Journal of Macromolecular Science, Part B

Physics

ISSN: 0022-2348 (Print) 1525-609X (Online) Journal homepage: https://www.tandfonline.com/loi/lmsb20

Influence of the Environment on the Phase II - I

Transformation of Isotactic Polybutene - 1

Martina Kaszonyiova & Frantisek Rybnikar

To cite this article: Martina Kaszonyiova & Frantisek Rybnikar (2019): Influence of the
Environment on the Phase II - I Transformation of Isotactic Polybutene - 1, Journal of
Macromolecular Science, Part B, DOI: 10.1080/00222348.2019.1574424

To link to this article: https://doi.org/10.1080/00222348.2019.1574424

Published online: 07 Mar 2019.

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JOURNAL OF MACROMOLECULAR SCIENCE, PART B
https://doi.org/10.1080/00222348.2019.1574424

Influence of the Environment on the Phase II - I

Transformation of Isotactic Polybutene - 1
Martina Kaszonyiova and Frantisek Rybnikar
Department of Polymer Engineering, Tomas Bata University, Zlin, Czech Republic

ABSTRACT ARTICLE HISTORY

The phase II to I transformation process of isotactic polybutene – 1 Received 20 December 2017
(iPB-1) is influenced by the environment besides the usual physical Accepted 12 January 2019
factors. The phase II ! I transformation rate depends, first of all, on
KEYWORDS
the segmental mobility of the polymer chains. Environmental sub-
Phase II - I transformation;
stances which are good solvents of iPB-1 increased the phase trans- isotactic polybutene - 1;
formation rate at room temperature. Other substances, such as air, environmental effects
water, some acids or blends with atactic polypropylene, decreased
the transformation rate in comparison with a sample exposed to a
phosphorus pentoxide desiccant environment. The environmental
effects also influence several other structural characteristics, such as
sample crystallinity and crystallite size.

1. Introduction
Isotactic poly-1-butene (iPB-1) has a polymorphic character. Its structure has four main
crystal forms I, I, II and III, with helix conformations 3/1, 11/3 or 4/1,[1–4] Table 1. The
forms I and I, both with 3/1 helices, are variations of a hexagonal crystal lattice depend-
ing on the preparation methods. Form III usually forms from precipitation of solutions
or by high pressure crystallization. The kinetically favored phase II forms after melt
cooling and its formation is followed by a spontaneous phase transformation of II to I.
Figure 1 shows the X- ray diffraction scans of the most important iPB-1 phases. We
propose that the II ! I transformation can proceed by three mechanisms, described
here as N (neutral), P (plus) or M (minus) type, according to the nucleation and growth
characteristics.[5] This natural phase transformation increased the majority of the iPB-1
characteristics (e.g. melting temperature, density and tensile strength) but on the other
hand it is relatively slow (days, weeks) which has resulted in research efforts for its
acceleration.[6–8] The transformation is fastest at room temperature and atmospheric
pressure. The transformation rate increases with pressure, orientation and some addi-
tives.[8–11] However, the use of solid additives for increasing the transformation rate has
been shown to be only partially effective.[2,6,9] Till now the main method for increasing
the phase transformation rate of iPB-1 has been based on sample deformation.[7,10]
In this article we primarily describe the effect of some environmental agents, in vapor
or liquid form at room temperature, on the II ! I transformation process and their

CONTACT Martina Kaszonyiova mhribova@ft.utb.cz Department of Polymer Engineering, Tomas Bata University,
Zlin, 760 01, Czech Republic.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lmsb.
ß 2019 Taylor & Francis Group, LLC
2 M. KASZONYIOVA AND F. RYBNIKAR

Table 1. Structures of isotactic polybutene-1.[5]

Helical Parameters of Characteristic
Phase Crystal lattice structure crystal lattice, nm Density, g/cm3 temperatures,  C
I Twined hexagonala 23/1 a ¼ b¼ 1,77 0,950 Tm ¼ 126–128
c¼ 0,65
I‘ Hexagonalb 23/1 a ¼ b¼ 1,77 0,950 Tm ¼ 95–100
c¼ 0,65
II Tetragonalc 211/3 a¼ 1,46 0,907 Tm ¼ 114–117
c¼ 2,12
III Rhombohedrald 24/1 a¼ 1,24 0,897 Tm ¼ 96
c¼ 0,56
Amorphous Amorphous – – 0,868 Tg ¼ 24,2
a
It forms by annealing of metastable phases I‘, II or III, or by crystallization from solution precipitation.
b
It forms by crystallization under pressure or from solution precipitation.
c
It forms by free melt cooling or by annealing of phase III. It is metastable and transforms to the stable phase I by age-
ing or physical deformations.
d
It forms by solution precipitation or by crystallization under pressure.

