U.S. patent application number 14/585906 was filed with the patent office on 2016-06-09 for aqueous-phase catalyst compositions and method for preparing polyphenylene ether.
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 Chi-Wei CHEN, Hou Yuan CHEN, Hsuan-Wei LEE, Chung-Cheng LIN, I-Hong LIN, Wei-Ta YANG.
Application Number | 20160159980 14/585906 |
Document ID | / |
Family ID | 56083020 |
Filed Date | 2016-06-09 |
United States Patent
Application |
20160159980 |
Kind Code |
A1 |
LIN; Chung-Cheng ; et
al. |
June 9, 2016 |
AQUEOUS-PHASE CATALYST COMPOSITIONS AND METHOD FOR PREPARING
POLYPHENYLENE ETHER
Abstract
An aqueous-phase catalyst composition including a metal ion
including copper, nickel, manganese or iron and a water-soluble
linear polymer having a molecular weight ranging from 1,000 to
20,000 is provided. The metal ion and the water-soluble linear
polymer have a weight ratio of 1:1 to 1:5. A method for preparing
polyphenylene ether including providing the disclosed aqueous-phase
catalyst composition and adding phenolic monomers to the
aqueous-phase catalyst composition to proceed to a polymerization
reaction to prepare polyphenylene ether is also provided.
Inventors: |
LIN; Chung-Cheng; (Kaohsiung
City, TW) ; LEE; Hsuan-Wei; (Pingtung City, TW)
; YANG; Wei-Ta; (Taoyuan City, TW) ; LIN;
I-Hong; (Luodong Township, TW) ; CHEN; Chi-Wei;
(Taipei City, TW) ; CHEN; Hou Yuan; (Taoyuan City,
TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE |
Hsinchu |
|
TW |
|
|
Assignee: |
INDUSTRIAL TECHNOLOGY RESEARCH
INSTITUTE
Hsinchu
TW
|
Family ID: |
56083020 |
Appl. No.: |
14/585906 |
Filed: |
December 30, 2014 |
Current U.S.
Class: |
528/217 ;
502/159 |
Current CPC
Class: |
C08G 65/44 20130101 |
International
Class: |
C08G 65/44 20060101
C08G065/44 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 5, 2014 |
TW |
103142304 |
Claims
1. An aqueous-phase catalyst composition, comprising: a metal ion
comprising copper, nickel, manganese or iron; and a water-soluble
linear polymer having a molecular weight ranging from 1,000 to
20,000, wherein the metal ion and the water-soluble linear polymer
have a weight ratio of 1:1 to 1:5.
2. The aqueous-phase catalyst composition as claimed in claim 1,
wherein the water-soluble linear polymer comprises polyethylene
glycol (PEG), polyvinyl alcohol (PVA) or polyitaconic acid
(PIA).
3. The aqueous-phase catalyst composition as claimed in claim 1,
wherein the water-soluble linear polymer comprises poly(itaconic
acid-co-acrylamide), poly(Ita-HEAMOBA-co-acrylic acid) or
poly(Ita-HEAMOBA-co-acrylamide).
4. The aqueous-phase catalyst composition as claimed in claim 1,
wherein the water-soluble linear polymer is represented by the
following structural formula: A .sub.x B .sub.y wherein A comprises
at least one carboxyl group or amide group, II comprises at least
one of at least one carboxyl group and carboxyl group and amide
group, x ranges from 1 to 100, and y ranges from 1 to 100.
5. The aqueous-phase catalyst composition as claimed in claim 4,
wherein the water-soluble linear polymer has a molecular weight
ranging from 4,000 to 8,500.
6. The aqueous-phase catalyst composition as claimed in claim 4,
wherein the water-soluble linear polymer comprises poly(itaconic
acid-co-acrylamide), poly(Ita-HEAMOBA-co-acrylic acid) or
poly(Ita-HEAMOBA-co-acrylamide).
7. The aqueous-phase catalyst composition as claimed in claim 1,
wherein the water-soluble linear polymer is represented by the
following formula: ##STR00006## wherein R1 comprises carboxyl group
or amide group, R2 comprises hydrogen, C1-C9 alkyl group or
carboxyl group, R3 comprises carboxyl group or amide group, R4
comprises carboxyl group, A ranges from 1 to 100, and B ranges from
1 to 100.
8. The aqueous-phase catalyst composition as claimed in claim 7,
wherein the water-soluble linear polymer has a molecular weight
ranging from 4000 to 8500.
