U.S. patent application number 15/394457 was filed with the patent office on 2017-11-30 for oligomer, composition and composite material employing the same.
This patent application is currently assigned to INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE. The applicant listed for this patent is INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE. Invention is credited to Yen-Yi CHU, Ming-Tsung HONG, Yun-Ching LEE, Li-Chun LIANG, Wei-Ta YANG, Meng-Song YIN.
Application Number | 20170342199 15/394457 |
Document ID | / |
Family ID | 60420966 |
Filed Date | 2017-11-30 |
United States Patent
Application |
20170342199 |
Kind Code |
A1 |
YANG; Wei-Ta ; et
al. |
November 30, 2017 |
OLIGOMER, COMPOSITION AND COMPOSITE MATERIAL EMPLOYING THE SAME
Abstract
An oligomer, composition, and composite material employing the
same are provided. The oligomer has a structure represented by
Formula (I) ##STR00001## wherein R.sup.1 and R.sup.2 are
independently hydrogen, C.sub.1-20 alkyl group, C.sub.2-20 alkenyl
group, C.sub.6-12 aryl group, C.sub.6-12 alkylaryl group,
C.sub.5-12 cycloalkyl group, C.sub.6-20 cycloalkylalkyl group,
alkoxycarbonyl group, or alkylcarbonyloxy group; R.sup.1 is not
hydrogen when R.sup.2 is hydrogen; a is 0 or 1; n.gtoreq.0;
m.gtoreq.1; n:m is from 0:100 to 99:1; the oligomer has a number
average molecular weight of less than or equal to 12,000; and the
repeat unit ##STR00002## and the repeat unit ##STR00003## are
arranged in a random or block fashion.
Inventors: |
YANG; Wei-Ta; (Taoyuan City,
TW) ; CHU; Yen-Yi; (Chiayi City, TW) ; HONG;
Ming-Tsung; (New Taipei City, TW) ; LIANG;
Li-Chun; (Qionglin Township, TW) ; LEE;
Yun-Ching; (Ji'an Township, TW) ; YIN; Meng-Song;
(Hsinchu City, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE |
Hsinchu |
|
TW |
|
|
Assignee: |
INDUSTRIAL TECHNOLOGY RESEARCH
INSTITUTE
Hsinchu
TW
|
Family ID: |
60420966 |
Appl. No.: |
15/394457 |
Filed: |
December 29, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62340686 |
May 24, 2016 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C03C 25/30 20130101;
C08F 36/20 20130101; C08G 2261/226 20130101; C08J 2371/12 20130101;
C08G 2261/65 20130101; C08J 5/04 20130101; C09D 125/10 20130101;
C09D 171/12 20130101; C08G 61/08 20130101; C08J 2345/00 20130101;
C08G 2261/1414 20130101; C08G 2261/64 20130101; C08L 65/00
20130101; C08G 2261/418 20130101; C08G 2261/3324 20130101; C03C
25/32 20130101; H05K 1/0326 20130101; C08J 5/24 20130101; C08G
2261/3327 20130101; C08G 2261/122 20130101; C08J 2465/00 20130101;
C08G 2261/228 20130101; C08G 61/12 20130101; H05K 1/024 20130101;
C08G 2261/224 20130101; C08L 25/10 20130101; H05K 1/0306 20130101;
C08J 2365/00 20130101; C08L 2203/20 20130101; C08G 2261/135
20130101; C08L 47/00 20130101; C08F 232/08 20130101; C08F 32/08
20130101; C08G 61/02 20130101; C08L 45/00 20130101; H05K 1/09
20130101; C08G 2261/76 20130101; H05K 1/0313 20130101; C08J 2453/02
20130101 |
International
Class: |
C08G 61/02 20060101
C08G061/02; C03C 25/30 20060101 C03C025/30; C08J 5/24 20060101
C08J005/24; H05K 1/03 20060101 H05K001/03; C03C 25/32 20060101
C03C025/32; H05K 1/09 20060101 H05K001/09; C09D 171/12 20060101
C09D171/12 |
Claims
1. An oligomer, having a structure represented by Formula (I)
##STR00047## wherein R.sup.1 and R.sup.2 are independently
hydrogen, C.sub.1-20 alkyl group, C.sub.2-20 alkenyl group,
C.sub.6-12 aryl group, C.sub.6-12 alkylaryl group, C.sub.5-12
cycloalkyl group, C.sub.6-20 cycloalkylalkyl group, alkoxycarbonyl
group, or alkylcarbonyloxy group; R.sup.1 is not hydrogen when
R.sup.2 is hydrogen; a is 0 or 1; n.gtoreq.0; m.gtoreq.1; n:m is
from 0:100 to 99:1; the oligomer has a number average molecular
weight of less than or equal to 12,000; and the repeat unit
##STR00048## and the repeat unit ##STR00049## are arranged in a
random or block fashion.
2. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00050## and wherein b is 0, or
an integer from 1 to 19; and R.sup.1 is not hydrogen when R.sup.2
is hydrogen.
3. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00051## wherein c is 0, or an
integer from 1 to 6; and R.sup.1 is not hydrogen when R.sup.2 is
hydrogen.
4. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00052## and wherein d is 0, or
an integer from 1 to 6; and R.sup.1 is not hydrogen when R.sup.2 is
hydrogen.
5. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00053## wherein e is 0, or an
integer from 1 to 6; and R.sup.1 is not hydrogen when R.sup.2 is
hydrogen.
6. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00054## and wherein f is 0, or
an integer from 1 to 6; R.sup.3 is C.sub.1-6 alkyl group; and
R.sup.1 is not hydrogen when R.sup.2 is hydrogen.
7. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00055## and wherein g is 0, or
an integer from 1 to 6; R.sup.4 is C.sub.1-6 alkyl group; and
R.sup.1 is not hydrogen when R.sup.2 is hydrogen.
8. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00056## wherein h is an integer
from 1 to 6; and R.sup.1 is not hydrogen when R.sup.2 is
hydrogen.
9. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00057## wherein i is 0, 1, 2,
3, 4, 5, or 6; and R.sup.1 is not hydrogen when R.sup.2 is
hydrogen.
10. The oligomer as claimed in claim 1, wherein R.sup.1 and R.sup.2
are independently hydrogen, or ##STR00058## wherein j is 0, 1, 2,
3, 4, 5, or 6; and R.sup.1 is not hydrogen when R.sup.2 is
hydrogen.
11. The oligomer as claimed in claim 1, wherein n:m is from 1:9 to
9:1.
12. A composition, comprising: 1-99 parts by weight of the oligomer
as claimed in claim 1; and 1-99 parts by weight of resin.
13. The composition as claimed in claim 12, wherein the resin is
polyolefin resin, epoxy resin, cyanate resin, phenol resin, novolac
resin, polystyrene resin, styrene-butadiene copolymer resin,
polyamide resin, polyimide resin, maleimide resin, bismaleimide
resin, polyphenylene ether resin, or a combination thereof.
14. The composition as claimed in claim 13, wherein the polyolefin
resin is polybutadiene resin, polyalkenamer resin, cyclic olefin
polymer resin, or cycloolefin copolymer resin.
15. A composite material, comprising: a cured product or a
semi-cured product prepared by the composition as claimed in claim
12; and a substrate, wherein the cured product or the semi-cured
product is disposed on the substrate or disposed within the
substrate.
