2019最新苯并恶嗪树脂及其在复合材料中的应用物理

1.2
1.1
1.0
0
5
10
15
Cure time (h)
Fig.4-3 Room temperature density changes of the isothermal curing of
B(1)(), B(2)() and B(3)() at 180
� A
Volumetric shrinkage (%)
0.05
45
BOZ-M/EP
� , MPa
� , MPa
� , MPa
�
25,
�
155,
�
180,
� , MPa
� , %
�
2.5h
�
114h
� , KJ/m2
�
�
� , N
325 402
557 466 402 138
0.031 0.062
195 42
7012
� Et�104MPa � %
� tMPa � Ef�103MPa � fMPa
4.7
4.71�1012 3.26�1013
4.78
3.8�1012 4.41�1013
4.94
Tan
0.0076
0.0060
0.0070
7 MDAPF-2-GF
a% g/cm3 % MPa
180 v�m 180 180 Tan 180 EbMV/m % () Tgb N KJ/m2
36 1.93 0.03
22
711
37.1
180
519.2
17.4
22
524
34.0
BOZ-M/PF/EP
MPa
22 180

459.9 389.2
GPa
27.1 24.0
22
326
23.2
BOZ-M/PF/EP
MPa
22
679
180
570
GPa
38.4 16.1
22
463
17.8
--------RTM
monomer() and polymer()
� 155180
� Tg, �
3 *
0
%
98
%
0.98
8
98
0.97
24
97
0.96
81
94.2
0.93
*39%
4
MPa
100
150
646.0
592
579
155
543.0
497
487
v �m S
3.54�1012 6.34�1013
1800
1600
Gel time at 150?
1400
1200
1000
800
600
400
0
2
4
6
8
10
content of imidazole in Benzoxazine( % )
1.
2.
3. 8
DSC
1.
2.
3.
4.
1 3 5 8 10
Tpeak ()
189/21 9
177/21 4
BOZ-M-
The glass transition temperature of benzoxazine-epoxy
Tg/
100/0 180
90/10 188
m(B)/m(E) 80/20 70/30 60/40 199 218 210
50/50 182
E5228 ./.200823215-18.
1.07 0.73 27.5
7.73 63.6
MDA
MPa 161
(GPa) 5.0
(MPa)
86.05
(GPa) 5.03
2.01%
BOZ-M/PF/EP
170.1
7.72
MDA
MPa GPa
22
458.7
27.4
180
405.2
25.2
22
333.4
24.4
MDA
MPa GPa
3.0
150 Smax=3.0 %
2.5
140 Smax=2.0 %
2.0
1.5
1.0
0.5
0.0 0
50 100 150 200 250 300
Cure time (min)
Fig. 4-6 Volumetric shrinkage as a function of time for isothermal cure of
5 ALPF
g/cm3
% Mpa
155
N
KJ/m2
v
�m
155
24hr
s
155
24hr
Tan
155
155
24hr
EbMV/m
24 %
720 603 7040 253 2.6�1012 5.9�1010 8.8�1010
0.0090 0.0691
5.1 4.8
24.8 44.2
1.80 0.4
646.0 543.0 8338 353 >244
3.54�1012 1.15�1011 3.40�1010
6.34�1013 7.75�1012 6.50�1011
0.0076 0.0610
4.7 5.1 5.1 21.8 25.1 21.8 44.2 FH1 FV0
400 240 105 103
39 1.79 0.22
537 416
626 520
1.1�1012 4.7�1010
1.0�1012 2.0�1010
5.0
4.9
6.1
0.017 24.5 47 V-0 262
269
0.0048 0.026 24.6
54
V-0
268 287 7318 244
400 250 1011 109
0.05 40
R1
O N R2
A t(160C)>2h
ON
t(160C)>2h
CH2
NO
R
R
t(160C) 1h 20m
DADBOZ
t(160C) 250s
NO
OH
ON
CH2
CH2
CH2
ON
1
90
s/160�1
237
%
2.68
%
2.76
%
92.3
2
%
1801gs 4# 25,s
----
RTM
ON
CH2
NO
Viscosity (Pa.s) Viscosity (Pa.s)
------
------"" ------
------ ------ ------ ------
,
,
RTM
-----" " ZL 94 1 11852.5
-----" " ZL95111413.1
-----" "
(ZL 03117779.4)
----Tg
800
Testing temperature: 30 "�" expansion "+" shrinkage E-44: Epoxy resin MDA: diphenylmethane�4, 4' �diamino
--
� 140
1.5
Density (g/cm3)
1.4
