Cooperative and Independent Effect of Modular Functionalization on Mesomorphic Performances and Microphase Separation of Well-Designed Liquid Crystalline Diblock Copolymers

Article abstract of DOI:10.1002/chem.202000268

Liquid crystalline block copolymers (LCBCPs) are promising for developing functional materials owing to an assembly of better functionalities. Taking advantage of differences in reactivity between alkynyl and vinyl over temperature during hydrosilylation, a series of LCBCPs with modular functionalization of the block copolymers (BCPs) are reported by independently and site-selectively attaching azobenzene moieties containing alkynyl (LC₁) and Si-H (LC₂) terminals into well-designed poly(styrene)-block-polybutadienes (PS-b-PBs) and poly(4-vinylphenyldimethylsilane)-block-polybutadienes (PVPDMS-b-PBs) produced from living anionic polymerization (LAP). By the principle of modular functionalization, it is demonstrated that mono-functionalized (PVPDMS-g-LC₁)-b-PB and PS-b-(PB-g-LC₂) not only maintain independence but also have cooperative contributions to bi-functionalized (PVPDMS-g-LC₁)-b-(PB-g-LC₂) in terms of mesomorphic performances and microphase separation, which is evident from differential scanning calorimetry (DSC) and polarized optical morphologies (POM) and identified by powder X-ray diffractions. With the application of the new principle of modular functionalization, local-crosslinked liquid crystalline networks (LCNs) with controlled functionality are successfully synthesized, which show well-controlled phase behaviors over molecular compositions.

Full text of DOI:10.1002/chem.202000268

A Journal of
Accepted Article
Title: Cooperative and Independent Effect of Modular Functionalization
on Mesomorphic Performances and Microphase Separation of
Well-Designed Liquid Crystalline Diblock Copolymers
Authors: Lan Lei, Li Han, Hongwei Ma, Ruixue Zhang, Shuai Huang,
Heyu Shen, Lincan Yang, Chao Li, Songbo Zhang, Hongyuan
Bai, Qingchi Ma, and Yang Li
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.202000268
Link to VoR: http://dx.doi.org/10.1002/chem.202000268
Supported by

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
Cooperative and Independent Effect of Modular Functionalization
on Mesomorphic Performances and Microphase Separation of
Well-Designed Liquid Crystalline Diblock Copolymers
Lan Lei, Li Han,* Hongwei Ma, Ruixue Zhang, Shuai Huang, Heyu Shen, Lincan Yang, Chao Li,
Songbo Zhang, Hongyuan Bai, Qingchi Ma, and Yang Li*
L. Lei, Dr. L. Han, Prof. H. W. Ma, R. X. Zhang, S. Huang, H. Y. Shen, L. C. Yang, C. Li, S. B. Zhang, H. Y. Bai, Q. C. Ma, and Prof. Y. Li
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning key Laboratory of Polymer Science and Engineering,
School of Chemical Engineering, Dalian University of Technology, Dalian Liaoning 116024, China.
E-mail: liyang@dlut.edu.cn (Y. Li), hanli.dlut.edu.cn (L. Han)
Supporting information for this article is given via a link at the end of the document.
Abstract: Liquid crystalline block copolymers (LCBCPs) are
promising for developing functional materials owing to assembly of
better functionality. Taking advantage of difference in reactivity
between alkynyl and vinyl over temperature during hydrosilylation, a
series of LCBCPs with modular functionalization of block copolymers
(BCPs) are reported by independently and site-selectively attaching
azobenzene moieties containing alkynyl (LC1) and Si-H (LC2)
terminals into well-designed poly(styrene)-block-polybutadienes (PS-
b-PBs) and poly(4-vinylphenyldimethylsilane)-block-polybutadienes
(PVPDMS-b-PBs) produced from living anionic polymerization (LAP).
By the principle of modular functionalization, it is demonstrated that
mono-functionalized (PVPDMS-g-LC1)-b-PB and PS-b-(PB-g-LC2)
not only maintain independence but also have cooperative
contributions to bi-functionalized (PVPDMS-g-LC1)-b-(PB-g-LC2) in
terms of mesomorphic performances and microphase separation,
which is evident from differential scanning calorimetry (DSC) and
polarized optical morphologies (POM) and identified by powder X-
ray diffractions. With the application of new principle of modular
functionalization, local-crosslinked liquid crystalline networks (LCNs)
with controlled functionality are successfully synthesized, which
show well-controlled phase behaviors over molecular compositions.
of new self-assembled morphologies, and the explorations of
their applications in different fields.[2d, 3c, 4] A variety of synthetic
methodologies have been developed to fabricate LCBCPs, for
example, macromolecular induced conventional free radical
polymerization of mesogenic moieties containing double bonds,
and post-modification of BCPs containing OH/Cl side groups
with mesogenic moieties, but they are lack of well-controlled
structures.[5] As is known, the well-designed molecular weight
and a narrow polydispersity index (PDI) are indispensable to
achieve a basic molecular control. In recent years, many
researches have applied macromolecular induced reversible
addition-fragmentation chain-transfer polymerization (RAFT) to
obtain the LCBCPs with well-controlled structures.[6] Therefore,
the self-assembled morphologies of microphase separation have
been well-controlled by varying chain length of BCPs and
grafting density of LCBCPs.[3b, 7] However, few attempts have
been made to reveal the independent and cooperative effect of
different functions on LC properties and microphase separation
of LCBCPs.[6a, 7b] The synthesis and complete characterization of
LCBCPs with well-designed functions in different blocks of BCPs,
i.e., modular functionalization, are challenging but valuable to be
explored.[4a, 7a]
From the perspective of molecular manipulation, living anionic
polymerization (LAP) is one of the best methods to obtain BCPs
with well-controlled molecular weight and narrow PDI.[8] With
regard to this field, our group has synthesized bi-functionalized
BCPs templates,[9] and LCBCPs with a well-controlled grafting
density in different blocks have been developed via highly
efficient post-functionalization of mesogenic moieties with BCPs
produced by LAP.[8a] However, a limitation remains regarding a
site-selective functionalization of BCPs. To reveal an interior
relationship between different functions, developing newly
designed LCBCPs with modular functionalization, in which the
specific functions are site-selectively incorporated into different
blocks, is highly important.
As is known, funtionalization based on general polymers has
become important to realize the synthesis of functioal materials
with high performance. For this reason, poly(styrene-block-
butadiene) (PS-b-PB) as a general polymer rubber has been
taken into consideration to the synthesis of LCBCPs, because
PS-b-PB rubbers that improve the mechanical performance and
transparency depending on compositions have been widely
used as thermoplastic elastomers.[10] However, unfunctionalized
PSs have difficulties in achieving a post-functionalization and a
site-selective manipulation in different blocks, which require a
rational molecular design.