9. The aqueous-phase catalyst composition as claimed in claim 7,
wherein the water-soluble linear polymer comprises poly(itaconie
acid-co-acrylamide), poly(Ita-HEAMOBA-co-acrylic acid) or
poly(Ita-HEAMOBA-co-acrylamide).
10. The aqueous-phase catalyst composition as claimed in claim 1,
wherein the metal ion and the water-soluble linear polymer have a
weight ratio of 1:1.5 to 1:4.5.
11. The aqueous-phase catalyst composition as claimed in claim 1,
wherein the water-soluble linear polymer has a molecular weight
ranging from 4,000 to 8,500.
12. A method for preparing polyphenylene ether, comprising:
providing an aqueous-phase catalyst composition as claimed in claim
1; and adding phenolic monomers to the aqueous-phase catalyst
composition to proceed to a polymerization reaction to prepare
polyphenylene ether.
13. The method for preparing polyphenylene ether as claimed in
claim 12, wherein the phenolic monomer is represented by the
following formula: ##STR00007## wherein R1 and R2 independently
comprises hydrogen, C1-C6 alkyl group or phenyl group.
14. The method for preparing polyphenylene ether as claimed in
claim 12, wherein the polymerization reaction is an oxidative
polymerization reaction.
15. The method for preparing polyphenylene ether as claimed, in
claim 12, further comprising adding a surfactant to the
aqueous-phase catalyst composition to proceed to the polymerization
reaction.
16. The method fix preparing polyphenylene ether as claimed in
claim 12, wherein the polymerization reaction is performed in an
aqueous solvent and/or basic reaction conditions.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This Application claims priority of Taiwan Patent
Application No. 103142304, filed on Dec. 5, 2014, the entirety of
which is incorporated by reference herein.
TECHNICAL FIELD
[0002] The technical field relates to an aqueous-phase catalyst
composition and a method for preparing polyphenylene ether (PPE)
using the aqueous-phase catalyst composition.
BACKGROUND
[0003] Polyphenylene ether (PPE) is classified as a
high-performance material which has the characteristics of heat
resistance, flame resistant, light weight, etc. It is widely
applied in various industries, such as the general industry, the
electronics industry, the automotive industry, the consumer goods
industry, etc. The global market demand for PPE is around 200,000
tons per year.
[0004] For the past few years, the technical development of
modified-PPE (m-PPE) has improved demand for polyphenylene ether
material and its application in various fields. The modified PPE
can be applied in compatibilizers, flame retardant additives, and
thermoplastic composite materials, and is especially appropriate
for adoption as high-frequency substrate raw material due to its
high dimension stability and low dielectric properties. However, in
industry, polyphenylene ether (PPE) is mainly produced through
solvent methods requiring the use of a great amount of organic
solvents, resulting in high manufacturing costs and causing severe
pollution and harm to the environment.
SUMMARY
[0005] In accordance with one embodiment of the disclosure, an
aqueous-phase catalyst composition is provided. The aqueous-phase
catalyst composition comprises a metal ion comprising copper,
nickel, manganese or iron and a water-soluble linear polymer having
a molecular weight ranging from 1,000 to 20,000, wherein the metal
ion and the water-soluble linear polymer have a weight ratio of 1:1
to 1:5.
[0006] In accordance with one embodiment of the disclosure, a
method for preparing polyphenylene ether is provided. The
preparation method comprises providing the disclosed aqueous-phase
catalyst composition and adding phenolic monomers to the
aqueous-phase catalyst composition to proceed to a polymerization
reaction to prepare polyphenylene ether (PPE).
[0007] A detailed description is given in the following
embodiments.
DETAILED DESCRIPTION
[0008] In the following detailed description, for purposes of
explanation, numerous specific details are set forth in order to
provide a thorough understanding of the disclosed embodiments. It
will be apparent, however, that one or more embodiments may be
practiced without these specific details. In other instances,
well-known structures and devices are shown schematically in order
to simplify the drawing.
[0009] In accordance with one embodiment of the disclosure, an
aqueous-phase catalyst composition is provided. The aqueous-phase
catalyst composition comprises a metal ion comprising copper,
nickel, manganese or iron and a water-soluble linear polymer having
a molecular weight ranging from 1,000 to 20,000. The metal ion and
the water-soluble linear polymer have a weight ratio of 1:1 to
1:5.