1.3
1.2
1.1 0
5
10
15
---
�
� � �
� /
�
�
-CO-C=C-CO-N-
-OCN
�
1944HollyCope 1949Burke
1973Schreiber
1990Ishida
2000 80
1993
(1000)
------
------
166/21 1
157/20 0
157/20 0
Tonset
H
() J/g
160
261
150
267
140
265
138
264
138
259
1. 2. 3. 4.8
+ M-
�
30% 20% 15% 10% 0%
1'31''
3'26'' 6'34'' 8'07'' 35'
s
500 400 300 200 100
B(1) )150)140
�
Volumetric shrinkage (%)
12
180 Smax=10 %
10
160 Smax=2.3 %
8
6
4
2
0
0
50
100
150
200
Cure time (min)
Fig. 4-7 Volumetric shrinkage as a function of time for isothermal cure of
� 0~40
6
�
�
� A DSC210 150132 130
� � - � � -
�
� ----( GB1033-86)
� ----
N
CH3
O
O
C
N
CH3
R1 R2
O N
B(1)
B(2): R1=H, R2=CH3 B(3): R1= R2=Cl
Tab.4-2 Density and apparent shrinkage of different systems
1/0
2/1 1.5/1 1.18/1 1/1.5 1/2
Tg/ 156
172 173
167
133
117
2 A-F-51
MPa (Gpa)
1/0 95.5 5.63
m(B)/m(E)
2/1
1.5/1
116.8
96.4
4.57
4.87
1.18/1 142 4.9
220
1 A-F-51 21
(BOZ-M)
B(2) )180)160
--
� --
Density (g/cm3)
b
a
Troom
Tg
Tcure
Temperature
Fig.4-13 Density changes of an expanding monomer with the thermal expansion
coefficient of the monomer higher than that of the polymer
-----2002 ----2002 ------2001 ------2006 2007
�
�
�
1602 2
�
� RTM
OH |
+ 2CH O + 2
NH |2
R1
R2
O N__
R1
N
O
O
N
R3
R4
CH 2
R2
R1R2R3R4=H-CH2-CH=CH-CH=CH2-CH2-C=CH -CH2-C=C-CH2--C=N-C=CH
of benzoxazines
System
Density (g/cm3)
Monomer
Polymer
Shrinkage (%)
B(1) B(2) B(3) E-44+MDA
1.2030 1.2107 1.4597 1.1998
1.1854 1.1896 1.4048 1.1989
� 1.48 � 1.77 � 3.90 � 0.075
0 0
20
40
60
80
100
%
6 - +
3 *
%
s
0.5
1
2
3
%
20
73
55
42
28
30
50
39
32
26
70
45
39
36
23
A-F-51
1/0
50
min)
160
m(B)/m(E) 2/1 1.5/1 1.18/1
25 30
26
1/1.5 1/2
33
36
1 A-F-51
m(B)/m(E)
monomer() and polymer()
--
� --
1.25
1.20
Density (g/cm3)
1.15
1.10
1.05
1.00 0
50
100
150
200
Temperature ()
Fig.4-11 Density changes as a function of temperature for B(2)
%
%
,
55.6 260
17 <3.56
70 >2
� ( DSC: 200 , 250; tg(160):2h �
2%, 130, 200 t(160 ):1-2min 1%, 130 ,190 ; t(160)1-2min � ():1min �
150
gel time(s)
"a" volumetric shrinkage during curing; "b" apparent volumetric expansion
--
� A--
1.22
1.20
Density (g/cm3)
1.18
1.16
1.14
1.12 0
50
100
150
200
Temperature ()
Fig. 4-10 Density changes as a function of temperature for B(1)
--
----
----180155 18080% 300 /
----2000/
----1.5
----
---- ----Tg200UL-
Vo,V1) RTM
7 4 -----"" ZL 94 1 11852.5 -----""ZL 95111413.1 -----"" ZL 99114603.4 -----"" (ZL 03117779.4) -----"" :03126518.9 -----"" :200610020857.5 -----" " :200610020858.X
5
10
15
Cure time (h) Fig.4-2 Room temperature density changes of the isothermal curing of
B(1)(), B(2)() and B(3)() at 160