Introduction
The principle of building “blocks” to assemble better functionality
into a single molecular is becoming attractive towards driving
specific functions.[1] To facilitate higher performance and gain
innovative functionality, liquid crystalline block copolymers
(LCBCPs) have received an unprecedented insight in molecular
engineering and multifunctional materials.[2] As liquid crystalline
(LC) and block copolymers (BCPs) with multiscale spatial orders
are representative of self-organized systems, LCBCPs have an
unpredictably cooperative and competitive motion between LC
and BCPs order with control of compositions.[3] Furthermore,
LCBCPs are generally composed of LC blocks and non-LC
blocks served as rigid and flexible segments, which will induce
spontaneous microphase separation due to thermodynamic
differences of different blocks.[3b,
3e]
For this reason, it is
necessary that LCBCPs with well-controlled structures are
developed to manipulate LC properties and microphase
separation by tuning the motions between LC and BCPs order,
as well as the thermodynamic differences of different blocks.
More and more researches of LCBCPs have been focused on
the development of new synthetic methodologies, the discovery
1
This article is protected by copyright. All rights reserved.

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
Synthesis of monomers and polymeric matrixes. Synthetic
details and characterization for PVPDMS-b-PBs and PS-b-PBs
with well-designed DP are according to previous report,[8a, 11c]
which are briefly described in Supporting Information. Since Azo
mesogens have been frequently incorporated into LCBCPs,
alkynyl and Si-H terminated Azo-alkynyl (LC1) and Azo-SiH (LC2)
have been synthesized and characterized as shown in
Supporting Information. The characteristic peaks and their
integrations in 1H NMR of PVPDMS-b-PBs and PS-b-PBs are in
good agreement with the designed structures, which are
displayed in Figure S4-S5. GPC curves show a narrow and
symmetric monomodal distribution (PDI=1.05-1.09) in Figure 1.
As summarized in Table 1, PVPDMS-b-PBs and PS-b-PBs have
well-controlled number-average molecular weight (Mn) and
narrow PDI in different blocks. The self-crosslinking reaction of
PVPDMS-b-PB occurred due to the hydrosilylation between Si-H
of PVPDMS and double bonds of local PB blocks at 60 °C in
previous work,[11c] and thus this work introduced alkynyl
terminals in pursuit of LCBCPs with modular functionalization.
Because alkynyl groups have a higher reactivity than double
bonds at room temperature, which is desirable to obtain a
selective addition in different blocks.[9c]
Scheme 1. Synthetic strategy of LCBCPs with modular functionalization.
In present work, much attention has been paid to poly(4-
vinylphenyldimethylsilane)-block-polybutadiene (PVPDMS-b-PB)
with Si-H in PVPDMS blocks and double bonds in PB blocks as
bi-functionalized sites, because polybutadiene (PB) and poly(4-
vinylphenyldimethylsilane) (PVPDMS) showed a high tunability
of additional functionality in previous studies.[11] Taking
advantage of difference in reactivity between alkynyl and vinyl
groups over temperature during hydrosilylation, Azo-alkynyl
(LC1) and Azo-SiH (LC2) with alkynyl and Si-H terminals are
independently and site-selectively attached into PVPDMS-b-PBs
and PS-b-PBs with well-designed degree of polymerization (DP)
produced from LAP. As shown in Scheme 1, it is desirable to
obtain LCBCPs with modular functionalization using a principle
of “building” blocks, where the functional positions of grafted
blocks and grafting density are controlled. The independent and
cooperative effect of different functions is confirmed by mixing
PB-g-LC2 and PVPDMS-g-LC1 in different mole ratios in
comparison with LCBCPs, which is evident from DSC and POM
results and identified on the basis of powder X-ray diffractions.
We are inspired to apply this new principle to obtain the local-
crosslinked liquid crystalline networks (LCNs) with reasonably
designed functionality (Figure 4), as researchers have devoted
much effort to the innovation of LCNs owing to the reversible
order-disorder phase transition,[12] which will contribute to
understanding the structure-property relations and further
designing materials.
Synthesis of mono-functionalized LCBCPs. In this work,
PVPDMS-b-PBs with different DP (Table 1) were firstly used for
post-modification with alkynyl-terminated Azo-Alkynyl (LC1).
After performing the hydrosilylation of PVPDMS-b-PBs with Azo-
1
Alkynyl (LC1) at 30 °C, the synthetic process was tracked by H
NMR and FT-IR. As shown in Figure 1c, the appearance of δ
(ppm) = 5.88 assigned to -Si(CH3)2-CH=CH- of LCBCPs and the
disappearance of peaks δ (ppm) = 4.45 assigned to Si-H of
PVPDMS blocks in 1H NMR indicated a complete addition of
PVPDMS blocks with Azo-Alkynyl (LC1). As shown in Figure S7,
the complete addition was further determined by FT-IR with the
disappearance of the absorption at 2116 cm-1 of Si-H groups in
PVPDMS blocks. Moreover, the typical signals δ (ppm)= 5.68-
4.85 of double bonds from PB blocks displayed no integral
1
changes in H NMR, which indicated that Si-H groups preferred
to react with alkynyl groups of Azo-Alkynyl (LC1) rather than
double bonds of PB blocks in PVPDMS-b-PBs around room
temperature when excessive Azo-Alkynyl (LC1) was used.
Therefore, a series of (PVPDMS-g-LC1)-b-PB showed a block
selective ability of mono-functionalization in PVPDMS blocks
and an almost 100% grafting density. To achieve the mono-
functionalizatin in PB blocks relative to PS blocks, PS-b-(PB-g-
LC2) as a contrast was synthesized after the treatment of Azo-
SiH (LC2) with PS-b-PB via hydrosilylation at 50 °C, which was
supported by 1H NMR (Figure 1d and S6a) and FT-IR (Figure S7)
and described in Supporting Information.
Results and Discussion
Table 1. Molecular compositions and thermal properties of the designed BCPs.