16. The composite material as claimed in claim 15, wherein the
substrate is glass fiber, or copper foil.
17. The composite material as claimed in claim 15, wherein the
composite material is a copper foil substrate, a printed circuit
board, or an integrated circuit carrier.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/340,686, filed on May 24, 2016, which is
incorporated herein by reference.
TECHNICAL FIELD
[0002] The disclosure relates to an oligomer, a composition and a
composite material employing the same.
BACKGROUND
[0003] The trend in electronic products has been toward smaller
sizes, lighter weights, higher operating speeds, and
higher-frequency transmission. Therefore, the distribution for
printed circuit boards is toward high-density. In order to maintain
the transmission rate and signal integrity, the ideal materials for
use in printed circuit boards must have a low dielectric constant
(dielectric constant, Dk) and a low dissipation factor (dissipation
factor, Df).
[0004] In general, conventional materials for printed circuit
boards have a high dielectric constant (dielectric constant, Dk)
and a high dissipation factor (dissipation factor, DO. Accordingly,
a novel material for use in printed circuit boards is desired in
order to improve performance and reduce Dk and Df without
sacrificing thermal resistance and mechanical strength.
SUMMARY
[0005] According to embodiments of the disclosure, the disclosure
provides an oligomer. The oligomer has a structure represented by
Formula (I)
##STR00004##
wherein R.sup.1 and R.sup.2 are independently hydrogen, C.sub.1-20
alkyl group, C.sub.2-20 alkenyl group, C.sub.6-12 aryl group,
C.sub.6-12 alkylaryl group, C.sub.5-12 cycloalkyl group, C.sub.6-20
cycloalkylalkyl group, alkoxycarbonyl group, or alkylcarbonyloxy
group, R.sup.1 is not hydrogen when R.sup.2 is hydrogen; a is 0 or
1; n.gtoreq.0; m.gtoreq.1; n:m is from about 0:100 to 99:1; the
oligomer number average molecular weight less than or equal to
12,000; and the repeat unit
##STR00005##
and the repeat unit
##STR00006##
are arranged in a random or block fashion.
[0006] According to embodiments of the disclosure, the disclosure
also provides a composition including about 1-99 parts by weight of
the aforementioned oligomer; and about 1-99 parts by weight of
resin.
[0007] According to embodiments of the disclosure, the disclosure
also provides a composite material including a cured product or a
semi-cured product prepared from the aforementioned composition;
and a substrate, wherein the cured product or the semi-cured
product is disposed on the substrate or disposed within the
substrate.
[0008] A detailed description is given in the following embodiments
with reference to the accompanying drawings.
DETAILED DESCRIPTION
[0009] Embodiments of the disclosure provide an oligomer, a
composition, and a composite material employing the same. The
oligomer of the disclosure can be prepared by copolymerizing a
first monomer (such as vinyl norbornene) and a second monomer (such
as norbornene) via ring-opening polymerization, and .alpha.-olefin
can be introduced during copolymerization in order to control the
molecular weight of the obtained copolymer (i.e. the obtained
copolymer can have a number average molecular weight less than or
equal to 12,000). As a result, due to the high solubility in
organic solvent, the oligomer exhibits high processability. In
addition, due to the low polarity and the crosslinkable functional
groups of the chemical structure of the oligomer, the oligomer can
enhance the mechanical strength of the substrate material when the
oligomer is used as a reactant for preparing the substrate
material. Embodiments of the disclosure also provide a composition
including the aforementioned oligomer and a composite material
(such as a prepreg) including a cured product or a semi-cured
product prepared from the composition. The cured product of the
composition of the disclosure exhibits a relatively low dielectric
constant (Dk) (less than 3.0 (at 10 GHz)) and a relatively low
dissipation factor (Df) (less than 0.0033 (at 10 GHz)), and can
serve as a good material for the high-frequency substrate in order
to improve the problem of insertion loss.
[0010] According to embodiments of the disclosure, the oligomer has
a structure represented by Formula (I)
##STR00007##
wherein R.sup.1 and R.sup.2 are independently hydrogen, C.sub.1-20
alkyl group, C.sub.2-20 alkenyl group, C.sub.6-12 aryl group,
C.sub.6-12 alkylaryl group, C.sub.5-12 cycloalkyl group, C.sub.6-20
cycloalkylalkyl group, alkoxycarbonyl group, or alkylcarbonyloxy
group, R.sup.1 is not hydrogen when R.sup.2 is hydrogen; a is 0 or
1; n.gtoreq.0 (such as n.gtoreq.1); m.gtoreq.1; n:m is from about
0:100 to 99:1; the oligomer number average molecular weight less
than or equal to 12,000; and the repeat unit
##STR00008##
and the repeat unit
##STR00009##
are arranged in a random or block fashion.
[0011] According to embodiments of the disclosure, the alkyl group
of the disclosure can be linear or branched alkyl group. For
example, R.sup.1 and R.sup.2 can be independently a linear or
branched alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. According to
embodiments of the disclosure, the alkenyl group of the disclosure
can be linear or branched alkenyl group. For example, R.sup.1 and
R.sup.2 can be independently a linear or branched alkenyl group
having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,
19, or 20 carbon atoms.
[0012] According to embodiments of the disclosure, R.sup.1 and
R.sup.2 can be independently hydrogen, or
##STR00010##
wherein b can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
15, 16, 17, 18, or 19; and R.sup.1 is not hydrogen when R.sup.2 is
hydrogen.
[0013] According to embodiments of the disclosure, the C.sub.6-12
aryl group of the disclosure can be phenyl group, biphenyl group,
or naphthyl group.
[0014] According to embodiments of the disclosure, R.sup.1 and
R.sup.2 are independently hydrogen, or
##STR00011##
wherein c can be 0, 1, 2, 3, 4, 5, or 6; and R.sup.1 is not
hydrogen when R.sup.2 is hydrogen.
[0015] According to embodiments of the disclosure, R.sup.1 and R2
can be independently hydrogen, or
##STR00012##
wherein d can be 0, 1, 2, 3, 4, 5, or 6; and R.sup.1 is not
hydrogen when R.sup.2 is hydrogen.
[0016] According to embodiments of the disclosure, R.sup.1 and
R.sup.2 can be independently hydrogen, or
##STR00013##
wherein e can be 0, 1, 2, 3, 4, 5, or 6; and R.sup.1 is not
hydrogen when R.sup.2 is hydrogen.
[0017] According to embodiments of the disclosure, R.sup.1 and
R.sup.2 can be independently hydrogen, or
##STR00014##
wherein f can be 0, 1, 2, 3, 4, 5, or 6, R.sup.3 can be C.sub.1-6
alkyl group, R.sup.1 is not hydrogen when R.sup.2 is hydrogen. For
example, R.sup.3 can be methyl group, ethyl group, propyl group,
isopropyl group, butyl group, isobutyl group, tert-butyl group,
pentyl group, or hexyl group.
[0018] According to embodiments of the disclosure, R.sup.1 and
R.sup.2 can be independently hydrogen, or
##STR00015##
wherein g can be 0, 1, 2, 3, 4, 5, or 6, R.sup.4 can be C.sub.1-6
alkyl group; and R.sup.1 is not hydrogen when R.sup.2 is hydrogen.
For example, R.sup.4 can be methyl group, ethyl group, propyl
group, isopropyl group, butyl group, isobutyl group, tert-butyl
group, pentyl group, or hexyl group.