[0010] In some embodiments, when the metal ion is selected from a
copper ion, the copper ion may be derived from copper (I) chloride,
copper (I) bromide, copper (II) chloride, copper (II) bromide,
copper (II) acetylacetonate or a combination thereof. When the
metal ion is selected from a nickel ion, the nickel ion may be
derived from nickel chloride, nickel bromide, nickel oxide, nickel
acetate or a combination thereof. When the metal ion is selected
from a manganese ion, the manganese ion may be derived from
manganese chloride, manganese bromide, manganese oxide, manganese
acetylacetonate or a combination thereof. When the metal ion is
selected from an iron ion, the iron ion may be derived from iron
(III) chloride, iron (III) bromide, iron (II) chloride, iron (II)
bromide, iron (III) acetylacetonate or a combination thereof.
[0011] In some embodiments, the water-soluble linear polymer may
comprise polyethylene glycol (PEG), polyvinyl alcohol (PVA) or
polyitaconic acid (PIA).
[0012] In some embodiments, the water-soluble linear polymer may be
represented by the following structural formula.
A .sub.x B .sub.y
[0013] In the structural formula, A may comprise at least one
carboxyl group (for example, --COOH, --CF.sub.2COOH,
--CH.sub.2COOH, --CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)) or amide group (for example,
--CONH.sub.2, --CONHCH.sub.3 or --CONHCH.sub.2CH.sub.2OH), B may
comprise at least one of at least one carboxyl group (for example,
--COOH, --CF.sub.2COOH, --CH.sub.2COOH, --CH.sub.3CH.sub.2COOH,
--C.sub.6H.sub.4COOH or --CHCO.sub.2H(CO.sub.2H)) and carboxyl
group (for example, --COOH, --CF.sub.2COOH, --CH.sub.2COOH,
--CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)) and amide group (for example,
--CONH.sub.2, --CONHCH.sub.3 or --CONHCH.sub.2CH.sub.2OH), x value
may range from 1 to 100, and y value may range from 1 to 100.
[0014] In some embodiments, A in the structural formula may
comprise acrylic acid, methacrylic acid, itaconic acid, crotonic
acid, maleic acid or fumaric acid, or acrylic amide, methacrylic
amide or 4-(2-hydroxyethylamino)-2-methylene-4-oxobutanoic acid
(HEAMOBA). B in the structural formula may comprise acrylic acid,
methacrylic acid, itaconic acid, crotonic acid, maleic acid or
fumaric acid, or acrylic amide, methacrylic amide or
4-(2-hydroxyethylamino)-2-methylene-4-oxobutanoic acid
(HEAMOBA).
[0015] In some embodiments, when the water-soluble linear polymer
is represented by the afore-mentioned structural formula ( A .sub.x
B .sub.y), the water-soluble linear polymer may have a molecular
weight ranging from 1,000 to 20,000 or 4,000 to 8,500.
[0016] In some embodiments, the water-soluble linear polymer may be
represented by the following formula.
##STR00001##
[0017] In the formula, R1 may comprise carboxyl group (for example,
--COOH, --CF.sub.2COOH, --CH.sub.2COOH, --CH.sub.3CH.sub.2COOH,
--C.sub.6H.sub.4COOH or --CHCO.sub.2H(CO.sub.2H)) or amide group
(for example, --CONH.sub.2, --CONHCH.sub.3 or
--CONHCH.sub.2CH.sub.2OH), R2 may comprise hydrogen, C1-C9 alkyl
group or carboxyl group (for example, --COOH, --CF.sub.2COOH,
--CH.sub.2COOH, --CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)), R3 may comprise carboxyl group (for
example, --COOH, --CF.sub.2COOH, --CH.sub.2COOH,
--CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)) or amide group (for example,
--CONH.sub.2, --CONHCH.sub.3 or --CONHCH.sub.2CH.sub.2OH), R4 may
comprise carboxyl group (for example, --COOH, --CF.sub.2COOH,
--CH.sub.2COOH, --CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)), A value may range from 1 to 100, and B
value may range from 1 to 100.
[0018] In the formula, when R1 is --COOH, R2 is --CH.sub.2COOH, R3
is --COOH and R4 is --CH.sub.2COOH, the water-soluble linear
polymer is "polyitaconic acid". When R1 is --COOH, R2 is --H, R3 is
--CONHCH.sub.2CH.sub.2OH and R4 is --COOH, the water-soluble linear
polymer is "poly(acrylic acid-co-Ita-HEAMOBA)". When R1 is
--CONH.sub.2, R2 is --H, R3 is --COOH and R4 is --COOH, the
water-soluble linear polymer is "poly(acrylamide-co-itaconic
acid)". When R1 is --CONH.sub.2, R2 is --H, R3 is
--CONHCH.sub.2CH.sub.2OH and R4 is --COOH, the water-soluble linear
polymer is "poly(acrylamide-co-Ita-HEAMOBA)".