BCPs [b]
Mn (kg/mol) [b]
PS/PVPDMS[c]
PB [d]
Mn (kg/mol)[d]
Thermal Properties
Designed BCPs [a]
PDI [b]
Mn (kg/mol)[c]
PDI [c]
1,4-PB(%) [e]
Tg1 (°C)[f]
Tg2 (°C)[f]
PS3k-b-PB6k
PS3k-b-PB12k
PS3k-b-PB18k
PVPDMS3k-b-PB6k
PVPDMS3k-b-PB18k
PVPDMS3k-b-PB30k
11.6
15.4
22.8
10.4
20.3
33.7
1.06
1.05
1.05
1.06
1.07
1.09
3.0
3.2
3.0
4.2
3.2
4.0
1.15
1.13
1.12
1.13
1.28
1.15
8.6
12.2
19.8
6.2
17.1
29.7
90.9
91.7
92.1
90.1
90.9
91.6
-93
-92
-94
-86
-91
-94
17
19
21
32
29
29
[a] BCPs with well-designed Mn (PS/PVPDMS) and Mn (PB) in different blocks. [b,c,d] Number-average molecular weight (Mn) and polydispersity index (PDI),
determined by GPC. [c] PS and PVPDMS blocks of PS-b-PBs and PVPDMS-b-PBs, obtained by sampling. [d] PB blocks, determined by formula: Mn (PB)=Mn
(BCPs)-Mn (PS/PVPDMS).
1,4-PB mole fraction (%), calculated by 1H NMR (shown in Figure S5). [f] The first glass transition temperature (Tg1) of
[e]
PVPDMS and PS blocks, and the second glass transition temperature (Tg2) of PB blocks, determined by DSC.
2
This article is protected by copyright. All rights reserved.

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
PVPDMS blocks while an approximate 20% grafting density in
PB blocks.
Fundamentally, the independent and cooperative effect of
different functions in different blocks on mesomorphic
performances and microphase separation can thus be
investigated in terms of LCBCPs with modular functionalization,
including mono-functionalized (PVPDMS-g-LC1)-b-PB and PS-b-
(PB-g-LC2), and bi-functionalized (PVPDMS-g-LC1)-b-(PB-g-
LC2) with different DP.
Polarized optical morphologies (POM). On the basis of POM
observations in Figure 2a, the broken focal conical and spherical
textures of Azo-Alkynyl (LC1) as well as the focal conical and
rod-like textures of Azo-SiH (LC2) formed when heated and
cooled. POM morphological variations of Azo-Alkynyl (LC1) and
Azo-SiH (LC2) were indicative of the presence of LC phases and
possible phase transitions. When Azo-Alkynyl (LC1) and Azo-SiH
(LC2) were attached into PVPDMS-b-PBs and PS-b-PBs, the
mesomorphic behaviors of mono/bi-functionalized LCBCPs were
investigated. As shown in Figure 2b, LC morphological textures
were observed in both mono/bi-functionalized LCBCPs. As in
previous work, the textures of polymers were not well-formed
due to highly flexible PB blocks.[8a] When adding pressure on the
polarized film, the colorful morphologies formed drawing near to
Ti. The morphological textures were observed in a brighter order:
PS-b-(PB-g-LC2)<(PVPDMS-g-LC1)-b-PB<(PVPDMS-g-LC1)-b-
(PB-g-LC2), which suggested that PB LC blocks and PVPDMS
LC blocks of LCBCPs had cooperative contributions to the
brighter textures of bi-functionalization.
Figure 1. The GPC traces of (a) PVPDMS-b-PBs and (b) PS-b-PBs; 1H NMR
comparisons in the synthetic process of mono/bi-functionalized LCBCPs with
Azo moieties (LC1 and LC2) and BCPs (PVPDMS-b-PBs and PS-b-PBs).
Thermal Properties. As indicated in Figure 2a, DSC traces
presented determinations of phase transitions of Azo-Alkynyl
(LC1) and Azo-SiH (LC2). Except the melting temperature (Tm)
and LC-isotropic temperature (Ti), the transition temperature of
mesogenic phase (Ts) appeared in both Azo-Alkynyl (LC1) and
Azo-SiH (LC2). Results indicated that Azo-SiH (LC2) (Ti=187 °C,
ΔT=116 °C) showed a much wider mesogenic temperature
range (ΔT) value than did Azo-Alkynyl (LC1) (Ti=90 °C,
ΔT=32 °C) because of different terminal groups.
As is known, BCPs with flexible and rigid segments generate
spontaneous microphase separation due to the thermodynamic
difference. As summarized in Table 1, PS-b-PBs and PVPDMS-
b-PBs showed the microphase separated characteristics of two
glass transition temperature (Tg) values, i.e., Tg1= -94~-86 °C
Synthesis of bi-functionalized LCBCPs. After performing the
hydrosilylation of (PVPDMS-g-LC1)-b-PB with Azo-SiH (LC2) at
50 °C, the synthetic process was also detected by H NMR. As
1
shown in Figure 1c, the appearance of the peaks δ (ppm)= 0.16-
0 of -Si-(CH3)2- from Azo-SiH (LC2) and the disappearance of δ
(ppm)=5.08-4.85 assigned to 1,2-PBs indicated the addition
between Azo-SiH (LC2) and 1,2-olefins of PB blocks. In addition,
the remnant of the peaks δ (ppm)=5.68-5.23 assigned to 1,4-
PBs was indicative of an incomplete addition in PB blocks. The
grafting density in PB blocks was calculated according to Figure
S8 and summarized in Supporting Information. Results strongly
indicated that a series of bi-functionalized (PVPDMS-g-LC1)-b-
(PB-g-LC2) were synthesized and showed a complete addition in
Table 2. Molecular compositions and thermal properties of LCBCPs and homo-mixtures.
Phase transition (2nd heating)[g]
Entry
Mn (kg/mol) [c]
PDI [c]
Tg1 (°C) [d]
Tg2 (°C)[d]
Ti (°C)[e] [ΔHi](J/g)[f]
T (°C) [h]
PS3k-b-(PB6k-g-LC2)[a]
PS3k-b-(PB12k-g-LC2)
PS3k-b-(PB18k-g-LC2)
(PVPDMS3k-g-LC1)-b-PB6k
(PVPDMS3k-g-LC1)-b-PB18k
(PVPDMS3k-g-LC1)-b-PB30k
(PVPDMS3k-g-LC1)-b-(PB6k-g-LC2)
(PVPDMS3k-g-LC1)-b-(PB18k-g-LC2)
(PVPDMS3k-g-LC1)-b-(PB30k-g-LC2)
(PVPDMS3k-g-LC1):(PB6k-g-LC2)/1:1 [b]
(PVPDMS3k-g-LC1):(PB6k-g-LC2)/1:2
(PVPDMS3k-g-LC1):(PB6k-g-LC2)/1:3
21.3
37.9
51.8
25.5
35.0
46.2
35.2
51.8
71.3
--
1.05
1.04
1.04
1.19
1.19
1.15
1.20
1.25
1.26
--
-83
-81
-80
-98
-95
-94
-63
-65
-63
-86
-82
-82
27
29
30
29
29
33
15
17
22
40
29
26
74 (0.2)
75 (0.1)
77 (0.1)
97 (4.5)
110 (5.5)
47
46
47
68
81
79
85
97
102
--
112 (4.3)
100 (1.9)
Ts:57 [i] (2.3)[j]; Ti:114 (1.3)
Ts:57 [i] (2.7)[j]; Ti:124 (1.3)
70 (5.2) 99(2.1)
70(7.0) 97(0.9) 125(0.1)
71(6.6) 96(0.1) 125(0.2)
--
--
--
--
--
--
[a] Mono/bi-functionalized LCBCPs with well-designed molecular weight in different blocks. [b] Mixed homopolymers of PVPDMS attached by LC1 (PVPDMS-g-
LC1) and PB attached by LC2 (PB-g-LC2) in different mole ratios. [c] Number-average molecular weight (Mn) and polydispersity index (PDI), determined by
GPC, [d] The first glass transition temperature (Tg1) and the second glass transition temperatures (Tg2) on the second heating cycle, [e] LC-isotropic phase
transition temperature (Ti) and [f] the corresponding thermal transition absorption enthalpy (ΔHi), [g] all determined by DSC, [h] mesomorphic temperature range
(ΔT = Ti-Tg2), [i] the smectic phase transition temperature (Ts) and [j] the corresponding thermal transition absorption enthalpy (ΔHs).