Figure 1. X-ray diffraction scans of the most important isotactic polybutene-1 phases, I, II and III.

influence on the resulting iPB-1 structure, extending a recent, briefer report.[5] The
tested substances of neutral, alkaline or acidic character which had no substantial effect
on the crystal transformation are labeled here as N - neutral. On the other hand, a
set of compounds, mainly iPB-1 solvents, effectively increased the II ! I phase trans-
formation rate. They act at room temperature as either vapors or liquids in contact with
the sample, without the sample totally dissolving. This group of solvents is here labeled
by P (plus). Besides the effect on the phase transformation rate, some of them also
influence the polymer phase structure after drying or precipitation from their solution
where, e.g., phase III or a blend of phases I, II and III formed. Another group of sub-
stances had the opposite effect on the phase transformation rate, in majority decreasing
the transformation rate as compared to the sample in the phosphorus pentoxide envir-
onment, because of the presence of an induction period during which the phase trans-
formation was stopped or significantly slowed down. These substances contained -OH
or acidic groups and iPB-1s blends with them and with atactic polypropylene are here
marked by M (minus).
 JOURNAL OF MACROMOLECULAR SCIENCE, PART B 3

2. Experimental
2.1. Samples
For the measurements commercial homopolymer samples (LyondellBasell Industries
N.V., Netherlands), differing in their molecular weight, PB 0110 M, PB 0300 M, DP
0400 M, and a random copolymer with ethylene, DP 8640, (Table 2), were used. After
standard melting of the granules 5 min at 160  C, the samples were free cooled to room
temperature at atmospheric pressure.[13]
The effect of vapors on the sample structure changes was measured using 1 mm thick
sheets of the sample located ca. 20 mm above the tested liquid surface in a closed con-
tainer kept at room temperature and atmospheric pressure. The samples were exposed
to the vapors for the whole testing period. For comparison, the results for the tested
samples were compared to those for a reference sample which was exposed to a desic-
cant, phosphorus pentoxide environment. All testing vapors sources were of the highest
possible purity. The swelling % (Dm) was characterized by regular weight changes
determinations.

2.2. X-ray diffraction

For X-ray diffraction measurements an X-pert Pro X-ray diffraction system (Malvern
PAN analytical B.V., Netherlands) was used. The X-ray radiation was CuKa (40 kV and
30 mA) filtered by nickel. The scans were measured in the reflexion mode (4,5 2H/
min) in the 2H range 5 – 30 at room temperature. The samples of N and M type were
measured every 24 h after crystallization started. The type P samples were analyzed at
the beginng of the experiment ca every 1 hour, and then at the end once.
In Table 3, the symbols XII, XI and Xt characterize the values of the sample crystallin-
ity in phase II, I and total crystallinity at the end of the phase transformation. As
described in more detail below, the Xt and XI values in Table 3 were determined
3 weeks after initial sample melting/crystallization, while the value of XII was determined
ca 20 min after initial sample crystallization. The XI and XII were determined as the
ratio of all the peak areas of the given crystalline phase and the amorphous background
(Figure 2). The half-time of the II ! I transformation, r, is the time at which XI equals
XII (Figure 3). The values of L, characterizing the polymer crystal size/perfection, were
calculated from the peak width at its half-height using the Scherrer equation[14] for the
most intense crystal peaks of phases I and II. The induction period, IP, corresponds to

Table 2. Material characteristics of PB-1.[5]

Ethylene content
MFI, percentage
Sample, Tm of g/10 min [12], mol by weight
Labeling phase I [12],  C 190  C/2.16 kg Composition % [11] mol% [11] Mw, 103 g/mol[11]
110 128 0,4 PB-1 homopolymer 0 0 711
300 127 4 PB-1 homopolymer 0 0 347
400 126 15 PB-1 homopolymer 0 0 293
8640 113 1 random copolymer 1,5 0,75 470
of PB-1 with a low content
of ethylene
Tm - test method ISO 11357-3.
 4

Table 3. The effects of environment on the iPB-1.