[0019] According to embodiments of the disclosure, R.sup.1 and
R.sup.2 can be independently hydrogen, or
##STR00016##
wherein h can be 1, 2, 3, 4, 5, or 6; and R.sup.1 is not hydrogen
when R.sup.2 is hydrogen.
[0020] According to embodiments of the disclosure, R.sup.1 and
R.sup.2 can be independently hydrogen, or
##STR00017##
wherein i can be 0, 1, 2, 3, 4, 5, or 6; and R.sup.1 is not
hydrogen when R.sup.2 is hydrogen.
[0021] According to embodiments of the disclosure, R.sup.1 and
R.sup.2 can be independently hydrogen, or
##STR00018##
wherein j can be 0, 1, 2, 3, 4, 5, or 6; and R.sup.1 is not
hydrogen when R.sup.2 is hydrogen.
[0022] According to embodiments of the disclosure, the ratio of the
repeat unit
##STR00019##
to the repeat unit
##STR00020##
(i.e. n:m) can be from about 0:100 to 99:1, such as from about 1:9
to 9:1, from about 2:8 to 8:2, from about 3:7 to 7:3, or from about
3:7 to 6:4. Due to the adjustment of the ratio between the two
repeat units of the oligomer, the properties of the cured product
prepared by crosslinking the oligomer and the resin can be
modified. For example, when increasing the amount of the repeat
unit
##STR00021##
the crosslinking density of the cured product can be increased.
[0023] In embodiments of the disclosure, due to the introduction of
the .alpha.-olefin when copolymerizing vinyl norbornene with
norbornene, the molecular weight of the coploymer can be
controlled. According to embodiments of the disclosure, the number
average molecular weight of the oligomer can be less than 12,000,
such as from about 800 to 12,000, from about 800 to 9,000, from
about 800 to 8,000, from about 800 to 7,000, from about 800 to
6,000, or from about 800 to 5,000. As a result, the oligomer can
have high solubility in organic solvent, thereby enhancing the
processability of the oligomer. In addition, in comparison with the
coploymer merely prepared from vinyl norbornene and norbornene, the
oligomer of the disclosure exhibits superior storability.
[0024] According to embodiments of the disclosure, the method for
preparing the aforementioned oligomer can include mixing and
reacting a first monomer, a second monomer, and .alpha.-olefin to
obtain the oligomer.
[0025] According to embodiments of the disclosure, the method for
preparing the aforementioned oligomer can include mixing and
reacting a metal catalyst, a first monomer, a second monomer, and
.alpha.-olefin to obtain the oligomer.
[0026] According to embodiments of the disclosure, the method for
preparing the aforementioned oligomer can include mixing and
reacting a photoredox initiator, a photoredox mediator, a first
monomer, a second monomer, and .alpha.-olefin to obtain the
oligomer. In particular, the photoredox initiator can be vinyl
ether, 1-methoxy-4-phenyl butene, 2-cyclohexyl-1-methoxyethylene,
or a combination thereof. The photoredox mediator can be pyrylium
salt, acridinium salt, or a combination thereof.
[0027] According to embodiments of the disclosure, the method for
preparing the aforementioned oligomer can include mixing and
reacting a first monomer, a second monomer, and .alpha.-olefin
under electrochemical condition to obtain the oligomer.
[0028] The metal catalyst can be Grubbs catalyst, such as
first-generation Grubbs catalyst, second-generation Grubbs
catalyst, Hoveyda-Grubbs catalyst, derivatives thereof, or a
combination including at least one of the above catalysts. The
first monomer can be
##STR00022##
wherein a is 0 or 1. For example, the first monomer is vinyl
norbornene. The second monomer can be norbornene
##STR00023##
The .alpha.-olefin can be
##STR00024##
wherein R.sup.5 can be C.sub.1-20 alkyl group, C.sub.2-20 alkenyl
group, C.sub.6-12 aryl group, C.sub.6-12 alkylaryl group,
C.sub.5-12 cycloalkyl group, C.sub.6-20 cycloalkylalkyl group,
alkoxycarbonyl group, or alkylcarbonyloxy group. for example,
.alpha.-olefin can be
##STR00025##
[0029] wherein b, c, d, e, f, g, h, i, j, R.sup.3, and R.sup.4 have
the same definition as above. In the aforementioned methods for
preparing the oligomer, the sequence in which components are added
is not limited. For example, a metal catalyst can be dissolved in a
solvent first, obtaining a metal-catalyst-containing solution.
Next, a solution including the first monomer and .alpha.-olefin is
mixed with the metal-catalyst-containing solution. Finally, the
second monomer is added into the above mixture. According to
embodiments of the disclosure, the molar ratio of the first monomer
to the second monomer can be from about 100:0 (i.e. there is no the
second monomer added) to 1:99, such as from about 9:1 to 1:9, from
about 8:2 to 2:8, from about 3:7 to 7:3, or from about 3:7 to 6:4.
In addition, the molar percentage of .alpha.-olefin can be from
about 1 mol % to 85 mol %, such as about from 5 mol % to 75 mol %,
or about from 10 mol % to 75 mol %, based on the total moles of the
first monomer and the second monomer.
[0030] In one embodiment, the amount of the .alpha.-olefin is
inversely proportional to the molecular weight of the oligomer, so
that the molecular weight of the oligomer can be controlled by
means of the amount of .alpha.-olefin. When the molar percentage of
.alpha.-olefin is too low, the oligomer would have relatively high
molecular weight and exhibit poor processability and storability.
Conversely, when the molar percentage of .alpha.-olefin is too
high, the oligomer would have a relatively low molecular weight and
the process for preparing the substrate is not easy to control.
[0031] According to embodiments of the disclosure, the disclosure
also provides a composition including the aforementioned oligomer,
and one or at least one resin. The composition can include about
1-99 parts by weight of the oligomer, about 10-90 parts by weight
of the oligomer, or about 20-80 parts by weight of the oligomer.
Furthermore, the composition can include about 1-99 parts by weight
of the resin, about 10-90 parts by weight of the resin, or about
20-80 parts by weight of the resin. The resin can be polyolefin
resin (such as polybutadiene resin), polyalkenamer resin, cyclic
olefin polymer resin, cycloolefin copolymer resin, epoxy resin,
cyanate resin, phenol resin, novolac resin, polystyrene resin,
styrene-butadiene copolymer resin (such as
polystyrene-butadiene-styrene resin), polyamide resin, polyimide
resin, maleimide resin, bismaleimide resin, polyphenylene ether
resin, or a combination thereof. In addition, According to
embodiments of the disclosure, the weight percentage of the
oligomer can be from about 1 wt % to 99 wt %, from about 10 wt % to
90 wt %, or from about 20 wt % to 80 wt %, and the weight
percentage of the resin can be from about 1 wt % to 99 wt %, from
about 10 wt % to 90 wt %, or from about 20 wt % to 80 wt %, based
on the total weight of the oligomer and resin.
[0032] According to an embodiment of the disclosure, the disclosure
also provides a composite material. The composite material can
include a cured product or a semi-cured product of the composition,
and a substrate. In particular, the cured product or semi-cured
product is disposed on the substrate or within the substrate.
According to an embodiment of the disclosure, the substrate can be
a glass fiber, or a copper foil. For example, the composite
material can include a prepreg, and the method for preparing the
prepreg includes immersing a glass fiber (serving as the substrate)
into the aforementioned composition. Next, the composition is
subjected to a semi-curing process, obtaining the prepreg. In
addition, the composite material can further include a copper foil,
and the composite material can be a copper foil substrate, a
printed circuit board, or an integrated circuit.