3
This article is protected by copyright. All rights reserved.

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
Figure 2. (a) DSC traces on heating and cooling cycles and representative POM (50 μm) images within mesogenic temperature range of Azo-alkynyl (LC1) and
Azo-SiH (LC2) (Sm: Smectic phase; Tm: melting temperature; Ts: mesogenic phase transition temperature; Ti: LC-isotropic temperature; ΔH: the corresponding
thermal transition absorption enthalpy); (b) DSC traces on the second heating cycle and the representative POM (50 μm) images within mesogenic temperature
range of LCBCPs.
and Tg2=17~32 °C, which could be attributed to the flexible PB
blocks and rigid PS/PVPDMS blocks. As shown in Figure S9, PB
blocks showed a noticeable change in the slope of the DSC
curves related with their Tg1. However, for PS-b-(PB-g-LC2) and
(PVPDMS-g-LC1)-b-(PB-g-LC2) with LC functionalization in PB
blocks, PB blocks exhibited a gradual change in the slope of the
DSC curves related with their Tg1, and Tg1 values increased
relative to those of (PVPDMS-g-LC1)-b-PB with no
functionalization in PB blocks, which are summarized in Table 2
and shown in Figure 2b. Tg1 values were recorded in the order of
(PVPDMS-g-LC1)-b-PB (-98~-94 °C) < PS-b-(PB-g-LC2) (-83~-
80 °C) < (PVPDMS-g-LC1)-b-(PB-g-LC2) (-65~-63 °C). With
regard to PS-b-(PB-g-LC2) with no LC functionalization in PS
blocks, Tg2 values (Tg2=27~30 °C) were higher than those of PS
blocks in PS-b-PBs (Tg2=17~21 °C). As the strong - stacking
as an internal driving force induced LC ordering,[13] Tg2 values
were probably attributed to the - stacking of Azo mesogens
aggregation. The above discussion strongly suggested the
microphase separation of LCBCPs which is different from the
original BCPs. We will discuss the microphase separation in
terms of microstructural diameters identified by powder SAXS in
the following section.
As shown in Figure 2b and Table 2, all the LCBCPs displayed
two obvious Tg and one Ti values, interestingly, an exception
was observed that (PVPDMS-g-LC1)-b-(PB-g-LC2) exhibited an
additional Ts=57 °C when PB chain length increased. To confirm
the appearance of Ts and attributions of Tg mentioned above,
PVPDMS3k-g-LC1 and PB6k-g-LC2 were synthesized (sample
preparations are shown in Supporting Information) and mixed in
comparable mole ratios (1:1; 1:2; 1:3) with LCBCPs. As shown
in Figure S10 and Table 2, Tg1 (-86~-82 °C) of the mixtures were
adjacent to those (-83~-80 °C) of PS-b-(PB-g-LC2), which
explained that Tg1 of LCBCPs should be attributed to PB blocks.
Moreover, the mixtures displayed different Ti values, for example,
Ti (70~71 °C) of mixtures were adjacent to those (74~77 °C) of
PS-b-(PB-g-LC2) and Ti (125 °C) of mixtures appeared when the
mole fractions of PB6k-g-LC2 in mixtures increased; Ti
(96~99 °C) of mixtures were adjacent to those (97~112 °C) of
(PVPDMS-g-LC1)-b-PB. Therefore, the additional Ts=57 °C of
(PVPDMS-g-LC1)-b-(PB-g-LC2) when the PB length increased
(Figure 2b and Table 2) could be attributed to the mesophase of
PB LC blocks.
These results discussed above of the appearance of Ts and
attributions of Tg demonstrated that PB LC blocks and PVPDMS
LC blocks probably maintained the independence of phase
transitions in bi-functionalized (PVPDMS-g-LC1)-b-(PB-g-LC2). In
addition, the competitive interactions between PVPDMS LC
blocks and PB LC blocks occurred, where the influence of PB
LC blocks on the phase transitions enlarged when the PB chain
length increased.
The temperature range of mesogenic formation (ΔT=Ti-Tg2) is
known as an important parameter of properties. In present work,
ΔT=Ti-Tg2 was taken for further discussions. As shown in Figure
2b and Table 2, (PVPDMS-g-LC1)-b-(PB-g-LC2) (ΔT=85~102 °C)
presented slightly wider ΔT values compared with (PVPDMS-g-
LC1)-b-PB (ΔT=68~81 °C), but generated dramatically wider ΔT
values compared with PS-b-(PB-g-LC2) (ΔT=46~47 °C). In
addition, although Azo-SiH (LC2) (ΔT=116 °C) showed a much
wider ΔT value compared with Azo-Alkynyl (LC1) (ΔT=32 °C),
(PVPDMS-g-LC1)-b-PB (ΔT=68~81 °C) with Azo-Alkynyl (LC1)
functionalization in PVPDMS blocks showed wider ΔT values
than did PS-b-(PB-g-LC2) (ΔT=46~47 °C) with Azo-SiH (LC2)
functionalization in PB blocks. The general tendency was
demonstrated in the order of PS-b-(PB-g-LC2) (ΔT=46~47 °C) <
(PVPDMS-g-LC1)-b-PB (ΔT=68~81 °C) < (PVPDMS-g-LC1)-b-
(PB-g-LC2) (ΔT=85~102 °C) in analogies.
4
This article is protected by copyright. All rights reserved.

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
There are three reasons for the above phenomenon as follows.
Firstly, PVPDMS LC blocks with a complete grafting could
probably contribute to a stronger molecular interaction in
LCBCPs compared with PB LC blocks with a low grafting density.