Environment
Sample Environment type Dm, % XII, % Xt , % XI, % IP, h r, h L200, Å L110, Å
110 gasoline P 10.47 38 57.86 56.7 x 2.6 553 375
trichloromethane P 26.07 41 47.86 47.9 x 2.6 618 261
toluene P 8.3 33.7 52.38 49.2 x 3.6 440 320
xylene P 7.33 37.5 57.33 55.5 x 3.9 588 382
benzene P 10.85 33.1 57.56 57.6 x 4.8 533 361
tetrachloromethane P 29.07 47.1 48.68 48.7 1.5 5.7 503 594
acetone M  35.6 58.2 52.5 21.0 30 323 357
phosphorus pentoxide N  37.6 57.2 53.1 x 34.5 420 527
methanol M 0.24 45.8 62.52 56.7 19.0 39.4 526 424
submerged in water M  38.5 58 52.1 20.0 41 349 403
vacuum N  39 56.87 48.3 x 43.4 355 410
phenol M 0.14 45 58.07 50.6 25.5 46.1 469 468
M. KASZONYIOVA AND F. RYBNIKAR

hydrochloric acid M 0.04 39.1 56.65 47.5 25.0 51.6 421 518
methylphenol M 0.04 42 60.34 51.4 25.5 52 462 451
natrium hydroxide M 0.04 43.5 59.2 49.2 25.5 53.5 458 488
ethanol M 0.81 40.4 55.47 45.9 24.0 54.8 436 478
water vapor M 0.04 41.7 59.38 48.7 24.0 59 450 409
air M  42.4 60.99 52.9 25.0 59.4 499 465
phosphoric acid M  38.5 51 32.0 22.0 67.5 403 414
ethane-1,2-diol M 0.29 39 57.11 44.2 25.0 68.9 415 426
acetic acid vapor M 1.24 38.4 58.05 48.5 25.0 69 311 420
Potassium M  38.6 54 42.8 24.0 69.3 438 423
permanganate þ Phosphoric acid
propane-1,2,3-triol M 0.07 43 56.89 46.6 25.0 70 458 497
potassium hydroxide M 0.03 40.6 57.45 47.1 26.0 71.5 460 473
hydrogen peroxide M  39.1 54.5 42.0 24.0 75.8 426 408
nitric acid M 0.32 43.7 56.19 45.9 24.0 82.3 480 433
ammonium hydroxide M 0.26 38.7 56.7 44.8 24.0 82.9 455 427
hydrofluoric acid M 0.16 40.5 60.63 49.6 24.0 83.6 436 435
110 þ 5 % paraffin xylene P  44.5 50 50.0 x 3 478 401
acetic acid P  44.5 58.3 58.3 x 11 478 423
water vapor P 0.17 44.5 58.6 57.4 x 11.6 478.0 394.0
air P  44.7 59.6 58.0 x 12.5 479
phosphorus pentoxide M  39.1 53.5 42.0 24.0 75.4 570 667
110 þ 5 % LPE xylene P  38.7 44.6 44.6 x 10.4 570 411
acetic acid M  38.7 56.4 52.8 20.0 32 570 467
phosphorus pentoxide M  38.7 53.9 52.2 24.0 37.2 566 436
 water vapor M 0.1 38.7 57.2 54.3 21.0 39.2 570 524
air M  38.7 53.8 50.6 20.0 42.5 570 470
110 þ 5 % iPP xylene P  49 x < 2,75
acetic acid P  42.2 55.2 53.7 x 19 486 571
air M  42.2 58.1 55.6 19.0 29.3 486 314
phosphorus pentoxide N  39 51.7 50.5 x 29.7 502 495
water vapor M 0.1 42.2 53.1 53.1 21.0 33.8 486 480
110 þ 5 % aPP xylene M  38.2 44.3 44.3 5.7 10.9 447 340
acetic acid M  36.8 52.3 43.3 20.0 64.9 415 445
air M  38 38.9 58.0 24.0 90 447 372
water vapor M  37 53 42.8 90.0 290 441 393
300 trichloromethane P 26.38 42.2 47.81 47.8 x 0.42 332 316
gasoline P 7.37 39.5 52.13 49.5 x 1.2 315 289
benzene P 12.58 37.4 52.35 52.4 x 2.2 399 302
toluene P 0.07 36.9 54.68 53.3 x 2.5 422 275
tetrachloromethane P 31.19 35.9 39.24 39.2 x 2.9 476 385
xylene P 7.29 35.2 52.78 48.9 x 11.4 409 342
acetone M  41 58.8 54.3 22.0 34 365 404
methanole M 0.25 37.5 53.83 43.6 22.0 52.6 392 413
ethanol M 0.39 42.3 58.64 49.3 19.0 53.9 458 529
vacuum N  39.4 54.22 48.3 x 54.4 467 410
acetic acid M 0.35 40.2 57.01 47.1 20.0 55.8 433 452
water vapor M 0.13 39 55.46 44.1 22.0 63 417 378
hydrochloric acid M 0.03 42.9 59.66 50.5 21.0 64.8 439 439
nitric acid M 0.15 39 57.35 46.6 20.0 66.9 440 443
phosphorus pentoxide M  38.9 53.5 43.5 24.0 69.3 407 405
methylphenol M 0.04 41 58 48.4 21.0 69.3 452 389
air M  37 55.11 44.6 21.0 70 396 403
ammonium hydroxide M 0.01 40 56.28 45.2 48.0 75.2 414 393
ethane-1,2-diol M 0.12 40 56.52 44.4 20.0 76.8 426 431
phenol M 0.07 40.5 58.62 47.3 21.0 77.7 443 413
propane-1,2,3-triol M 0.01 41.1 58.64 46.9 20.0 78.6 446 401
hydrofluoric acid M 0.06 47 54 41.0 20.0 92 472 453
400 xylene P  43.2 54.3 54.3 x 7.2 362 363
acetone M  42.9 58.4 57.4 21.0 30 219 252
vacuum M  38.3 63.16 59.9 20.0 47.6 538 481
hydrofluoric acid M 0.06 43.5 58.2 51.5 20.0 58.5 480 629
acetic acid M 0.16 45.5 58.9 52.5 22.0 59 519 362
air M  46.4 59.7 49.7 24.0 64 537 472
JOURNAL OF MACROMOLECULAR SCIENCE, PART B