[0019] In some embodiments, when the water-soluble linear polymer
is represented by the afore-mentioned formula
##STR00002##
the water-soluble linear polymer may have a molecular weight
ranging from 1,000 to 20,000 or 4,000 to 8,500.
[0020] In one embodiment, the metal ion and the water-soluble
linear polymer may have a weight ratio of 1:1 to 1:5 or 1:1.5 to
1:4.5.
[0021] In accordance with one embodiment of the disclosure, a
method for preparing polyphenylene ether (PPE) is provided. The
preparation method comprises providing an aqueous-phase catalyst
composition and adding phenolic monomers to the aqueous-phase
catalyst composition to proceed to a polymerization reaction to
prepare polyphenylene ether (PPE).
[0022] In some embodiments, the aqueous-phase catalyst composition
comprises a metal ion, for example, copper, nickel, manganese or
iron, and a water-soluble linear polymer having a molecular weight
ranging from 1,000 to 20,000. The metal ion and the water-soluble
linear polymer may have a weight ratio of 1:1 to 1:5.
[0023] In some embodiments, when the metal ion is selected from a
copper ion, the copper ion may be derived from copper (I) chloride,
copper (I) bromide, copper (II) chloride, copper (II) bromide,
copper (II) acetylacetonate or a combination thereof. When the
metal ion is selected from a nickel ion, the nickel ion may be
derived from nickel chloride, nickel bromide, nickel oxide, nickel
acetate or a combination thereof. When the metal ion is selected
from a manganese ion, the manganese ion may be derived from
manganese chloride, manganese bromide, manganese oxide, manganese
acetylacetonate or a combination thereof. When the metal ion is
selected from an iron ion, the iron ion may be derived from iron
(III) chloride, iron (III) bromide, iron (II) chloride, iron (II)
bromide, iron (III) acetylacetonate or a combination thereof.
[0024] In some embodiments, the water-soluble linear polymer may
comprise polyethylene glycol (PEG), polyvinyl alcohol (PVA) or
polyitaconic acid (PIA).
[0025] In some embodiments, the water-soluble linear polymer may be
represented by the following structural formula.
A .sub.x B .sub.y
[0026] In the structural formula, A may comprise at least one
carboxyl group (for example, --COOH, --CF.sub.2COOH,
--CH.sub.2COOH, --CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)) or amide group (for example,
--CONH.sub.2, --CONHCH.sub.3 or --CONHCH.sub.2CH.sub.2OH), B may
comprise at least one of at least one carboxyl group (for example,
--COOH, --CF.sub.2COOH, --CH.sub.2COOH, --CH.sub.3CH.sub.2COOH,
--C.sub.6H.sub.4COOH or --CHCO.sub.2H(CO.sub.2H)) and carboxyl
group (for example, --COOH, --CF.sub.2COOH, --CH.sub.2COOH,
--CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)) and amide group (for example,
--CONH.sub.2, --CONHCH.sub.3 or --CONHCH.sub.2CH.sub.2OH), x value
may range from 1 to 100, and y value may range from 1 to 100.
[0027] In some embodiments, A in the structural formula may
comprise acrylic acid, methacrylic acid, itaconic acid, crotonic
acid, maleic acid or fumaric acid, or acrylic amide, methacrylic
amide or 4-(2-hydroxyethylamino)-2-methylene-4-oxobutanoic acid
(HEAMOBA). B in the structural formula may comprise acrylic acid,
methacrylic acid, itaconic acid, crotonic acid, maleic acid or
fumaric acid, or acrylic amide, methacrylic amide or
4-(2-hydroxyethylamino)-2-methylene-4-oxobutanoic acid
(HEAMOBA).
[0028] In some embodiments, when the water-soluble linear polymer
is represented by the afore-mentioned structural formula ( A .sub.x
B .sub.y), the water-soluble linear polymer may have a molecular
weight ranging from 1,000 to 20,000 or 4,000 to 8,500.
[0029] In some embodiments, the water-soluble linear polymer may be
represented by the following formula.