Secondly, the flexibility and low grafting density of PB LC blocks
largely disturbed the formation of LC phase, as PVPDMS-b-PBs
and PS-b-PBs were designed with rigid PVPDMS/PS blocks in
the minority of molecular weight (Mn=3 kg/mol) and flexible PB
blocks in the majority (Mn=6~30 kg/mol) to manipulate the
motions of matrixes. Thirdly, alkynyl terminals of Azo-Alkynyl
(LC1) had a stronger polar effect on the stability of LC phase
than Si-H terminals of Azo-SiH (LC2), which explained that Azo-
SiH (LC2) showed a much wider ΔT and a higher Ti than did
Azo-Alkynyl (LC1). However, the polarity decreased when
alkynyl terminals of Azo-Alkynyl (LC1) reacted with PVPDMS.
Thus, the flexibility of both Si-O-Si spcers and PB LC blocks
probably cooperatively contributed to the narrow ΔT values.
These results demonstrated that PB LC blocks and PVPDMS
LC blocks had a cooperative contribution to bi-functionalized
(PVPDMS-g-LC1)-b-(PB-g-LC2) in terms of the temperature
range of mesogenic formation (ΔT).
X-ray analysis. The independent and cooperative effect of PB
LC blocks and PVPDMS LC blocks is evident from DSC and
POM results. In order to further confirm this effect and the
precise arrangement of LC phase, powder WAXD and SAXS
were cooperatively performed within the temperature range of
mesomorphic formation. At first, it should be noted that the
polymer backbone of side-chain liquid crystalline polymers
(SCLCPs) tends to keep the Gaussian chain conformation while
the mesogenic side groups tend to align parallel to one another
to form the molecular interaction of LC phase. Hence, although
the lengths of side groups should be variable depending on their
conformations, we only need to measure the longest theoretical
coplanar molecular length (L), because these values are
generally smaller than the layer spacing values when taking
Gaussian chain conformation into consideration, which is basic
and convincing enough to confirm the arrangement of LC phase
of SCLCPs. In previous work, the side groups were measured
while spacers were not taken into consideration.[14] In this work,
we measured the lengths of repeated units of polymers instead
of side groups,[8a, 11a, 11b] which meant that the spacers were
taken into consideration. As shown in Figure S11, not only Azo-
Alkynyl (LC1) and Azo-SiH (LC2) but also repeated units of
LCBCPs were simulated to obtain the longest theoretical
coplanar molecular length (L) upon energy minimization.
Figure 3. (a) Temperature-dependent 1D powder WAXD curves with Lorentz
correction traces inside and (b) SAXS traces of LCBCPs. (Lorentz correction
equation: X-axis= q= [4 sinθ]/λ, λ=1.54 Å; Y-axis= I*q2, I=Intensity)
As for LCBCPs, there were no signals observed within 2θ<5°
in 1D WAXD (Figure 3a), because the highly flexible PB blocks
decreased side interactions and further disturbed the
microstructural order. And then, Lorentz corrections in terms of
X-axis (q=4sinθ/λ, λ=1.54 Å) and Y-axis (I*q2, I=Intensity) were
applied, and the correction curves were observed inside the
Figure 3a. After Lorentz correction of PS-b-(PB-g-LC2) (L=19.7
Å), two signals at q=1.40 nm-1 and q=2.80 nm-1 (55 °C) were
observed, suggesting
a
smectic phase with
a
bilayer
arrangement (d=44.9 Å  2L). However, there were no obvious
diffractions within 2θ<5° of (PVPDMS-g-LC1)-b-PB, which could
be attributed to the flexibility of unfunctionalized PB blocks. As
shown in Figure 3a and Figure S12c, a wide diffraction (60 °C)
within 5°<2θ<30° in 1D WAXD and a halo near the equator in 2D
WAXD indicated the nematic phase of (PVPDMS-g-LC1)-b-PB.
In addition, (PVPDMS-g-LC1)-b-(PB-g-LC2) (L=28.9 Å) showed a
sharp peak shift depending on temperature, i.e., q=1.03 nm-1
(d=61.0 Å  2L, 40 °C) and q=1.21 nm-1 (2L>d=51.9 Å>L, 80 °C),
suggesting a possible bilayer molecular packing and an
interpenetrative arrangement of smectic phase, and further a
phase transition of smectic phase. In particular, it should be
noted that (PVPDMS-g-LC1)-b-(PB-g-LC2) showed a phase
transition of LC phase (Ts=57 °C) between 40 °C and 80 °C in
above mentioned DSC results, which determined the
appearance of PB LC blocks. In this section, we can see that
WAXD. As shown in Figure S12a, Azo-Alkynyl (LC1) (L =25.6 Å)
showed two weak first-order and second-order diffractions at
2θ=2.70° (layer domain spacing: d=32.7 Å, calculated from the
Bragg diffraction equation: 2dsinθ=λ, λ=1.54 Å) and 5.40° with a
ratio of 1:2 in 1D WAXD (65 °C), meanwhile, the bright halo
appeared near the equator and center in 2D WAXD as shown in
Figure S12b. Azo-SiH (LC2) (L=20.3 Å) showed a first-order
sharp peak shift depending on temperature, i.e., 2θ=2.00°
(d=44.1 Å  2L, 80 °C ) and 2θ=2.18° (d=40.5 Å  2L, 120 °C ), as
well as the two peaks (80 °C) and a diffuse diffraction (120 °C)
at wide angles. The results indicated a smectic phase of Azo-
Alkynyl (LC1) with an interpenetrative molecular bilayer packing
(2L > d=32.7 Å > L) and a phase transition of smectic phase
between 65 °C and 80 °C in combination with POM and DSC
results. Similarly, the above results indicated a smectic phase
transition and a possible bilayer arrangement of Azo-SiH (LC2).
(PVPDMS-g-LC1)-b-(PB-g-LC2) showed
a peak shift over
temperature, which further confirmed DSC results. And it was
clear that PB LC blocks and PVPDMS LC blocks maintained the
independence into bi-functionalized (PVPDMS-g-LC1)-b-(PB-g-
LC2).
5
This article is protected by copyright. All rights reserved.

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
Figure 4. (a) Chemical structures of local-crosslinked LCNs with different compositions and (b) DSC curves on the second heating cycle of LCNs.
PS-b-(PB-g-LC2) were observed in Figure 3b. The former
represented the order of smectic phase, while the latter should
be attributed to the microphase separated order. With the
decrease of the thermodynamic difference between PS in the
minority of molecular weight (Mn=3 kg/mol) and PB blocks
containing rigid LC side groups, a weak signal from microphase
separated order in SAXS of PS-b-(PB-g-LC2) was identified.