[0033] The inventive concept of the disclosure may be embodied in
various forms without being limited to the exemplary embodiments
set forth herein.
Example 1
[0034] 0.045 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 10 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.604 mol of 1-hexene (as .alpha.-olefin), 73.6 g of
vinyl norbornene, 128 ml of toluene, and the
metal-catalyst-containing solution were added into another reaction
bottle. After stirring completely, a norbornene-containing solution
(57.7 g of norbornene (NB) dissolved in 50 ml of toluene) was added
into the reaction bottle. Herein, .alpha.-olefin (1-hexene) had a
molar percentage of 50 mol %, based on the total moles of vinyl
norbornene and norbornene. After stopping the reaction, 63 ml of
ethyl vinyl ether was added into the reaction bottle. After
stirring overnight, the catalyst of the result was removed and then
was purified by a reprecipitation with methanol. After
concentration, Copolymer (I) was obtained, wherein the ratio of the
repeat unit
##STR00026##
to the repeat unit
##STR00027##
of Copolymer (I) was about 1:1.
[0035] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (I) were determined, and the results
are shown in Table 1.
Example 2
[0036] 0.045 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 10 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.362 mol of 1-hexene (.alpha.-olefin), 73.6 g of vinyl
norbornene, 128 ml of toluene, and the metal-catalyst-containing
solution were added into another reaction bottle. After stirring
completely, a norbornene-containing solution (57.7 g of norbornene
dissolved in 50 ml of toluene) was added into the reaction bottle.
Herein, .alpha.-olefin (1-hexene) had a molar percentage of 30 mol
%, based on the total moles of vinyl norbornene and norbornene.
After stopping the reaction, 63 ml of ethyl vinyl ether was added
into the reaction bottle. After stirring overnight, the catalyst of
the result was removed and then was purified by a reprecipitation
with methanol. After concentration, Copolymer (II) was obtained,
wherein the ratio of the repeat unit
##STR00028##
to the repeat unit
##STR00029##
of Copolymer (II) was about 1:1
[0037] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (II) were determined, and the
results are shown in Table 1.
Example 3
[0038] 0.09 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 15 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.483 mol of 1-hexene (.alpha.-olefin), 147 g of vinyl
norbornene, 260 ml of toluene, and the metal-catalyst-containing
solution were added into another reaction bottle. After stirring
completely, a norbornene-containing solution (115 g of norbornene
dissolved in 100 ml of toluene) was added into the reaction bottle.
Herein, .alpha.-olefin (1-hexene) had a molar percentage of 20 mol
%, based on the total moles of vinyl norbornene and norbornene.
After stopping the reaction, 125 ml of ethyl vinyl ether was added
into the reaction bottle. After stirring overnight, the catalyst of
the result was removed and then was purified by a reprecipitation
with methanol. After concentration, Copolymer (III) was obtained,
wherein the ratio of the repeat unit
##STR00030##
to the repeat unit
##STR00031##
of Copolymer (III) was about 1:1
[0039] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (III) were determined, and the
results are shown in Table 1.
Example 4
[0040] 0.045 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 10 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.362 mol of 1-hexene (.alpha.-olefin), 52.1 g of vinyl
norbornene, 87 ml of toluene, and the metal-catalyst-containing
solution were added into another reaction bottle. After stirring
completely, a norbornene-containing solution (75 g of norbornene
dissolved in 90 ml of toluene) was added into the reaction bottle.
Herein, .alpha.-olefin (1-hexene) had a molar percentage of 20 mol
%, based on the total moles of vinyl norbornene and norbornene.
After stopping the reaction, 63 ml of ethyl vinyl ether was added
into the reaction bottle. After stirring overnight, the catalyst of
the result was removed and then was purified by a reprecipitation
with methanol. After concentration, Copolymer (IV) was obtained,
wherein the ratio of the repeat unit
##STR00032##
to the repeat unit
##STR00033##
of Copolymer (IV) was about 0.5:1.
[0041] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (IV) were determined, and the
results are shown in Table 1.
Example 5
[0042] 0.054 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 15 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.145 mol of 1-hexene (.alpha.-olefin), 88.3 g of vinyl
norbornene, 150 ml of toluene, and the metal-catalyst-containing
solution were added into another reaction bottle. After stirring
completely, a norbornene-containing solution (69.3 g of norbornene
dissolved in 60 ml of toluene) was added into the reaction bottle.
Herein, .alpha.-olefin (1-hexene) had a molar percentage of 10 mol
%, based on the total moles of vinyl norbornene and norbornene.
After stopping the reaction, 75 ml of ethyl vinyl ether was added
into the reaction bottle. After stirring overnight, the catalyst of
the result was removed and then was purified by a reprecipitation
with methanol. After concentration, Copolymer (V) was obtained,
wherein the ratio of the repeat unit
##STR00034##
to the repeat unit
##STR00035##
of Copolymer (V) was about 1:1
[0043] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (V) were determined, and the results
are shown in Table 1.
Example 6
[0044] 0.018 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 10 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.0245 mol of 1-hexene (.alpha.-olefin), 29.4 g of
vinyl norbornene, 45 ml of toluene, and the
metal-catalyst-containing solution were added into another reaction
bottle. After stirring completely, a norbornene-containing solution
(23.06 g of norbornene dissolved in 20 ml of toluene) was added
into the reaction bottle. Herein, .alpha.-olefin (1-hexene) had a
molar percentage of 5 mol %, based on the total moles of vinyl
norbornene and norbornene. After stopping the reaction, 25 ml of
ethyl vinyl ether was added into the reaction bottle. After
stirring overnight, the catalyst of the result was removed and then
was purified by a reprecipitation with methanol. After
concentration, Copolymer (VI) was obtained, wherein the ratio of
the repeat unit
##STR00036##
to the repeat unit
##STR00037##
of Copolymer (VI) was about 1:1.
[0045] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (VI) were determined, and the
results are shown in Table 1.
Example 7
[0046] 0.009 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, 6 ml of toluene was added into the
reaction bottle, obtaining a metal-catalyst-containing solution.
After the metal catalyst was dissolved in toluene completely,
0.0073 mol of 1-hexene (.alpha.-olefin), 14.7 g of vinyl
norbornene, 23 ml of toluene, and the metal-catalyst-containing
solution were added into another reaction bottle. After stirring
completely, a norbornene-containing solution (11.5 g of norbornene
dissolved in 10 ml of toluene) was added into the reaction bottle.
Herein, .alpha.-olefin (1-hexene) had a molar percentage of 3 mol
%, based on the total moles of vinyl norbornene and norbornene.
After stopping the reaction, 13 ml of ethyl vinyl ether was added
into the reaction bottle. After stirring overnight, the catalyst of
the result was removed and then was purified by a reprecipitation
with methanol. After concentration, Copolymer (VII) was obtained,
wherein the ratio of the repeat unit
##STR00038##
to the repeat unit
##STR00039##
of Copolymer (VII) was about 1:1.
[0047] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (VII) were determined, and the
results are shown in Table 1.
Example 8
[0048] 0.054 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, 30 ml of toluene was added into the
reaction bottle, obtaining a metal-catalyst-containing solution.