##STR00003##
[0030] In the formula, R1 may comprise carboxyl group (for example,
--COOH, --CF.sub.2COOH, --CH.sub.2COOH, --CH.sub.3CH.sub.2COOH,
--C.sub.6H.sub.4COOH or --CHCO.sub.2H(CO.sub.2H)) or amide group
(for example, --CONH.sub.2, --CONHCH.sub.3 or
--CONHCH.sub.2CH.sub.2OH), R2 may comprise hydrogen, C1-C9 alkyl
group or carboxyl group (for example, --COOH, --CF.sub.2COOH,
--CH.sub.2COOH, --CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)), R3 may comprise carboxyl group (for
example, --COOH, --CF.sub.2COOH, --CH.sub.2COOH,
--CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)) or amide group (for example,
--CONH.sub.2, --CONHCH.sub.3 or --CONHCH.sub.2CH.sub.2OH), R4 may
comprise carboxyl group (for example, --COOH, --CF.sub.2COOH,
--CH.sub.2COOH, --CH.sub.3CH.sub.2COOH, --C.sub.6H.sub.4COOH or
--CHCO.sub.2H(CO.sub.2H)), A value may range from 1 to 100, and B
value may range from 1 to 100.
[0031] In some embodiments, when the water-soluble linear polymer
is represented by the afore-mentioned formula
##STR00004##
the water-soluble linear polymer may have a molecular weight
ranging from 1,000 to 20,000 or 4,000 to 8,500.
[0032] In one embodiment, the metal ion and the water-soluble
linear polymer may have a weight ratio of 1:1 to 1:5 or 1:1.5 to
1:4.5.
[0033] In some embodiments, the phenolic monomer may be represented
by the following formula.
##STR00005##
[0034] In the formula, R1 and R2 may independently comprise
hydrogen, C1-C6 alkyl group or phenyl group.
[0035] In one embodiment, the polymerization reaction may be an
oxidative polymerization reaction.
[0036] In one embodiment, the method for preparing polyphenylene
ether (PPE) further comprises adding a surfactant to the
aqueous-phase catalyst composition to proceed to the polymerization
reaction.
EXAMPLES
Example 1
Preparation of the Polyphenylene Ether (1) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition: PEG
(Mn=1,000); Metal Ion: Water-Soluble Linear Polymer=1:1.8 (Weight
Ratio))
[0037] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 1 g of polyethylene
glycol (PEG1000) and 40 mL of water were added to a 100-mL
double-neck bottle and heated to 50.degree. C. while being stirred
for 30 minutes.
[0038] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0039] After purification, the first product was dissolved in
tetrahydrofuran (THF) and added to methanol to perform
re-precipitation. A second product was then collected through the
air-extracting apparatus. Next, the second product was dried in an
oven to prepare the polyphenylene ether (PPE). Finally, the yield,
molecular weight and polydispersity index (PDI) of the
polyphenylene ether (PPE) were then calculated and are shown in
Table 1.
Example 2
Preparation of the Polyphenylene Ether (2) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition: PVA
(Mn=10,000); Metal Ion: Water-Soluble Linear Polymer=1:1.8 (Weight
Ratio))
[0040] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 1 g of polyvinyl
alcohol (PVA) and 40 mL of water were added to a 100-mL double-neck
bottle and heated to 50.degree. C. while being stirred for 30
minutes.
[0041] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0042] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 1.
Example 3
Preparation of the Polyphenylene Ether (3) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition: PIA
(Mn=3,500); Metal Ion: Water-Soluble Linear Polymer=1:1.8 (Weight
Ratio))
[0043] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 1 g of polyitaconic
acid (PIA) and 40 mL of water were added to a 100-mL double-neck
bottle and heated to 50.degree. C. while being stirred for 30
minutes.
[0044] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0045] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 1.
Example 4
Preparation of the Polyphenylene Ether (4) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition:
Poly(Itaconic Acid-Co-Acrylamide)(Mn=6,700); Metal Ion:
Water-Soluble Linear Polymer=1:1.5 (Weight Ratio))
[0046] (I) Preparation of the Poly(Itaconic Acid-Co-Acrylamide)
[0047] First, 6 g of itaconic acid (46.1 mmol), 4 g of acrylic
amide (56.3 mmol) and 0.5 g of azobisisobutyronitrile (AIBN) (0.31
mmol) were dissolved in 130 mL of water under 70.degree. C. while
being stirred for 5 days to perform a polymerization reaction to
obtain a resulting solution. After the reaction was completed, most
of water was evaporated under reduced pressure. The resulting
solution was then added to methanol/ethyl acetate to perform
re-precipitation to obtain poly(itaconic acid-co-acrylamide). The
poly(itaconic acid-co-acrylamide) was analyzed by .sup.1H NMR and
the data are shown as follows.
[0048] .sup.1H NMR (d-MeOH, 400 MHz): .delta.=3.0-2.4 (2H), 2.4-1.8
(3H), 1.8-1.2 (2H).