(PVPDMS-g-LC1)-b-PB showed a strong and constant signal at
q=0.22 nm-1 over temperature because of the enlargement of
thermodynamic difference between rigid PS blocks containing
rigid LCs and flexible PB blocks. The microscopically orientated
q=0.22 nm-1 indicated a disordered bicontinuous phase with
phase separated microdomain diameter d=28.6 nm.[16] For
(PVPDMS-g-LC1)-b-(PB-g-LC2), there was one peak shift from
q=0.30 nm-1 (d=20.9 nm, 40 °C) to q=0.27 nm-1 (d=23.3 nm,
80 °C) over temperature. The changes in the microdomains of
microphase separation might be attributed to the smectic phase
transition (Ts=57 °C) of (PVPDMS-g-LC1)-b-(PB-g-LC2), which
was best defined for the results of WAXD and DSC. Furthermore,
the microphase separated microdomain diameters showed the
SAXS. Due to the limitation of the WAXD instrument, SAXS was
further performed to assess microscopical orientation in small
angle regions in combination with WAXD. As shown in Figure 3b,
no signals of LC phase were detected in SAXS of (PVPDMS-g-
LC1)-b-PB, indicating a nematic phase. While a signal at q=0.22
nm-1 remained consistent at different temperatures, which
should be ascribed to phase separated microdomain spacings
(d=28.6 nm, d=2/q) because of the rigid and flexible segments
involved in diblock copolymer. In addition, PS-b-(PB-g-LC2)
showed a weak signal at q=2.5 nm-1 (d=25.1 Å, 55 °C). Because
the flexibility and low grafting density of PB LC blocks largely
disturbed the formation of LC phase, which led to a weak
interaction of smectic phase. (PVPDMS-g-LC1)-b-(PB-g-LC2)
showed an obvious peak shift depending on temperature, i.e.,
q=0.8 nm-1 (d=78.5 Å, 40 °C) and q=1.14 nm-1 (d=55.1 Å, 80 °C),
which was in good accordance with the peak shift from q=1.03
nm-1 (d=61.0 Å, 40 °C) to q=1.21 nm-1(d=51.9 Å, 80 °C) in 1D
WAXD (Figure 3a). The results also provided a critical evidence
for a phase transition Ts=57 °C between 40 °C and 80 °C. It was
found that the layer domain spacing of (PVPDMS-g-LC1)-b-(PB-
g-LC2) was much longer than that of PS-b-(PB-g-LC2), further
indicating that PVPDMS LC blocks and PB LC blocks not only
maintained the independence but also had a cooperative effect
on bi-functionalized (PVPDMS-g-LC1)-b-(PB-g-LC2).
order
of
PS-b-(PB-g-LC2)
<(PVPDMS-g-LC1)-b-(PB-g-
LC2)<(PVPDMS-g-LC1)-b-PB. These results suggested that
PVPDMS LC blocks of (PVPDMS-g-LC1)-b-PB and PB LC
blocks of PS-b-(PB-g-LC2) did have a cooperative contribution to
(PVPDMS-g-LC1)-b-(PB-g-LC2).
Microphase separation. Generally, BCPs with characteristic
rigid-flexible components tend to promote spontaneous
Application of modular design in local-crosslinked LCNs. In
the above discussion, LCBCPs with modular functionalization
have been synthesized and well characterized. We are inspired
to obtain local-crosslinked LCNs with reasonably designed
functionality in different blocks, which will contribute to designing
materials from basic molecular control, as researchers have
devoted much effort to the innovation and application of LCNs in
multiple functional materials.[17]
As shown in Figure 4, local-crosslinked LCNs were designed
by performing a quantitative hydrosilylation of PVPDMS3k-b-
PB18k and Azo-Alkynyl (LC1) with control over temperature. At
first, (PVPDMS-g-LC1)-b-PB with rationally designed 50 mol%
and 70 mol% grafting density in PVPDMS blocks were obtained
at 30 °C . Afterwards, an asymmetric cross-linker (ACA)
containing a pair of asymmetric double bonds, where the acrylic
group was designed for a further photo-crosslinking and had no
reactivities with Si-H groups, was introduced to PVPDMS blocks
at 50 °C. Meanwhile, local-crosslinked LCNs with rationally
designed 50 mol% and 70 mol% grafting density of (PVPDMS-g-
LC1)-b-PB were obtained through the local-crosslinked treatment
of (PVPDMS-g-LC1)-b-PB between remaining Si-H of PVPDMS
blocks and double bonds of PB blocks at 50 °C.
microphase separation due to the thermodynamic differences[15]
.
As discussed above, PS-b-PBs and PVPDMS-b-PBs showed
the characteristics of phase separation in terms of physical
principles, i.e., Tg1= -94~-86 °C and Tg2=17~32 °C, which could
be attributed to flexible PB and rigid PS/PVPDMS, respectively.
In present work, the effect of different modular funtions on
microphase separation was discussed, as the cooperative and
competitive motion between different modular blocks would
change the thermodynamic balance. As summarized in Table 2,
DSC results displayed two Tg signals, indicating a spontaneous
microphase separation. According to the above discussions, we
have made a description on the attributions of different Tg values
of LCBCPs. Herein, SAXS profiles were conducted to provide
convincing evidence for microphase separated microdomain
diameters of LCBCPs.
As mentioned above, except some signals of LC order were
observed in SAXS profiles of LCBCPs, some additional signals
of microphase separated order were obviously observed. For
example, two weak signals at q=2.5 nm-1 (layer domain spacing
of smectic phase: d=25.1 Å, 55 °C) and q=0.35 nm-1
(microphase separated microdomain diameter: d=18.0 nm) of
6
This article is protected by copyright. All rights reserved.

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
GPC as well as experimental details and related characterization results
are also shown in Supporting information.
To confirm the above modular functionalization, this process
was tracked by FT-IR and 1H NMR. As indicated in Figure S13a,
the disappearance in FT-IR of peak at 2116 nm-1 assigned to Si-
H groups indicated a complete addition in PVPDMS blocks. By
1
comparison in H NMR, the double bonds in PB blocks were
Acknowledgements
consumed, but PB LC blocks showed a low grafting density
served as a local-crosslinking point for good processability.
According to the design in Figure 4, PVPDMS blocks had an
almost 100% grafting density, where (PVPDMS-g-LC1)-b-PB had
50%/70% moles of Azo-Alkynyl (LC1), low density of ACA as
photo-croslinkers, and low local-crosslinking density.
Thankful for the financial support of the National Natural Science
Foundation of China (No. 21805025, No. 21674017) and
National Key R&D Program of China (2017YFB0307101) and
Fundamental Research Funds for the Central Universities
DUT19RC (4)001.