water vapor M 0.95 40.2 56.4 48.5 24.0 70 313 226

phosphorus pentoxide N  39.2 55.7 49.4 x 108 461 418
(continued)
5
 6

Table 3. Continued.
Environment
Sample Environment type Dm, % XII, % Xt , % XI, % IP, h r, h L200, Å L110, Å
8640 xylene P  27.4 28.6 15.9 x 5 304 219
acetone P  31.8 49 47.7 x 11 323 206
vacuum M  27 51.68 46.3 22.0 15 359
hydrofluoric acid N  30.6 46.3 39.0 x 19.6 385 295
acetic acid N 0.21 30.6 47.2 40.1 x 21 385 318
phosphorus pentoxide N  29.6 47.7 42.0 x 24.2 390 410
air N  31.1 51.8 46.7 x 32 348 329
water vapor N 0.05 26.3 49.7 42.1 x 32 263 394
not measured.
M. KASZONYIOVA AND F. RYBNIKAR
 JOURNAL OF MACROMOLECULAR SCIENCE, PART B 7

Figure 2. The typical resolution of the crystal peaks of isotactic polybutene-1 I and II phases and the
amorphous scattering for the sample PB 0110 M measured 3 weeks after melt/crystallization,
P2O5 atmosphere.

the time during which the transformation process didn’t yet take place; its length was
determined as the time up to that at which the crystallinity (Xt or XI) started to increase
faster then in the initial period (e.g. Figure 3c), with X ray scans being taken every 24 h.

3. Results and discussion

The most important results in this report concern the influence of some environmental
media on the iPB-1 structure and, mainly, on the phase II to I transformation rate at
room temperature. The tested samples were always melted at and for the same tempera-
ture and time, then free cooled to room temperature, which is the optimal temperature
for the fastest phase II to I transformation.[13] Our extended results described here
proved that the environmental effects we initially described in reference [5] that influ-
ence the phase II transformation can be divided into the 3 types, N, P and M, as
described above.
Typical changes for PB 0110 M of total crystallinity (Xt), and of phases I (XI) and II
(XII) as a function of time for the principal environmental effects are shown in Figure
3. The results for a dry, vapor free atmosphere (i.e. the phosphorus pentoxide environ-
ment), labeled N, is presented in Figure 3a. The results for exposure to solvent vapors
(such as gasoline, trichloromethane, toluene, xylene, tetrachloromethane or benzene) are
shown in Figure 3b (labeled P effect). Those substances are very good solvents for iPB-1
and most polyolefines. Gasoline is an exception, because it dissolves iPB-1 only partially.
The third example, for the exposure to non-solvents such as water, acids etc., labeled
M, are shown in Figure 3c.
The results concerning the effects of the environment on the sample crystallinity (Xt),
phase I amount (XI) and the half time of the transformation (r) are summarized in
Table 3. The environmental effects differed physically and/or chemically, were numer-
ous and were mostly combined; thus it was difficult to quantitatively determine their
individual contributions. The most important effects, except for physical effects
described earlier,[8–11] are here linked to good solvents or additives containing –CH2
8 M. KASZONYIOVA AND F. RYBNIKAR