After the metal catalyst was dissolved in toluene completely, 0.725
mol of 1-hexene (.alpha.-olefin), 177 g of vinyl norbornene, 300 ml
of toluene, and the metal-catalyst-containing solution were added
into another reaction bottle. Herein, .alpha.-olefin (1-hexene) had
a molar percentage of 50 mol %, based on the mole of vinyl
norbornene. After stopping the reaction, 75 ml of ethyl vinyl ether
was added into the reaction bottle. After stirring overnight, the
catalyst of the result was removed and then was purified by a
reprecipitation with methanol. After concentration, Copolymer
(VIII) was obtained, wherein the only repeat unit of Copolymer
(VIII) was
##STR00040##
[0049] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (VIII) were determined, and the
results are shown in Table 1.
Example 9
[0050] 0.0018 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, 1 ml of toluene was added into the
reaction bottle, obtaining a metal-catalyst-containing solution.
After the metal catalyst was dissolved in toluene completely,
0.0005 mol of 1-hexene (.alpha.-olefin), 3 g of vinyl norbornene,
4.5 ml of toluene, and the metal-catalyst-containing solution were
added into another reaction bottle. After stirring completely, a
norbornene-containing solution (2.36 g of norbornene dissolved in 2
ml of toluene) was added into the reaction bottle. Herein,
.alpha.-olefin (1-hexene) had a molar percentage of 1 mol %, based
on the total moles of vinyl norbornene and norbornene. After
stopping the reaction, 2.5 ml of ethyl vinyl ether was added into
the reaction bottle. After stirring overnight, the catalyst of the
result was removed and then was purified by a reprecipitation with
methanol. After concentration, Copolymer (IX) was obtained, wherein
the ratio of the repeat unit
##STR00041##
to the repeat unit
##STR00042##
of Copolymer (IX) was about 1:1.
[0051] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (IX) were determined, and the
results are shown in Table 1.
Comparative Example 1
[0052] 0.018 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 10 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.245 mol of methylacrylate (.alpha.-olefin), 29.4 g of
vinyl norbornene, 45 ml of toluene, and the
metal-catalyst-containing solution were added into another reaction
bottle. After stirring completely, a norbornene-containing solution
(23.06 g of norbornene dissolved in 20 ml of toluene) was added
into the reaction bottle. Herein, methylacrylate had a molar
percentage of 50 mol %, based on the total moles of vinyl
norbornene and norbornene. After stopping the reaction, 25 ml of
ethyl vinyl ether was added into the reaction bottle. After
stirring overnight, the catalyst of the result was removed and then
was purified by a reprecipitation with methanol. After
concentration, Copolymer (X) was obtained, wherein the ratio of the
repeat unit
##STR00043##
to the repeat unit
##STR00044##
of Copolymer (X) was about 1:1.
[0053] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (X) were determined, and the results
are shown in Table 1.
Comparative Example 2
[0054] 0.018 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 10 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 29.4 g of vinyl norbornene, 35 ml of toluene, and the
metal-catalyst-containing solution were added into another reaction
bottle. After stirring completely, a norbornene-containing solution
(23.06 g of norbornene dissolved in 20 ml of toluene) was added
into the reaction bottle. After stopping the reaction, 25 ml of
ethyl vinyl ether was added into the reaction bottle. After
stirring overnight, the catalyst of the result was removed and then
was purified by a reprecipitation with methanol. After
concentration, Copolymer (XI) was obtained, wherein the ratio of
the repeat unit
##STR00045##
to the repeat unit
##STR00046##
of Copolymer (XI) was about 1:1
[0055] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (XI) were determined, and the
results are shown in Table 1.
TABLE-US-00001 TABLE 1 Compar- Compar- ative ative Example Example
Example Example Example Example Example Example Example Example
Example 1 2 3 4 5 6 7 8 9 1 2 VNB(g) 73.6 73.6 147 52.1 88.3 29.4
14.7 177 3 29.4 29.4 NB(g) 57.7 57.7 115 75.0 69.3 23.06 11.5 0
2.36 23.06 23.06 .alpha.-olefin 1- 1- 1- 1- 1- 1- 1- 1- 1- methyl-
-- hexene hexene hexene hexene hexene hexene hexene hexene hexene
acrylate .alpha.-olefin 50 30 20 20 10 5 3 50 1 50 0 (mol %) number
1,033 1,433 1,939 1,683 3,089 4,916 5,291 1,225 11,017 19,402
33,488 average molecular weight (Mn) Td.sub.5%(.degree. C.) 166 254
338 295 430 208 400 167 205 421 411 solubility >70 >70 >70
>70 >60 >60 >40 >70 20 <10 <10 (wt %)
[0056] As shown in Table 1, with copolymerization of vinyl
norbornene and norbornene, the number average molecular weight
(Mn), the polydispersity index (PDI) of the obtained copolymer can
be controlled by means of the addition of 1-hexene
(.alpha.-olefin). Therefore, the obtained copolymer has a molecular
weight less than or equal to 12,000, thereby increasing the
solubility of the copolymer and promoting the subsequent
process.
Example 10
[0057] 0.018 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 10 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.247 mol of 1-octadecene (.alpha.-olefin), 29.4 g of
vinyl norbornene, 45 ml of toluene, and the
metal-catalyst-containing solution were added into another reaction
bottle, obtaining a metal-catalyst-containing solution. After
stirring completely, a norbornene-containing solution (23.06 g of
norbornene dissolved in 20 ml of toluene) was added into the
reaction bottle. Herein, .alpha.-olefin (1-octadecene) had a molar
percentage of 50 mol %, based on the total moles of vinyl
norbornene and norbornene. After stopping the reaction, 25 ml of
ethyl vinyl ether was added into the reaction bottle. After
stirring overnight, the catalyst of the result was removed and then
was purified by a reprecipitation with methanol. After
concentration, Copolymer (XII) was obtained.
[0058] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (XII) were determined, and the
results are shown in Table 2.
Example 11
[0059] Example 11 was performed in the same manner as Example 10
except that the amount of 1-octadecene was reduced from 0.247 mol
to 0.049 mol, obtaining Copolymer (XIII). The number average
molecular weight (Mn), the polydispersity index (PDI), the
solubility (in toluene), and the temperature corresponding to a
thermogravimetric analysis (TGA) weight loss of 5% of Copolymer
(XIII) were determined, and the results are shown in Table 2.
Example 12
[0060] Example 12 was performed in the same manner as Example 10
except that the 1-octadecene was replaced with styrene, obtaining
Copolymer (XIV). The number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (XIV) were determined, and the
results are shown in Table 2.
Example 13
[0061] 0.006 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 4 ml of toluene was added into
the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.008 mol of vinylcyclohexene (.alpha.-olefin), 9.8 g
of vinyl norbornene, 15 ml of toluene, and the
metal-catalyst-containing solution were added into another reaction
bottle. After stirring completely, a norbornene-containing solution
(7.69 g of norbornene dissolved in 7 ml of toluene) was added into
the reaction bottle. Herein, .alpha.-olefin (vinylcyclohexene) had
a molar percentage of 5 mol %, based on the total moles of vinyl
norbornene and norbornene. After stopping the reaction, 8 ml of
ethyl vinyl ether was added into the reaction bottle. After
stirring overnight, the catalyst of the result was removed and then
was purified by a reprecipitation with methanol. After
concentration, Copolymer (XV) was obtained.
[0062] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (XV) were determined, and the
results are shown in Table 2.
