第
35
卷第
2
期
2008
年
3
月
浙江大学学报(理学版)
Journal
of
Zhejiang
University{ Science
Edition)
http://www.journals.zju.edu.cn/sci
三挂基苯甲基氨基均三曝与双盼
A
型
环氧树脂的固化反应研究
张兴宏黄丽华成国荣
l
骨
Vo
l.
35
NO.2
Mar.
2008
O.
浙江大学高分子科学研究所,浙江杭州
310027;
2.
深圳高级技工学校应用生物系,广东深圳
518048)
摘
要:采用等转化率法研究了
2
,
4 ,
6
三(务基苯甲基氨基)-均三嗓
(MFP)
与双盼
A
型环氧树脂
CDGEBA)
在等
温和非等温条件下的固化反应行为,两种条件下
MFP/DGEBA
固化反应的表观活化能
(E
,
)均随转化率
(α)
增加呈
先减后增的趋势
(α=
0.25
时取得最小值)
.由于仲接基和盼发基对环氧基反应的不等活性,非等温罔化反应时两
种反应先后发生,形成
Triazine-NCH
,
-CH
(OH)-
结构后,再形成
ArO-CH
,
-CH(OH)-
结构并产生交联,前后两阶段
E
,分别为
69.8
、
86.
8 kJ •
mol-
1
•
对等温固化反应,由于起始反应温度高,仲膝基和盼务基几乎同步与环氧基发生
反应,两者的相互催化作用使反应前期
E
,相对较低
(59.1
kJ.
mol-
1
)
,固化反应速度较快,引起体系粘度迅速增
大,扩散控制反应提前,从而造成反应后期
E
,
(89.7
kJ •
mol-
1
)
相对较大.
关键词:环氧树脂;因化;动力学;等转化率法
中图分类号
:0633.13
文献标识码
:A
文章编号:
1008-
9497(2008)02-185
- 06
ZHANG
Xing-hong
1
,
HUANG
Li-hua'
,
QI
Guo-rong
1
怜
(1.
Institute
0/
Polymer
Science ,
Zhejiang
University
,
Hangzhou
310027 ,
China;
2.
Department
0/
A
ρρ
lied
Biology
,
Shenzhen
Senior
Technical
I
η
stitute
,
Shenzhen
518048
,
China)
Study
on
the
curing
behavior
of
2 , 4 ,
6-tri
(hydroxylphenylamine)
-s-triazine
and
diglycidyl
ether
of
bisphenol A. J 0 ur
nal of Zhejiang
University(Science
Edition)
, 2008 ,
35(2):
185~
190
Abstract:
The
curing
behavior
of
2 , 4,
6-tri
(hydroxylphenylmethylmino)-s-triazine
(MFP)
and
diglycidyl
ether
of
bisphenol A
(DGEBA)
was
investigated
intensively
by DSC via isoconversional
method.
An
obvious non-
/i
near
rela-
tionship
of
the
apparent
activation
energy
(E
,)
vs.
conversion
(,,)
was
found for
isothermal
and
non-isothermal
cu-
ring process.
E
,
αof
both
curing
process
reached
to
a
minimum
value
when
α=
O.
25.
For
non-isothermal
curing
process
,
the
occurrence
of reaction of
triazine-NH
with
oxirane
ring
was
prior
to
the
reaction
of
Ar-OH
with
oxirane
ring
due
to
the
unequal activity of
them
,
so
the
structure
of
Triazin
e--
NCH
,
-CH
(OH)-
was
formed before
the
for-
mation
of
ArO-CH
,
-CH
(OH)-
,
and
the
average
E,
was
69.8
kJ •
mol-
1
when
α<0.
25
,
and
86.8
kJ •
mol-
1
when
α>0.
25.
The
formation
of local
ordered
structure
during
the
non-isothermal
curing
process
might
be
responsible
for
the
relationship
of E,
vs.α.
For
isothermal
curing
reaction
process
,
three-dimensional
chain
extension
occurred
at
the
beginning of
reaction
for
high
curing
temperatures.
An
intermolecular
associated
catalytic
effect of
Triazine-NH
and
Ar-OH
on
their
reactivity
towards
oxirane
group
was
the
main
reason
for low E, value in
the
beginning
stage
of
isothermal
curing
process.
The
average
E,
was
59. 1 kJ •
mol-
1
whenα<0.25
,
and
89. 7 kJ •
mol-
1
when
α>0.25.
Key words:
epoxy
resin;
curing
kinetics;
isoconversional
环氧树脂由于具有优异的综合性能而成为目前
最为重要的电子化学材料之→.然而随着人们环保
意识的增强,要求用于电子产品的环氧树脂需达到
"元卤"阻燃和"无铅"焊接的要求"元卤"即要求树
收稿日期:
2007-03-12.
脂基体中不含卤素,以防止其在燃烧或降解过程中
产生有毒物"无铅"则要求承载电器元件的树脂基
体具有更高热稳定性,以满足"元铅"焊接加工制程
的需求.为此,近年来人们发展了一系列含氮、磷和
作者简介:张兴宏
0977
一),男,讲师,博士,主要从事
CO
,的化学固定和高性能热固性树脂合成研究.
精通讯作者,教授.
E-mail: q;guorong@zju.edu.cn