Figure 3. Typical changes of total crystallinity (Xt), phases I (XI) and II (XII) as a function of time for
the principal environmental effects; the data shown are for in a) PB 0110 M, P2O5 atmosphere, b) PB
0110 M, xylene vapor, c) PB 0110 M, H2O vapor environment.
 JOURNAL OF MACROMOLECULAR SCIENCE, PART B 9

groups which sped up the phase transformation significantly due to the additives rela-
tively high segmental mobility. On the other hand, an important transformation rate
decrease (increased r) in the case of PB 0110 M (only), relative to the same sample type
exposed to the phosphorous pentoxide environment was induced by, e.g., strong acids,
strong alkaline substances, diols, water and, most significantly, by addition of atactic
polypropylene (aPP) or other amorphous polymers into the iPB-1 blends [contribution
in preparation]. The important structural changes due to environmental effects that
were observed can be described in terms of the sample’s crystallinity and phase trans-
formation rate:

3.1. Crystallinity
The sample crystallinity values were evaluated from the courses of crystallinity changes
with time (see Figure 3) and are listed in Table 3:

1. XII is the original sample crystallinity value, describing the amount of phase II in the
sample after melting/crystallization before the phase II ! I transformation started. The
values were 33–47% for sample PB 0110M) and similar results were found for samples
PB 0300M and DP 0400M. The crystallinity values for copolymer DP 8640 were naturally
lower (26–32%). The variation in values are suggested to be due to different samples
being prepared for each test, with some resulting variations in processing and time of
measurements.
2. Another characteristic was the final total crystallinity (Xt), determined 3 weeks after the
end of the phase II ! I transformation in the various environments; it includes the sum
of crystallinities of new phase I and residual phase II content (e.g. 48–63% for sample
PB 0110M).
3. The XI was evaluated as the final phase I crystallinity 3 weeks after sample melting.
(32–57.6% for sample PB 0110M).

The observed differences between values of the XII at the start and Xt after the end of
the transformation suggests that part of the initially amorphous content was crystallized
into the phase I (as a part of the secondary crystallization process or some still crystal-
lized as phase II after the transformation started and then transformed).
The samples used here (PB 0110 M, PB 0300 M and DP 0400M) differed in molecular
weight (Table 2). There was a general tendency that, with increasing sample molecular
weight, the total crystallinity (Xt) was slightly lower in the samples with a similar envir-
onmental, thermal and time history.
The final total crystallinity (Xt) values varied in the range 46–62.5% for all PB
0110 M samples subjected to the explored environment types, a range larger than for
the range for XII and, as described above, of larger crystallinity. The samples exposed to
the good solvent vapors (P) were characterized by two important effects: 1. a higher
transformation rate (lower r) compared to the other samples and 2. by a full phase II –
I transformation.
The samples with environments of type M and N had higher r values than those in P
environments, leading to higher Xt than those in the P type vapors, which means that,
from the point of view of ordering or re-ordering, a longer time was required for the
full phase transformation.
10 M. KASZONYIOVA AND F. RYBNIKAR

The variation in crystal size, L110 (form I) and L200 (form II), values were not consist-
ent enough to be fully explainable.
Generally, we see that about one half of the final sample volume was amorphous.
The details of this amorphous phase structure are not known; it may consists of poly-
mer chains with physical entanglements or with a different tacticity or helical structure.
A part of the amorphous phase could crystallize to phase I under favorable conditions
or phase II could continue to be formed by secondary crystallization after the start of
the II ! I transformation in other areas of the sample.

3.2. Phase transformation rate

The phase transformation rate is, practically, the most important aspect of the structural
changes of iPB-1. The results in this article disclose that there are three different trans-
formation courses characterized mainly by the transformation rate and details of the
nucleation and growth processes. Figure 3a and b differ in the rate of nucleation of
phase I and its growth; whereas Figure 3b shows very fast nucleation and growth,
Figure 3a has much slower nucleation and growth processes. The sample shown in
Figure 3c has almost the same nucleation and growth rate as the sample in Figure 3a,
but there is an induction period prolonging the phase transformation. The effects influ-
encing the phase II ! I transformation rate are suggested to be as follows.