Example 14
[0063] 0.0018 g of
1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy-
)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II)
dichloride (as metal catalyst) was added into a reaction bottle
under nitrogen atmosphere, and then 0.5 ml of toluene was added
into the reaction bottle, obtaining a metal-catalyst-containing
solution. After the metal catalyst was dissolved in toluene
completely, 0.043 mol of methylacrylate (.alpha.-olefin), 3 g of
vinyl norbornene, 4.5 ml of toluene, and the
metal-catalyst-containing solution were added into another reaction
bottle. Herein, methylacrylate had a molar percentage of 85 mol %,
based on the total moles of vinyl norbornene and norbornene. After
stopping the reaction, 2.5 ml of ethyl vinyl ether was added into
the reaction bottle. After stirring overnight, the catalyst of the
result was removed and then was purified by a reprecipitation with
methanol. After concentration, Copolymer (XVI) was obtained.
[0064] Next, the number average molecular weight (Mn), the
polydispersity index (PDI), the solubility (in toluene), and the
temperature corresponding to a thermogravimetric analysis (TGA)
weight loss of 5% of Copolymer (XVI) were determined, and the
results are shown in Table 2.
Example 15
[0065] Example 15 was performed in the same manner as Example 10
except that the 1-octadecene was replaced with allyl acetate,
obtaining Copolymer (XVII). The number average molecular weight
(Mn), the polydispersity index (PDI), the solubility (in toluene),
and the temperature corresponding to a thermogravimetric analysis
(TGA) weight loss of 5% of Copolymer (XVII) were determined, and
the results are shown in Table 2.
Example 16
[0066] Example 16 was performed in the same manner as Example 10
except that the 1-octadecene was replaced with 1,5-hexadiene,
obtaining Copolymer (XVIII). The number average molecular weight
(Mn), the polydispersity index (PDI), the solubility (in toluene),
and the temperature corresponding to a thermogravimetric analysis
(TGA) weight loss of 5% of Copolymer (XVIII) were determined, and
the results are shown in Table 2.
TABLE-US-00002 TABLE 2 Example Example Example Example Example
Example Example 10 11 12 13 14 15 16 VNB(g) 29.4 29.4 29.4 9.8 3
29.4 29.4 NB(g) 23.06 23.06 23.06 7.69 2.36 23.06 23.06
.alpha.-olefin 1- 1- styrene vinyl- methyl- allyl 1,5- octadecene
octadecene cyclohexene acrylate acetate hexadiene .alpha.-olefin 50
10 50 5 85 50 50 (mol %) number 871 2,736 1,936 1,988 3,699 2,779
1,072 average molecular weight (Mn) Td.sub.5% (.degree. C.) 152 118
290 126 378 320 214 solubility >70 >70 >70 >70 >50
>70 >70 (wt %)
[0067] As shown in Table 2, with copolymerization of vinyl
norbornene and norbornene, the number average molecular weight
(Mn), the polydispersity index (PDI) of the obtained copolymer can
be controlled by means of the addition of .alpha.-olefin. As shown
in Tables 1 and 2, when the .alpha.-olefin is methylacrylate, the
suitable amount (mol %) of .alpha.-olefin is larger than about 70
mol %, such as larger than 80 mol %.
[0068] Test of Storability
[0069] The copolymers prepared from Examples 1-6 and 9-16 and
Comparative Examples 1-2 were kept for one day (or two days), and
then the solubility (in toluene) and viscosity of the copolymer
were measured. The results are shown in Table 3.
TABLE-US-00003 TABLE 3 Example Example Example Example Example
Example Example 1 2 3 5 6 9 10 solubility kept >70 >70 >70
>60 >60 20 >70 in toluene for one (wt %) day kept >70
>70 >70 >60 >60 >15 >70 for 2 days viscosity(cP)
100 534 11,260 376,200 2,754 solid 18 Example Example Example
Example Comparative Comparative 11 12 15 16 Example 1 Example 2
solubility kept >70 >70 >70 >70 <10 <10 in
toluene for one (wt %) day kept >70 >70 >70 >70 <1
insoluble for 2 days viscosity(cP) 2,869 11,260 52,140 78 solid
solid
[0070] As shown in Table 3, the copolymers prepared from Examples
(i.e. the oligomer of the disclosure) exhibit superior solubility
after two days, since the molecular weight and polydispersity index
of the copolymer can be controlled by means of the addition of
.alpha.-olefin (the obtained copolymers have a molecular weight
less than or equal to 12,000). Accordingly, the oligomer of the
disclosure exhibits superior storability.
[0071] Composition and properties measurement of cured product
thereof
Example 17
[0072] Copolymer (I) (40 parts by weight) of Example 1,
polyphenylene ether (PPE, manufactured and sold by SABIC with a
trade No. of SA9000 (with a molecular weight of about 2,300) (60
parts by weight), and a suitable quantity of initiator were added
into a reaction bottle, and then dissolved in toluene. After mixing
completely, a composition was obtained. Next, the aforementioned
composition was coated on a copper foil (manufactured and sold by
Furukawa Circuit Foil Co., Ltd.). Next, the copper foil coated with
the composition was heated at 100.degree. C. for a period of time.
Next, the above copper foil was then heated gradually and then the
composition was subjected to a crosslinking reaction under a
temperature less than 250.degree. C. (in order to achieve the best
crosslinking density), obtaining Film (I). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (I) were
measured at 10 GHz, and the results are shown in Table 4.
Example 18
[0073] Example 18 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(III) of Example 3, obtaining Film (II). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (II) were
measured at 10 GHz, and the results are shown in Table 4.
Example 19
[0074] Example 19 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(IV) of Example 4, obtaining Film (III). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (III) were
measured at 10 GHz, and the results are shown in Table 4.
Example 20
[0075] Example 20 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(V) of Example 5, obtaining Film (IV). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (IV) were
measured at 10 GHz, and the results are shown in Table 4.
Example 21
[0076] Example 21 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(VI) of Example 6, obtaining Film (V). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (V) were
measured at 10 GHz, and the results are shown in Table 4.
Example 22
[0077] Example 22 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(VIII) of Example 8, obtaining Film (VI). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (VI) were
measured at 10 GHz, and the results are shown in Table 4.
Example 23
[0078] Example 23 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XII) of Example 10, obtaining Film (VII). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (VII) were
measured at 10 GHz, and the results are shown in Table 4.
Example 24
[0079] Example 24 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XIII) of Example 11, obtaining Film (VIII). Next, the dielectric
constant (Dk) and the dissipation factor (DO of Film (VIII) were
measured at 10 GHz, and the results are shown in Table 4.
Example 25
[0080] Example 25 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XIV) of Example 12, obtaining Film (XI). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XI) were
measured at 10 GHz, and the results are shown in Table 4.
Example 26
[0081] Example 26 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XV) of Example 13, obtaining Film (X). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (X) were
measured at 10 GHz, and the results are shown in Table 4.
Example 27
[0082] Example 27 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XVI) of Example 14, obtaining Film (XI). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XI) were
measured at 10 GHz, and the results are shown in Table 4.
Example 28
[0083] Example 28 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XVII) of Example 15, obtaining Film (XII). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XII) were
measured at 10 GHz, and the results are shown in Table 4.
Example 29
[0084] Example 29 was performed in the same manner as Example 17
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XVIII) of Example 16, obtaining Film (XIII). Next, the dielectric
constant (Dk) and the dissipation factor (DO of Film (XIII) were
measured at 10 GHz, and the results are shown in Table 4.