[0049] (II) Preparation of the Polyphenylene Ether
[0050] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 0.84 g of
poly(itaconic acid-co-acrylamide) and 40 mL of water were added to
a 100-mL double-neck bottle and heated to 50.degree. C. while being
stirred for 30 minutes.
[0051] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0052] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 1.
Example 5
Preparation of the Polyphenylene Ether (5) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition:
Poly(Ita-HEAMOBA-Co-Acrylic Acid)(Mn=4,800); Metal Ion:
Water-Soluble Linear Polymer=1:1.5 (Weight Ratio))
[0053] (I) Preparation of the Poly(Ita-HEAMOBA-Co-Acrylic Acid)
[0054] First, 6.4 g of Ita-HEAMOBA (37 mmol), 4 g of acrylic acid
(55.6 mmol) and 0.5 g of AIBN (0.31 mmol) were dissolved in 130 mL
of water under 75.degree. C. while being stirred for 5 days to
perform a polymerization reaction to obtain a resulting solution.
After the reaction was completed, most of water was evaporated
under reduced pressure. The resulting solution was then added to
methanol/ethyl acetate to perform re-precipitation to obtain
poly(Ita-HEAMOBA-co-acrylic acid). The poly(Ita-HEAMOBA-co-acrylic
acid) was analyzed by .sup.1H NMR and the data are shown as
follows.
[0055] .sup.1H NMR (d-MeOH, 400 MHz): .delta.=3.71 (t, 2H),
3.69-3.35 (1H), 3.02 (t, 2H), 2.8-2.4 (1H), 2.4-2.1 (1H), 2.1-1.8
(1H), 1.8-1.2 (2H).
[0056] (II) Preparation of the Polyphenylene Ether
[0057] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 0.84 g of
poly(Ita-HEAMOBA-co-acrylic acid) and 40 mL of water were added to
a 100-mL double-neck bottle and heated to 50.degree. C. while being
stirred for 30 minutes.
[0058] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0059] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 1.
Example 6
Preparation of the Polyphenylene Ether (6) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition:
Poly(Ita-HEAMOBA-Co-Acrylic Acid)(Mn=5,600); Metal Ion:
Water-Soluble Linear Polymer=1:4.5 (Weight Ratio))
[0060] (I) Preparation of the Poly(Ita-HEAMOBA-Co-Acrylic Acid)
[0061] First, 6.4 g of Ita-HEAMOBA (37 mmol), 4 g of acrylic acid
(55.6 mmol) and 0.5 g of AIBN (0.31 mmol) were dissolved in 130 mL
of water under 75.degree. C. while being stirred for 5 days to
perform a polymerization reaction to obtain a resulting solution.
After the reaction was completed, most of water was evaporated
under reduced pressure. The resulting solution was then added to
methanol/ethyl acetate to perform re-precipitation to obtain
poly(Ita-HEAMOBA-co-acrylic acid). The poly(Ita-HEAMOBA-co-acrylic
acid) was analyzed by .sup.1H NMR and the data are shown as
follows.
[0062] .sup.1H NMR (d-MeOH, 400 MHz): .delta.=3.71 (t, 2H),
3.69-3.35 (1H), 3.02 (t, 2H), 2.8-2.4 (1H), 2.4-2.1 (1H), 2.1-1.8
(1H), 1.8-1.2 (2H).
[0063] (II) Preparation of the Polyphenylene Ether
[0064] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 2.52 g of
poly(Ita-HEAMOBA-co-acrylic acid) and 40 mL of water were added to
a 100-mL double-neck bottle and heated to 50.degree. C. while being
stirred for 30 minutes.
[0065] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0066] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 1.
Example 7
Preparation of the Polyphenylene Ether (7) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition:
Poly(Ita-HEAMOBA-Co-Acrylamide)(Mn=8,200); Metal Ion: Water-Soluble
Linear Polymer=1:1.5 (Weight Ratio))
[0067] (I) Preparation of the Poly(Ita-HEAMOBA-Co-Acrylamide)
[0068] First, 6.4 g of Ita-HEAMOBA (37 mmol), 4 g of acrylamide
(56.3 mmol) and 0.5 g of AIBN (0.31 mmol) were dissolved in 130 mL
of water under 75.degree. C. while being stirred for 5 days to
perform a polymerization reaction to obtain a resulting solution.
After the reaction was completed, most of water was evaporated
under reduced pressure. The resulting solution was then added to
methanol/ethyl acetate to perform re-precipitation to obtain
poly(Ita-HEAMOBA-co-acrylamide). The
poly(Ita-HEAMOBA-co-acrylamide) was analyzed by .sup.1H NMR and the
data are shown as follows.