3.2.1. The effect of sample molecular weight

The effect of sample molecular weight was here evaluated with three samples PB
0110 M, PB 0300 M and DP 0400 M (Table 2). Together with different molecular
weights the samples were subjected to some generally neutral environments such as air,
vacuum or phosphorus pentoxide. The sample crystallinities XII for these three environ-
ments before the start of the phase transformation were in the range 37–46.4% and the
resulting XI, after the phase transformation, were 48.3–59.9% which testifies that,
besides the full transformation of phase II, also 4.6–13.5% of phase I was formed during
the secondary crystallization from the amorphous phase or additional II formed while
the II ! I transformation occurred. The differences in the XII (determined at the begin-
ning of phase transformation) and XI (3 weeks after sample melting and phase trans-
formation) (37.6; 53.1, 38.9;43,5 and 39.2;49.4 for XII, XI, of PB 0110 M, PB 0300 M and
DP 0400 M, respectively, in phosphorus pentoxide environment) values testify that the
samples differed not only in molecular weight, but also in other factors influencing the
phase transformation.
The transformation rate values, characterized by the r values, lay in a broad interval
(2.6–290 h) depending on the sample molecular weight and environment. In the three
previously mentioned tested environments (air, vacuum and phosphorus pentoxide) the
sample PB 0110 M had r values of 34.5–59.4 h, the lower molecular weight PB 0300 M
had r ¼ 54.4 to 70 h and in the even lower molecular weight sample DP 0400 M the r
values were 47.6–108 h. Although there were differences in the ordering of the rate for
the various neutral environments the general trend of a decrease of the transformation
rate with increasing sample molecular weight was obvious. We suggest that the longer
 JOURNAL OF MACROMOLECULAR SCIENCE, PART B 11

molecules can form higher amounts of different chain conformations from which some
can have the conformation approaching that of a crystal nucleus.
The relatively broad range of XII values for a given sample measured at the beginning
of the phase transformation (Table 3) is not only due to the experimental errors but is
suggested to be due to possible further effects which are not known to us, such as the
local presence of initiators remnants or other additives, impurities in the samples, etc.
Repeated experiments on any given sample proved the same general trends and the
transformation type (P, M, N).

3.2.2. The effect of an increased segmental mobility

The phase transformation rate naturally depends on the polymer chain segmental
mobility. E.g., the iPB-1 random ethylene copolymers (copolymer DP 8640) with flexible
comonomer groups, such as –CH2 –, had a higher transformation rate (lower value of
r) than the iPB-1 homopolymers except in the xylene environment. The chain segmental
mobility could also be enhanced by blending iPB-1 with miscible substances containing
supposed higher mobility segments (paraffin, linear polyethylene or isotactic polypropyl-
ene) which resulted in a faster transformation rate (Table 3).
A second possible method to increase the segmental mobility is to add solvents. The
adsorption of solvent vapors by the iPB-1 samples (Dm), which was up to 29% for PB
0110 M and 31% for PB 0300 M, both for the high density tetrachloromethane at room
temperature, was higher compared to the adsorbtion of the other environments (P, M),
such as water, hydrofluoric acid, alkalies or phenol, where the adsorption was an order
of magnitude lower. The adsorbed solvent molecules separated the polymer chains seg-
ments and permited easier conformation changes. All this led to a greater transform-
ation rate.

3.2.3. The effect of the type of environment

The general chemical nature of the environments, such as acids, alkalies, oxidants, alco-
hols or phenols, all of M type, influenced mainly the transformation rate (r). For the
samples BP 0110 M and PB 0300 M the r values lay in a relatively broad range, 30–92 h,
and the induction period values (IP) were in a small range 19–48 h. Other substances,
without strong chemical effect, that decreased the phase transformation rate relative to
phosphorous pentoxide environment, were water vapors or the addition of the aPP and
also the substances of the generally neutral group (air, vacuum).