The properties of local-crosslinked LCNs were further idetified
by POM and DSC analysis. As seen in POM observations in
Figure S13b, LCNs presented the morphological textures of LCs
upon heating and cooling. More importantly, LCNs with well-
designed compositions showed room temperature Tg
(Tg=27~30 °C) and well-controlled Ti values (Ti=78~102 °C) for
easily processable conditions (Figure 4b). These results
confirmed the design of local-crosslinked LCNs by applying the
principle of building “blocks”and modular functionalization.
This design provides a new principle for designing local-
crosslinked LCNs, which is of both fundamental interest and
potential implications.
Keywords: Living Anionic Polymerization • Liquid Crystal Block
Copolymers • Building “Blocks” • Modular Functionalization •
Hydrosilylation
[1]
[2]
a) E. Elacqua, A. Croom, K. B. Manning, S. K. Pomarico, D. Lye, L.
Young, M. Weck, Angew. Chem. Int. Ed. 2016, 55, 15873-15878; b) Y.
Wang, H. Xu, X. Zhang, Adv. Mater. 2009, 21, 2849-2864.
a) P. Deshmukh, M. Gopinadhan, Y. Choo, S. K. Ahn, P. W. Majewski,
S. Y. Yoon, O. Bakajin, M. Elimelech, C. O. Osuji, R. M. Kasi, ACS
Macro Lett. 2014, 3, 462-466; b) F. Liao, L. Y. Shi, L. C. Cheng, S. Lee,
R. Ran, K. G. Yager, C. A. Ross, Nanoscale 2019, 11, 285-293; c) M.
Komura, A. Yoshitake, H. Komiyama, T. Iyoda, Macromolecules 2015,
48, 672-678; d) H. L. Xu, J. Bijleveld, M. Hedge, T. Dingemans, Polym.
Chem. 2019, 10, 5052-5069; e) M. Petr, B. A. Katzman, W. DiNatale, P.
T. Hammond, Macromolecules 2013, 46, 2823-2832; f) S. Nagano, Y.
Koizuka, T. Murase, M. Sano, Y. Shinohara, Y. Amemiya, T. Seki,
Angew. Chem. Int. Ed. 2012, 51, 5884-5888.
Conclusion
In summary, LCBCPs with modular functionalization have been
designed by the principle of building “blocks”, where Azo-Alkynyl
(LC1) and Azo-SiH (LC2) were independently and site-selectively
incorporated into PVPDMS-b-PBs and PS-b-PBs in combination
with LAP and hydrosilylation. The cooperative and independent
influence of modular functionalization on mesophase and
microphase separation was demonstrated. At first, PB LC blocks
and PVPDMS LC blocks had cooperative contributions to the
mesogenic properties and microphase separation of (PVPDMS-
g-LC1)-b-(PB-g-LC2), where polarized optical morphologies
showed a brighter order as PS-b-(PB-g-LC2) < (PVPDMS-g-
LC1)-b-PB< (PVPDMS-g-LC1)-b-(PB-g-LC2), thermal properties
were recorded as PS-b-(PB-g-LC2) (ΔT=46~47°C) < (PVPDMS-
g-LC1)-b-PB (ΔT=68~81 °C) < (PVPDMS-g-LC1)-b-(PB-g-LC2)
(ΔT=85~102 °C), and the microphase separated microdomain
diameters showed an order as PS-b-(PB-g-LC2) <(PVPDMS-g-
LC1)-b-(PB-g-LC2)<(PVPDMS-g-LC1)-b-PB. Secondly, PB LC
blocks and PVPDMS LC blocks showed their independence in
(PVPDMS-g-LC1)-b-(PB-g-LC2) because of an additional
[3]
a) H. F. Yu, Prog. Polym. Sci. 2014, 39, 781-815; b) H. B. Pan, W.
Zhang, A. Q. Xiao, X. L. Lyu, P. P. Hou, Z. H. Shen, X. H. Fan, Polym.
Chem. 2019, 10, 991-999; c) L. Y. Shi, F. Liao, L. C. Cheng, S. H. Lee,
R. Ran, Z. H. Shen, C. A. Ross, ACS Macro Lett. 2019, 8, 852-858; d)
K. Yuan, L. Chen, Y. W. Chen, J. Mater. Chem. C 2014, 2, 3835-3845;
e) T. J. Wang, X. Li, Z. J. Dong, S. Huang, H. F. Yu, ACS Appl. Mater.
Interfaces 2017, 9, 24864-24872.
[4]
[5]
a) F. Zhou, K. H. Gu, Z. Y. Zhang, M. Y. Zhang, S. Zhou, Z. H. Shen, X.
H. Fan, Angew. Chem. Int. Ed. 2016, 55, 15007-15011; b) Z. Z. Tong, Y.
M. Li, H. A. Xu, H. Chen, W. J. Yu, W. Q. Zhuo, R. K. Zhang, G. H.
Jiang, ACS Macro Lett. 2016, 5, 867-872.
a) I. E. Serhatli, T. Kacar, J. Appl. Polym. Sci. 2006, 99, 3187-3194; b)
F. Yilmaz, F. Kasapoglu, Y. Hepuzer, Y. Yagci, L. Toppare, E. G.
Fernandes, G. Galli, Des. Monomers Polym. 2005, 8, 223-236; c) G. P.
Mao, J. G. Wang, S. R. Clingman, C. K. Ober, J. T. Chen, E. L. Thomas,
Macromolecules 1997, 30, 2556-2567; d) J. Sanger, W. Gronski,
Macromol. Chem. Phys. 1998, 199, 555-561.
[6]
[7]
a) N. I. Boiko, M. A. Bugakov, E. V. Chernikova, A. A. Piryazev, Y. I.
Odarchenko, D. A. Ivanov, V. P. Shibaev, Polym. Chem. 2015, 6, 6358-
6371; b) A. Zenati, S. Thammalangsy, J. Polym. Sci., Part A: Polym.
Chem. 2018, 56, 1617-1629; c) J. Q. Jin, M. J. Tang, Z. H. Zhang, K.
Zhou, Y. Gao, Z. G. Zheng, W. A. Zhang, Polym. Chem. 2018, 9, 2101-
2108; d) B. Mu, X. Li, K. Y. Chen, Y. M. Zeng, J. L. Fang, D. Z. Chen, J.
Polym. Sci., Part A: Polym. Chem. 2017, 55, 2544-2553.
Ts=57
°C
observed
in
(PVPDMS-g-LC1)-b-(PB-g-LC2)
determined using powder X-rays analysis of LCBCPs and
charactering the mixtures of PVPDMS3k-g-LC1 and PB6k-g-LC2.