[0069] .sup.1H NMR (d-MeOH, 400 MHz): .delta.=3.75 (t, 1H),
3.75-3.40 (2H), 3.12 (t, 111), 2.8-2.4 (1H), 2.4-1.8 (2H), 1.8-1.2
(2H).
[0070] (II) Preparation of the Polyphenylene Ether
[0071] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 0.84 g of
poly(Ita-HEAMOBA-co-acrylamide) and 40 mL of water were added to a
100-mL double-neck bottle and heated to 50.degree. C. while being
stirred for 30 minutes.
[0072] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0073] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 1.
Example 8
Preparation of the Polyphenylene Ether (8) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition:
Poly(Ita-HEAMOBA-Co-Acrylamide)(Mn=8,200); Metal Ion: Water-Soluble
Linear Polymer=1:4.5 (Weight Ratio))
[0074] (I) Preparation of the Poly(Ita-HEAMOBA-Co-Acrylamide)
[0075] First, 6.4 g of Ita-HEAMOBA (37 mmol), 4 g of acrylamide
(56.3 mmol) and 0.5 g of AIBN (0.31 mmol) were dissolved in 130 mL
of water under 75.degree. C. while being stirred for 5 days to
perform a polymerization reaction to obtain a resulting solution.
After the reaction was completed, most of water was evaporated
under reduced pressure. The resulting solution was then added to
methanol/ethyl acetate to perform re-precipitation to obtain
poly(Ita-HEAMOBA-co-acrylamide). The
poly(Ita-HEAMOBA-co-acrylamide) was analyzed by .sup.1H NMR and the
data are shown as follows.
[0076] .sup.1H NMR (d-MeOH, 400 MHz): .delta.=3.75 (t, 1H),
3.75-3.40 (2H), 3.12 (t, 1H), 2.8-2.4 (1H), 2.4-1.8 (2H), 1.8-1.2
(2H).
[0077] (II) Preparation of the Polyphenylene Ether
[0078] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 2.52 g of
poly(Ita-HEAMOBA-co-acrylamide) and 40 mL of water were added to a
100-mL double-neck bottle and heated to 50.degree. C. while being
stirred for 30 minutes.
[0079] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0080] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 1.
Example 9
Preparation of the Polyphenylene Ether (9) (the Water-Soluble
Linear Polymer in the Aqueous-Phase Catalyst Composition:
Poly(Ita-HEAMOBA-Co-Acrylic Acid)(Mn=4,800); Metal Ion:
Water-Soluble Linear Polymer=1:1.5 (Weight Ratio))
[0081] (I) Preparation of the Poly(Ita-HEAMOBA-Co-Acrylic Acid)
[0082] First, 6.4 g of Ita-HEAMOBA (37 mmol), 4 g of acrylic acid
(55.6 mmol) and 0.5 g of AIBN (0.31 mmol) were dissolved in 130 mL
of water under 75.degree. C. while being stirred for 5 days to
perform a polymerization reaction to obtain a resulting solution.
After the reaction was completed, most of water was evaporated
under reduced pressure. The resulting solution was then added to
methanol/ethyl acetate to perform re-precipitation to obtain
poly(Ita-HEAMOBA-co-acrylic acid). The poly(Ita-HEAMOBA-co-acrylic
acid) was analyzed by .sup.1H NMR and the data are shown as
follows.
[0083] .sup.1H NMR (d-MeOH, 400 MHz): .delta.=3.71 (t, 2H),
3.69-3.35 (1H), 3.02 (t, 2H), 2.8-2.4 (1H), 2.4-2.1 (1H), 2.1-1.8
(1H), 1.8-1.2 (2H).
[0084] (II) Preparation of the Polyphenylene Ether
[0085] First, 0.62 g of Nickel (II) acetate tetrahydrate (2.5
mmol), 0.84 g of poly(Ita-HEAMOBA-co-acrylic acid) and 40 mL of
water were added to a 100-mL double-neck bottle and heated to
50.degree. C. while being stirred for 30 minutes.
[0086] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0087] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 1.