3.2.3.1. The accelerating environments. The environmental effects could, in the case of
those solvents classified here as P type, consist of the solvent absorption by the polymer
or by a partial (local) dissolution (plastication) which basically supports a higher seg-
mental mobility and permits the conformation changes which resulted in a higher trans-
formation rate.
The most significant environmental effect on the transformation rate was noticed in
the case of the good solvents vapors for iPB-1 alone, such as gasoline, trichloromethane,
toluene, xylene, benzene and tetrachloromethane. The organic solvent vapors, contrary
12 M. KASZONYIOVA AND F. RYBNIKAR

to the other environmental types, increased the transformation rate so that the r values
were lower than 5.7 hours for sample PB 0110 M (in comparison with e.g., PB 0110 M
in the phosphorus pentoxide environment, where r ¼ 34.5h). In the case of gasoline
vapors, the increase in transformation rate was very high (PB 0110 M had r ¼ 2.6 hours
and in the sample PB 0300 M, 1.2 hours) while in the case of trichloromethane PB
0110 M had r ¼ 2.6 hours and the sample PB 0300 M, 0.6 hours. The effect of good solv-
ent vapors, we suggest, is due mainly to a higher segmental mobility and, consequently,
a higher possibility to form the transformation nuclei. The solvents influence the seg-
mental mobility so strongly that the whole phase II content changed into phase I. This
higher segmental mobility had a similar influence as physical effects, such as microwave
or electrical fields,[15,16] in changing the sample conformation. The segmental mobility
was also increased by the presence of the chemical groups – CH2 – in the copolymer
and in the iPB-1 blends.
The vapors of a good solvent for iPB-1 containing Cl atoms (triclorometane and tet-
rachloromethane) significantly increased the segmental mobility but the resulting
samples had the lowest total crystallinity, Xt relative to the reference sample exposed
to phosphorous pentoxide environment. The solvent vapors mainly containing Cl
atoms or an aromatic hydrocarbon caused a high swelling of the sample, up to 31%
(for BP 0300 M in tetracholomethane), in contrast to the other environmental cate-
gories where the swelling was usually lower than 1%. However, the amount of
absorbed solvent in the sample was not quantitatively connected with the increased
transformation rate.

3.2.3.2. Materials chemically neutral to iPB-1. In the case of strong inorganic acids
(hydrochloric acid, hydrofluoric acid, phosphoric acid, nitric acid etc.) and bases
(ammonium hydroxide), their vapors probably also include the activity of water. The
FTIR measurements did not verify the presence of chemical groups stemming from the
acids, bases or environmental substances being attached to or interspersed in the poly-
mer chains. There was only a slight increase of the 1718 cm1 band, which means a
slight increase of the C ¼ O groups, probably by an oxidation which could decrease the
transformation rate.
The effects of environmental species other than good solvents resulted not only in a
slower phase transformation rate than phosphorus pentoxide (Figure. 3a and c), but
also in the fact that the transformation of phase II was only partial. A remaining ques-
tion is why the initial higher transformation rate decreased for non-good solvents and
had no tendency to approach the total phase II transformation. The curves in Figure 3a
and c show that in the time from the beginning to, e.g. 25 h, the transformation rate
was much slower than in Figure 3b.

3.2.3.3. The retarding environments. The data in Table 3 also shows many cases where
the environmental effects clearly decreased the phase transformation rate (M effect)
compared to the rate in, e.g., solvents. They were, first of all, for particular substances
containing –OH groups (H2O, ethane-1,2-diol, propane-1,2,3-triol and ammonium
hydroxide) and numerous acids. The M effect is, in fact, an opposite effect to the P
effect. The cause of the M effect is higher r values due to a limited segmental mobility.
 JOURNAL OF MACROMOLECULAR SCIENCE, PART B 13

The decreased segmental mobility of iPB-1 could, for instance, be connected with the
formation of moderately strong hydrogen bonding between water and hydrogen atoms
in the iPB-1 chain.[17,18]
A strong effect on the transformation rate was found in the case of water vapors (PB
0110 M had r ¼ 59 h or 80 h in the case of PB 0300 M and 70 h for DP 0400M) where
the phase II ! I transformation rate markedly decreased. A remaining question is how
water vapors can block the transformation or growth rate. The retarding effect of water
was confirmed by the increased transformation rate in the case of a sample PB 0110 M
exposure to a vacuum or phosphorus pentoxide atmosphere which decreased the water
content in the sample. We suggest that the effect of many environmental agents may be
simply attributed to the presence of water vapors.
The phase transformation influence by the substances marked M (Figure 3c) was
characterized by several facts: In the transformation course there was always present an
induction period where the transformation rate was minimal or absent. Another
important characteristic of the (M) transformation course was that it did not take place
in the whole phase II, but about 10–20% of the phase II remained unchanged (same as
N type) in contrast to the course P process where the entire phase II was converted to
phase I (Figure 3b and c).