Comparative Example 3
[0085] 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione
(TAIL) (40 parts by weight), polyphenylene ether (PPE, manufactured
and sold by SABIC with a trade No. of SA9000 (with a molecular
weight of about 2,300) (60 parts by weight), and a suitable
quantity of initiator were added into a reaction bottle, and then
dissolved in toluene. After mixing completely, a composition was
obtained. Next, the aforementioned composition was coated on a
copper foil (manufactured and sold by Furukawa Circuit Foil Co.,
Ltd.). Next, the copper foil coated with the composition was heated
at 100.degree. C. for a period of time. Next, the above copper foil
was then heated gradually and then the composition was subjected to
a crosslinking reaction under a temperature less than 250.degree.
C. (in order to achieve the best crosslinking density), obtaining
Film (XIV). Next, the dielectric constant (Dk) and the dissipation
factor (Df) of Film (XIV) were measured at 10 GHz, and the results
are shown in Table 4.
TABLE-US-00004 TABLE 4 dielectric dissipation constant factor
Components of composition (10 GHz) (10 GHz) Example 17 40 wt %
Copolymer (I) 60 wt % PPE 2.49 0.0019 Example 18 40 wt % Copolymer
(III) 60 wt % PPE 2.39 0.0022 Example 19 40 wt % Copolymer (IV) 60
wt % PPE 2.46 0.0023 Example 20 40 wt % Copolymer (V) 60 wt % PPE
2.46 0.0022 Example 21 40 wt % Copolymer (VI) 60 wt % PPE 2.43
0.0023 Example 22 40 wt % Copolymer (VII) 60 wt % PPE 2.47 0.0028
Example 23 40 wt % Copolymer (XII) 60 wt % PPE 2.34 0.0016 Example
24 40 wt % Copolymer (XIII) 60 wt % PPE 2.44 0.0021 Example 25 40
wt % Copolymer (XIV) 60 wt % PPE 2.45 0.0018 Example 26 40 wt %
Copolymer (XV) 60 wt % PPE 2.41 0.0028 Example 27 40 wt % Copolymer
(XVI) 60 wt % PPE 2.45 0.0025 Example 28 40 wt % Copolymer (XVII)
60 wt % PPE 2.48 0.0030 Example 29 40 wt % Copolymer (XVIII) 60 wt
% PPE 2.51 0.0018 Comparative 40 wt % TAIC 60 wt % PPE 2.66 0.0048
Example 3
Example 30
[0086] Copolymer (I) (31 parts by weight) of Example 1,
polyphenylene ether (PPE, manufactured and sold by SABIC with a
trade No. of SA9000 (with a molecular weight of about 2,300) (46
parts by weight), polystyrene-butadiene-styrene (SBS, manufactured
by Cray Valley with a trade No. of Ricon100) (with a molecular
weight of about 4,500) (23 parts by weight) and a suitable quantity
of initiator were added into a reaction bottle, and then dissolved
in toluene. After mixing completely, a composition was obtained.
Next, the aforementioned composition was coated on a copper foil
(manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next,
the copper foil coated with the composition was heated at
100.degree. C. for a period of time. Next, the above copper foil
was then heated gradually and then the composition was subjected to
a crosslinking reaction under a temperature less than 250.degree.
C. (in order to achieve the best crosslinking density), obtaining
Film (XV). Next, the dielectric constant (Dk) and the dissipation
factor (Df) of Film (XV) were measured at 10 GHz, and the results
are shown in Table 5.
Example 31
[0087] Example 31 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(III) of Example 3, obtaining Film (XVI). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XVI) were
measured at 10 GHz, and the results are shown in Table 5.
Example 32
[0088] Example 32 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(IV) of Example 4, obtaining Film (XVII). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XVII) were
measured at 10 GHz, and the results are shown in Table 5.
Example 33
[0089] Example 33 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(V) of Example 5, obtaining Film (XVIII). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XVIII) were
measured at 10 GHz, and the results are shown in Table 5.
Example 34
[0090] Example 34 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(VI) of Example 6, obtaining Film (XIX). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XIX) were
measured at 10 GHz, and the results are shown in Table 5.
Example 35
[0091] Example 35 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(VIII) of Example 8, obtaining Film (XX). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XX) were
measured at 10 GHz, and the results are shown in Table 5.
Example 36
[0092] Example 36 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XII) of Example 10, obtaining Film (XXI). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XXI) were
measured at 10 GHz, and the results are shown in Table 5.
Example 37
[0093] Example 37 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XIII) of Example 11, obtaining Film (XXII). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XXII) were
measured at 10 GHz, and the results are shown in Table 5.
Example 38
[0094] Example 38 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XIV) of Example 12, obtaining Film (XXIII). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XXIII) were
measured at 10 GHz, and the results are shown in Table 5.
Example 39
[0095] Example 39 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XV) of Example 13, obtaining Film (XXIV). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XXIV) were
measured at 10 GHz, and the results are shown in Table 5.
Example 40
[0096] Example 40 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XVI) of Example 14, obtaining Film (XXV). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XXV) were
measured at 10 GHz, and the results are shown in Table 5.
Example 41
[0097] Example 41 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XVII) of Example 15, obtaining Film (XXVI). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XXVI) were
measured at 10 GHz, and the results are shown in Table 5.
Example 42
[0098] Example 42 was performed in the same manner as Example 30
except that Copolymer (I) of Example 1 was replaced with Copolymer
(XVIII) of Example 16, obtaining Film (XXVII). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XXVII) were
measured at 10 GHz, and the results are shown in Table 5.
Comparative Example 4
[0099] 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione
(TAIL) (31 parts by weight), polyphenylene ether (PPE, manufactured
and sold by SABIC with a trade No. of SA9000 (with a molecular
weight of about 2,300) (46 parts by weight),
polystyrene-butadiene-styrene (SBS, manufactured by Cray Valley
with a trade No. of Ricon100) (with a molecular weight of about
4,500) (23 parts by weight) and a suitable quantity of initiator
were added into a reaction bottle, and then dissolved in toluene.
After mixing completely, a composition was obtained. Next, the
aforementioned composition was coated on a copper foil
(manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next,
the copper foil coated with the composition was heated at
100.degree. C. for a period of time. Next, the above copper foil
was then heated gradually and then the composition was subjected to
a crosslinking reaction under a temperature less than 250.degree.
C. (in order to achieve the best crosslinking density), obtaining
Film (XXVIII). Next, the dielectric constant (Dk) and the
dissipation factor (Df) of Film (XXVIII) were measured at 10 GHz,
and the results are shown in Table 5.