Thirdly, DSC results and SAXS profiles provided convincing
microstructural evidence for the phase separation of LCBCPs.
More importantly, by applying the principle of building“blocks”
and modular functionalization, local-crosslinked LCNs were
obtained and showed room temperature Tg and well-controlled Ti
values (Ti=78~102 °C) for easily processable conditions by
controlling molecular compositions.
a) Y. Choo, L. H. Mahajan, M. Gopinadhan, D. Ndaya, P. Deshmukh, R.
M. Kasi, C. O. Osuji, Macromolecules 2015, 48, 8315-8322; b) Y. Zhu,
Y. Q. Zhou, Z. Chen, R. Lin, X. G. Wang, Polymer 2012, 53, 3566-
3576; c) X. F. Chen, Z. H. Shen, X. H. Wan, X. H. Fan, E. Q. Chen, Y.
G. Ma, Q. F. Zhou, Chem. Soc. Rev. 2010, 39, 3072-3101; d) Y. Liu, W.
Wei, H. M. Xiong, Polym. Chem. 2015, 6, 583-590; e) Y. C. Xu, C. M.
Dong, J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 1216-1225; f) M.
Huo, Z. Y. Wan, M. Zeng, Y. Wei, J. Y. Yuan, Polym. Chem. 2018, 9,
3944-3951.
[8]
a) L. Han, H. W. Ma, S. Q. Zhu, P. B. Liu, H. Y. Shen, L. C. Yang, R.
Tan, W. Huang, Y. Li, Macromolecules 2017, 50, 8334-8345; b) M.
Yamada, T. Iguchi, A. Hirao, S. Nakahama, J. Watanabe,
Macromolecules 1995, 28, 50-58; c) M. Walther, H. Faulhammer, H.
Finkelmann, Macromol. Chem. Phys. 1998, 199, 223-237.
Experimental Section
The materials used in the experiment and the characterizations are
shown in Supporting Information. In addition, synthetic routes and related
1
characterization results including H NMR, FT-IR, DSC, X-ray, POM and
7
This article is protected by copyright. All rights reserved.

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
[9]
a) Q. C. Ma, L. Han, H. W. Ma, P. B. Liu, H. Y. Shen, L. C. Yang, C. Li,
X. Y. Hao, Y. Li, Polymer 2019, 184, 121907; b) L. C. Yang, L. Han, H.
W. Ma, P. B. Liu, H. Y. Shen, C. Li, S. B. Zhang, Y. Li, Chin. J. Polym.
Sci. 2019, 37, 841-850; c) W. Huang, H. W. Ma, L. Han, P. B. Liu, L. C.
Yang, H. Y. Shen, X. Y. Hao, Y. Li, Macromolecules 2018, 51, 3746-
3757.
[10] a) Y. Tsai, J. H. Wu, C. H. Li, Y. T. Wu, M. T. Leu, J. Appl. Polym. Sci.
2010, 116, 172-178; b) A. Hasebe, Y. Suematsu, S. Takeoka, T.
Mazzocchi, L. Vannozzi, L. Ricotti, T. Fujie, ACS Biomater. Sci. Eng.
2019, 5, 5734-5743.
[11] a) L. Han, H. W. Ma, Y. Li, J. Wu, H. Y. Xu, Y. R. Wang,
Macromolecules 2015, 48, 925-941; b) L. Han, H. W. Ma, Y. Li, S. Q.
Zhu, L. C. Yang, R. Tan, P. B. Liu, H. Y. Shen, W. Huang, X. C. Gong,
Macromolecules 2016, 49, 5350-5365; c) B. Wang, H. W. Ma, K. H.
Shen, D. Jun, Y. Li, Chin. Chem. Lett. 2012, 23, 1419-1422.
[12] a) Z. C. Jiang, Y. Y. Xiao, X. Tong, Y. Zhao, Angew. Chem. Int. Ed.
2019, 58, 5332-5337; b) T. Ube, K. Kawasaki, T. Ikeda, Adv. Mater.
2016, 28, 8212-8217; c) Y. Y. Liu, W. Wu, J. Wei, Y. L. Yu, ACS Appl.
Mater. Interfaces 2017, 9, 782-789.
[13] M. Anthamatten, J. S. Wu, P. T. Hammond, Macromolecules 2001, 34,
8574-8579.
[14] E. Verploegen, T. Zhang, N. Murlo, P. T. Hammond, Soft Matter 2008,
4, 1279-1287.
[15] a) S. Suarez-Suarez, G. A. Carriedo, A. P. Soto, Chem. Eur. J. 2016,
22, 4483-4491; b) W. Lee, S. Park, Y. Kim, V. Sethuraman, N. Rebello,
V. Ganesan, D. Y. Ryu, Macromolecules 2017, 50, 5858-5866.
[16] a) J. M. Widin, A. K. Schmitt, A. L. Schmitt, K. Im, M. K. Mahanthappa,
J. Am. Chem. Soc. 2012, 134, 3834-3844; b) I. Villaluenga, X. C. Chen,
D. Devaux, D. T. Hallinan, N. P. Balsara, Macromolecules 2015, 48,
358-364; c) L. Y. Zhang, T. T. Cui, X. Cao, C. J. Zhao, Q. Chen, L. X.
Wu, H. L. Li, Angew. Chem. Int. Ed. 2017, 56, 9013-9017.
[17] a) T. H. Ware, M. E. McConney, J. J. Wie, V. P. Tondiglia, T. J. White,
Science 2015, 347, 982-984; b) Y. Yang, E. M. Terentjev, Y. B. Zhang,
Q. M. Chen, Y. Zhao, Y. Wei, Y. Ji, Angew. Chem. Int. Ed. 2019, 58,
17474-17479.
8
This article is protected by copyright. All rights reserved.

10.1002/chem.202000268
Chemistry - A European Journal
FULL PAPER
Cooperative and Independent Effect of Modular Functionalization on Mesomorphic
Performances and Microphase Separation of Well-Designed Liquid Crystalline Diblock
Copolymers
Lan Lei, Dr. Li Han,* Prof. Hongwei Ma, Ruixue Zhang, Shuai Huang, Heyu Shen, Lincan Yang, Chao Li, Songbo Zhang, Hongyuan
Bai, Qingchi Ma, and Prof. Yang Li*
By the principle of building “blocks”, site-selective functionalized LCBCPs with modular functionalization were synthesized through
LAP and temperature dependent hydrosilylation. The mono-functionalized LCBCPs showed the independence and cooperativity of
different functions in bi-functionalized LCBCPs. Furthermore, LCNs with a low local-crosslinking density displayed easily processable
conditions and were capable of a further photo-crosslinking.
9
This article is protected by copyright. All rights reserved.