TABLE-US-00001 TABLE 1 Water-soluble Molecular Polydispersity
Examples linear polymer Yield (%) weight index (PDI) 1 PEG 68 5,500
2.4 2 PVA 62 6,000 2.5 3 PIA 62 5,200 1.8 4 Poly(itaconic 46 3,700
1.6 acid-co- acrylamide) 5 Poly(Ita- 40 3,233 1.48 HEAMOBA-
co-acrylic acid) 6 Poly(Ita- 64 2,056 1.30 HEAMOBA- co-acrylic
acid) 7 Poly(Ita- 66 2,842 1.60 HEAMOBA- co-acrylamide) 8 Poly(Ita-
81 2,205 1.58 HEAMOBA- co-acrylamide) 9 Poly(Ita- 25 1,645 1.15
HEAMOBA- co-acrylic acid)
Comparative Example 1
Preparation of the Polyphenylene Ether (the Water-Soluble Compound
in the Aqueous-Phase Catalyst Composition: Itaconic Acid
(Mn=130.1); Metal Ion: Water-Soluble Compound=1:1.8 (Weight
Ratio))
[0088] First, 0.56 g of copper bromide (CuBr.sub.2)(2.5 mmol), 1 g
of itaconic acid (IA) and 40 mL of water were added to a 100-mL
double-neck bottle and heated to 50.degree. C. while being stirred
for 30 minutes.
[0089] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0090] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 2.
Comparative Example 2
Preparation of the Polyphenylene Ether (the Water-Soluble Linear
Polymer in the Aqueous-Phase Catalyst Composition: PEG (Mn=400);
Metal Ion: Water-Soluble Linear Polymer=1:1.8 (Weight Ratio))
[0091] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 1 g of polyethylene
glycol and 40 mL of water were added to a 100-mL double-neck bottle
and heated to 50.degree. C. while being stirred for 30 minutes.
[0092] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0093] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 2.
Comparative Example 3
Preparation of the Polyphenylene Ether (the Water-Soluble Linear
Polymer in the Aqueous-Phase Catalyst Composition: PVA (Mn=10,000);
Metal Ion: Water-Soluble Linear Polymer=1:8 (Weight Ratio))
[0094] First, 0.56 g of CuBr.sub.2 (2.5 mmol), 4.48 g of polyvinyl
alcohol (PVA) and 40 mL of water were added to a 100-mL double-neck
bottle and heated to 50.degree. C. while being stirred for 30
minutes.
[0095] Next, 3.1 g of dimethyl phenol monomer (25 mmol), 1.0 g of
sodium hydroxide (25 mmol) and 0.91 g of sodium hexadecyl sulfate
(SHDS)(2.5 mmol) dissolved in 40 mL of water were added to the
double-neck bottle with conducting oxygen gas and stirring for 12
hours to obtain a resulting solution. After the reaction was
completed, a few drops of hydrochloric acid were added to the
resulting solution to stop the reaction. The resulting solution was
then added to 650 mL of methanol to perform re-precipitation. A
first product was then collected through an air-extracting
apparatus.
[0096] After purification, the first product was dissolved in THF
and added to methanol to perform re-precipitation. A second product
was then collected through the air-extracting apparatus. Next, the
second product was dried in an oven to prepare the polyphenylene
ether (PPE). Finally, the yield, molecular weight and
polydispersity index (PDI) of the polyphenylene ether (PPE) were
then calculated and are shown in Table 2.
TABLE-US-00002 TABLE 2 Comparative Water-soluble Molecular
Polydispersity Examples linear polymer Yield (%) weight index (PDI)
1 IA 56 4,700 2.0 2 PEG 66 5,900 2.9 3 PVA 68 5,300 3.1
[0097] In the disclosure, a novel environmental process for
preparing polyphenylene ether (PPE) is developed. In this process,
an oxidative polymerization reaction between phenolic monomers and
a stable complex (i.e. aqueous-phase catalyst) formed of a
water-soluble linear polymer having a molecular weight ranging from
1,000 to 20,000 and a metal ion with a specific ratio (for example,
metal ion: water-soluble linear polymer=1:1 to 1:5) is performed.
Compared to the current solvent process for industrial production,
in the present aqueous-phase polymerization method for synthesizing
polyphenylene ether (PPE), polyphenylene ether (PPE) is effectively
prepared under an aqueous environment, having the advantages of low
environmental hazard and low cost. Additionally, in accordance with
the structure and composition of water-soluble linear polymers
(i.e. obtaining various expected copolymers using free-radical
polymerization methods) in the processes, in addition to
improvement of the yield, the polydispersity index (PDI) of
polyphenylene ether (PPE) is also effectively decreased to about
1.3, obtaining polyphenylene ether (PPE) with a high uniformity,
which is quite beneficial to the future development and application
of high-order precision electronic materials.
[0098] It will be apparent to those skilled in the art that various
modifications and variations can be made to the disclosed
embodiments. 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.
* * * * *