TABLE-US-00005 TABLE 5 dielectric dissipation constant factor
Components of composition (10 GHz) (10 GHz) Example 30 31 wt %
Copolymer (I) 23 wt % SBS 46 wt % PPE 2.32 0.0012 Example 31 31 wt
% Copolymer (III) 23 wt % SBS 46 wt % PPE 2.42 0.0016 Example 32 31
wt % Copolymer (IV) 23 wt % SBS 46 wt % PPE 2.41 0.0015 Example 33
31 wt % Copolymer (V) 23 wt % SBS 46 wt % PPE 2.39 0.0018 Example
34 31 wt % Copolymer (VI) 23 wt % SBS 46 wt % PPE 2.30 0.0015
Example 35 31 wt % Copolymer (VIII) 23 wt % SBS 46 wt % PPE 2.42
0.0025 Example 36 31 wt % Copolymer (XII) 23 wt % SBS 46 wt % PPE
2.34 0.0015 Example 37 31 wt % Copolymer (XIII) 23 wt % SBS 46 wt %
PPE 2.38 0.0015 Example 38 31 wt % Copolymer (XIV) 23 wt % SBS 46
wt % PPE 2.37 0.0015 Example 39 31 wt % Copolymer (XV) 23 wt % SBS
46 wt % PPE 2.43 0.0022 Example 40 31 wt % Copolymer (XVI) 23 wt %
SBS 46 wt % PPE 2.41 0.0021 Example 41 31 wt % Copolymer (XVII) 23
wt % SBS 46 wt % PPE 2.46 0.0023 Example 42 31 wt % Copolymer
(XVIII) 23 wt % SBS 46 wt % PPE 2.47 0.0015 Comparative 31 wt %
TAIC 23 wt % SBS 46 wt % PPE 2.61 0.0028 Example 4
Example 43
[0100] Copolymer (I) (70 parts by weight) of Example 1,
polystyrene-butadiene-styrene (SBS, manufactured by Cray Valley
with a trade No. of Ricon100) (with a molecular weight of about
4,500) (30 parts by weight) and a suitable quantity of initiator
were added into a reaction bottle, and then dissolved in toluene.
After mixing completely, a composition was obtained. Next, the
aforementioned composition was coated on a copper foil
(manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next,
the copper foil coated with the composition was heated at
90.degree. C. for a period of time. Next, the above copper foil was
then heated gradually and then the composition was subjected to a
crosslinking reaction under a temperature less than 250.degree. C.
(in order to achieve the best crosslinking density), obtaining Film
(XXIX). Next, the dielectric constant (Dk) and the dissipation
factor (Df) of Film (XXIX) were measured at 10 GHz, and the results
are shown in Table 6.
Example 44
[0101] Example 44 was performed in the same manner as Example 39
except that Copolymer (I) of Example 1 was replaced with Copolymer
(VIII) of Example 8, obtaining Film (XXX). Next, the dielectric
constant (Dk) and the dissipation factor (Df) of Film (XXX) were
measured at 10 GHz, and the results are shown in Table 6.
Example 45
[0102] Copolymer (III) (31 parts by weight) of Example 3,
polyphenylene ether (PPE, manufactured and sold by SABIC with a
trade No. of SA9000 (with a molecular weight of about 2,300) (46
parts by weight), polybutadiene (PB, manufactured by Nippon Soda
with a trade No. of B2000) (with a molecular weight of about 2,100)
(23 parts by weight) and a suitable quantity of initiator were
added into a reaction bottle, and then dissolved in toluene. After
mixing completely, a composition was obtained. Next, the
aforementioned composition was coated on a copper foil
(manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next,
the copper foil coated with the composition was heated at
100.degree. C. for a period of time. Next, the above copper foil
was then heated gradually and then the composition was subjected to
a crosslinking reaction under a temperature less than 250.degree.
C. (in order to achieve the best crosslinking density), obtaining
Film (XXXI). Next, the dielectric constant (Dk) and the dissipation
factor (Df) of Film (XXXI) were measured at 10 GHz, and the results
are shown in Table 6.
Example 46
[0103] Copolymer (V) (38 parts by weight) of Example 5,
polyphenylene ether (PPE, manufactured and sold by SABIC with a
trade No. of SA9000 (with a molecular weight of about 2,300) (57
parts by weight), bismaleimide (manufactured and sold by Daiwa
Kasei Kogyo Co. with a trade No. of BMI-5,100) (with a molecular
weight of about 2,100) (5 parts by weight) and a suitable quantity
of initiator were added into a reaction bottle, and then dissolved
in toluene. After mixing completely, a composition was obtained.
Next, the aforementioned composition was coated on a copper foil
(manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next,
the copper foil coated with the composition was heated at
100.degree. C. for a period of time. Next, the above copper foil
was then heated gradually and then the composition was subjected to
a crosslinking reaction under a temperature less than 250.degree.
C. (in order to achieve the best crosslinking density), obtaining
Film (XXXII). Next, the dielectric constant (Dk) and the
dissipation factor (DO of Film (XXXII) were measured at 10 GHz, and
the results are shown in Table 6.
TABLE-US-00006 TABLE 6 dielectric dissipation constant factor
Components of composition (10 GHz) (10 GHz) Example 43 70 wt %
Copolymer (I) 30 wt % SBS -- 2.35 0.0021 Example 44 70 wt %
Copolymer (VIII) 30 wt % SBS -- 2.25 0.0030 Example 45 31 wt %
Copolymer (III) 23 wt % PB 46 wt % PPE 2.35 0.0018 Example 46 38 wt
% Copolymer (V) 5 wt % BMI 57 wt % PPE 2.48 0.0026
Example 47
[0104] Copolymer (III) (17 parts by weight) of Example 3,
polyphenylene ether (PPE, manufactured and sold by Mitsubishi Gas
Chemical with a trade No. of OPE-2st (with a molecular weight of
about 2,200) (70 parts by weight), polystyrene-butadiene-styrene
(manufactured and sold by Cray Valley. with a trade No. of
Ricon100) (with a molecular weight of about 4,500) (13 parts by
weight) and a suitable quantity of initiator were added into a
reaction bottle, and then dissolved in toluene. After mixing
completely, a composition was obtained. After stirring completely,
a composition was obtained. Next, glass fiber (sold by Asahi Fiber
Glass with a trade No. of L2116) was immersed in the aforementioned
composition, wherein the impregnated amount was about 59%. After
removing the glass fiber from the composition, the glass fiber was
baked at 140.degree. C. by hot air circulating oven to control the
crosslinking degree of about 50%, obtaining a prepreg. Four
prepregs were stacked, and a copper foil, a mirror plate, and a
Kraft paper were disposed on the top surface and the bottom surface
of the stacked structure. The obtained structure was heated to
210.degree. C. gradually by vacuum molding machine for 3 hr,
obtaining Copper foil substrate (I) with a thickness of 0.558 mm.
Next, the dielectric constant (Dk) and the dissipation factor (Df)
of Copper foil substrate (I) were measured at 10 GHz, and the
results are shown in Table 7.
TABLE-US-00007 TABLE 7 dielectric dissipation constant factor
Components of composition (10 GHz) (10 GHz) Example 47 17 wt %
Copolymer (III) 70 wt % PPE 13 wt % SBS 2.96 0.0033
[0105] As shown in Tables 4-7, since the composition includes an
oligomer having a structure represented by Formula (I), the cured
product exhibits a relatively low dielectric constant (less than or
equal to 3.0 (at 10 GHz) and a relatively low dissipation factor
(less than or equal to 0.0033 (at 10 GHz)), thereby serving as a
good material for a high-frequency substrate. As shown in the above
Examples, the composition of the disclosure can be crosslinked at a
temperature less than 250.degree. C., and the obtained oligomer
exhibits superior crosslinking density. Furthermore, the oligomer
can achieve optimal crosslinking density which is checked by means
of the crosslinking exotherm determined by differential scanning
calorimetry.
[0106] It will be clear that various modifications and variations
can be made to the disclosed methods and materials. It is intended
that the specification and examples be considered as exemplary
only, with the true scope of the disclosure being indicated by the
following claims and their equivalents.
* * * * *