3.2.3.4. Induction period. During the induction period of the M process the phase I
nuclei were obviously not formed or were less effective and the transformation process
could only effectively procede after 20–90 h. In most cases the induction period lay in
the range 20–26 h (Table 3, Figure 3c), with this being the time of first measuring the
changes. This fact suggests that the number of pertinent transformation nuclei were
almost the same and probably stemed from the amount of initial heterogeneities, or
from phase I or II crystallization nuclei already present in the sample. We can speculate
that the role of polymerization initiators (solid heterogeneities) may also play the role
of phase transformation nuclei. Following the induction period the phase transform-
ation process continued with a rate similar to cases without environmental influences.
The action of chemical effects of the environment on the phase transformation nuclei is
acceptable in practice in spite of not knowing the details of this process. By the addition
of amorphous polymer, labeled aPP, into the blend a strong M effect appeared (mostly
in the presence of water vapor). Possibly aPP could influence the direction of the iPB-1
helical structures. The xylene vapors, which by themselves accelerated the phase trans-
formation, effectively eliminated the effect of aPP addition on the phase transition rate.
So, the normal effects of those two main actions resulted in opposite reactions on the
transformation nuclei. In both cases the detailed mechanism of this interaction is not
yet apparent.

3.2.3.5. Combined effects. The combined effect for our samples includes the simultaneous
influence of at least two different substances or chemical groups. In reality, most cases of
environmental effects are combined, being the results of the simultaneous presence of air
with water vapors plus any additional factor, which is difficult to quantify.
In iPB-1 there are –CH2- groups in the polymer chain backbone. Further, the poly-
mer blends and the copolymer and a number of the various environmental factors
14 M. KASZONYIOVA AND F. RYBNIKAR

contained –CH2- groups. For instance, in the case of acetic acid influencing the homo-
polymer PB 0110 M alone the r was 69 h while for the acetic acid in the homopolymer
blends of PB 0110 M with paraffin the r value decreased to 11 h, in blends with linear
polyethylene to 32 h, with iPP to 19 h and in the random copolymer DP 8640 the r was
21 h. In all mentioned cases the combined effects of acetic acid and the –CH2- groups
increased the transformation rate.
On the other hand, the combined effects of aPP or other amorphous polymers
[report in preparation] in the blend with iPB-1 and air or water vapor resulted in a
decrease of the transformation rate (e.g. compare the r ¼ 90 h for air with r ¼ 290 h for
water vapors for PB 0110 M and aPP). On the other hand, the combination of blend PB
0110 M with aPP and xylene vapors substantially increased the transformation rate
(r ¼ 12h) compared to 3.9 h for PB 0110 M and xylene alone.

4. Conclusions
In neutral environments (N) iPB-1 samples with a higher molecular weight have a
lower transformation rate of phase II to I than those with lower molecular weight.
More important practically was the influence of the P and M environmental effects
on the structure and transformation rate. The individual environments influenced the
sample crystallinity, the crystal phase composition and quality, the final amount of
phase I and, also, the mechanism and type of the transformation process.
Due to the action of various different environments there are basically three
types of the phase II ! I transformation mechanisms, those which accelerate
(P type), are neutral (N type) or decreased (M type) the phase transformation
rates. The first mechanism (P) is supported by the presence of solvent vapors or
flexible molecular segments which increase the polymer segmental mobility
and facilitate the phase nucleation and growth process (solvent vapors or –CH 2 -
groups in blend component and copolymers). The rate decreasing action of envir-
onmental substances is attributed to the presence of – OH groups in water, acids
or other compounds. The possible effect of moderately strong hydrogen bonds
between water and hydrocarbons cannot be excluded. [17,18] It is interesting that
the most efficient transformation rate retarding effect was due to the addition of
atactic polypropylene. The details of these effects on the transformation rate II !
I are not yet fully known.
The environmental effects only slightly affected the final sample crystallinity for most
environments. However, tetrachloromethane and trichloromethane decreased the sample
crystallinity by approximately 10% in comparison with the other environments.
The most important finding is that specific solvents can influence the full transition
of phase II to phase I. Also, the interaction of the solvent vapor with the sample’s
amorphous phase played an important role. The solvent vapors dissolve preferentially in
the sample’s amorphous phase, increase its segmental mobility and so support the phase
transformation process. This effect of increased segmental mobility was confirmed in
copolymers with ethylene and in blends with linear polyethylene, paraffin and isotactic
polypropylene, all containing –CH2- groups.
 JOURNAL OF MACROMOLECULAR SCIENCE, PART B 15

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