, O., Polyisobutene-Based Pressure-Sensitive Adhesives.
In Technology of Pressure-Sensitive Adhesives and Products, 4th ed. Benedek, I.,
Feldstein, M. M., Eds.; (CRC, Taylor & Francis, Boca Raton, 2009), pp. 162–169.
[2] Nasrollahzadeh, M., Ganji, F., Taghizadeh, S.-M., and Vasheghani-Farahani, E., Int. J.
Adhes. Adhes. 78, 28–37 (2017). DOI: 10.1016/j.ijadhadh.2017.06.005.
[3] Antonov, S.-V., and Kulichikhin, V.-G., Shear Resistance. In Handbook of Pressure-
Sensitive Adhesives and Products: Fundamentals of Pressure Sensitivity, 8th ed. Benedek,
I., Feldstein, -M.-M., Eds.; (CRC, Taylor & Francis, Boca Raton, 2009), pp. 204–221.
[4] Geiss, P.-L., and Brockmann, W., J. Adhes. 63, 253–263 (1997). DOI: 10.1080/
00218469708017222.
[5] Sehgal, K. C., J. Adhes. 83, 509–511 (2007). DOI: 10.1080/00218460701389243.
[6] Goettler, L.-A., Lee, K.-Y., and Thakkar, H., Polym. Rev. 47, 291–317 (2007). DOI:
10.1080/15583720701271328.
[7] Aranda, P., and Ruiz-Hitzky, E., Chem. Mater. 4, 1395–1403 (1992). DOI: 10.1021/
cm00024a048.
[8] Hosseinzadeh, H., Zoroufi, S., and Mahdavinia, G.-R., Polym. Bull. 72, 1339–1363
(2015). DOI: 10.1007/s00289-015-1340-5.
12 X. PENG ET AL.

[9] López, D.-G., Mitre, I.-G., Fernández, J.-F., Merino, J.-C., and Pastor, J. M., Polymer.
46, 2758–2765 (2005). DOI: 10.1016/j.polymer.2005.01.038.
[10] Sadhu, S., and Bhowmick, A.-K., Rubber Chem. Technol. 76, 860–875 (2003). DOI:
10.5254/1.3547777.
[11] Mičušík, M., Bonnefond, A., Paulis, M., and Leiza, J.-R., Eur. Polym. J. 48, 896–905
(2012). DOI: 10.1016/j.eurpolymj.2012.03.002.
[12] Pang, B., Ryu, C.-M., and Kim, H.-I., Mater. Sci. Eng. 178, 1212–1218 (2013). DOI:
10.1016/j.mseb.2013.08.005.
[13] Kostyuk, A., Ignatenko, V., Smirnova, N., Brantseva, T., Ilyin, S., and Antonov, S., J.
Adhes. Sci. Technol. 29, 1831–1848 (2015). DOI: 10.1080/01694243.2014.980616.
[14] Brantseva, T., Antonov, S., Kostyuk, A., Ignatenko, V., Smirnova, N., Korolev, Y.,
Tereshin, A., and Ilyin, S., Eur. Polym. J. 76, 228–244 (2016). DOI: 10.1016/j.
eurpolymj.2016.01.040.
[15] Brantseva, T.-V., Antonov, S.-V., and Gorbunova, I.-Y., Int. J. Adhes. Adhes. 82, 263–
281 (2018). DOI: 10.1016/j.ijadhadh.2018.01.001.
[16] Elfeky, S.-A., Mahmoud, S.-E., and Youssef, A.-F., J. Adv. Res. 8, 435–443 (2017). DOI:
10.1016/j.jare.2017.06.002.
[17] Ho, K.-Y., and Dodou, K., Int. J. Pharm. 333, 24–33 (2007). DOI: 10.1016/j.
ijpharm.2006.09.043.
[18] Micutz, M., Aricov, L., Ilie, C., and Staicu, T., Int. Adhes. Adhes. 70, 10–16 (2016). DOI:
10.1016/j.ijadhadh.2016.05.001.
[19] Kim, H.-J., Lim, D.-H., and Park, Y.-J., Peel Resistance. In Handbook of Pressure-
Sensitive Adhesives and Products: Fundamentals of Pressure Sensitivity, 7th ed. Benedek,
I., Feldstein, -M.-M., Eds.; (CRC, Taylor & Francis, Boca Raton, 2009), pp. 170–171.