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 |  موضوع: كتاب Reaction Injection Molding الثلاثاء 10 سبتمبر 2019, 10:56 pm | |
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أخوانى فى الله
أحضرت لكم كتاب
Reaction Injection Molding
Polymer Chemistry and Engineering
Jiri E. Kresta, EDITOR
University ofDetroit
Based on a symposium sponsored by
the Division of Polymeric Materials Science and Engineering at the 186th Meeting
of the American Chemical Society,
Washington, D.C.
و المحتوى كما يلي :
Future of RIM Development in the U S
1
RIM and RRIM Development in Japan
11
Studies of the Formation and Properties
31
RIM Urethanes StructureProperty Relationships
55
The Effect of Hard Segment Content on a Cross
63
The Effect of Annealing on the Thermal Properties
77
Experimental Studies of Phase Separation
95
Thermal Stability
119
High Modulus IsocyanurateUrethane RIM Elastomers 1 65
164
Potential of Crown EtherAssisted Anionic Polymer
181
Recent Chemical and Reinforcement Development
209
Fiber Glass Reinforced Reaction Injection Molding
219
Refining of the RRIM Process Materials
231
Metering and Mixing of RIM Reactants
243
Simulation of Cavity Filling and Curing in RIM
263
Computer Analysis of RIM Moldability from
279
Polyamide RIM Systems
133
The Catalysis of the Polycyclotrimerization
147
Index
Author Index
Alberino, L. Μ., 3,125
Alfonso, Giovanni Carlo, 163
Barksby, N. 83
Blackwell, John, 53
Camargo, R. Ε., 27
Chiappori, Carmen, 163
C o r n e l l , M. C , 15
Cross, M. M . , 97
Damusis, A . , 65
Dunn, D . , 83
Gabbert, J . D . , 135
G i r g i s , M i k h a i l ,
Granger, R., 279
Hedrick, R. M . , 135
Kaye, Α., 83,97
Kresta, J . E . , 111
Lee, Chun Dong, 53
L i n , T. B . , 65
Lloyd, E. T. , 15
Lockwood, R. J . , 125
Macdonald, Christine E . , 53
Macosko, C. W., 27
McClellan, T. R., 3
Menges, G . , 237
Meyer, Louis W., 195
Mrotzek, W., 237
M i l l i e r , Η., 237
Plevyak, Joseph E . , 213
Quay, Jeffrey R., 53
Razore, Sandro, 163
Regelman, D. F . , 125
Russo, Saverio, 163
Sadr, Α., 279
Schneider F r i t z W. 259
Stepto, R. F. T., 83,97
T i r r e l l , Μ., 27
Turner, Robert B . , 53
van der Loos, J . L . M . , 181
van Geenen, Α. Α., 181
Vergnaud, J . M . , 279
Wellinghoff, S. T., 27
Wohl, M. H . , 135
Wongkamolsesh, K . , 111
Subject Index
A
Acetylcaprolactam, 138
Acyllactam(s), 142
nylon copolymer formation, 144
reaction with primary amines, 139f
structure, 138
Adiabatic reaction(s), 67
Adiabatic reactor data, urethane
elastomers, 71-73f
Adipoylbiscaprolactam, 138
After-mixers, 247-48
Agglomeration(s), i n s t r a i g h t - l i n e
dependence deviations, 65
Alkene(s), r e a c t i v i t y toward
isocyanates, 126
Alkoxyacetylene(s), formation of
ketene aminals, 133
Amine(s), primary, reaction with
acyllactams, 139f
3-Aminopropyl triethoxysilane, 140
Amorphous systems, polyurethane
elastomers, 33
Anionic polymerization,
caprolactams, 136-38
i n i t i a t i o n , 138
thermal i n i t i a t i o n , 137f
termination reaction, 136
Annular cone and plate, 100-102
Annular vs. truncated cones, 101f
Aromatic diisocyanate(s), RIM
elastomers, 81
Arrhenius equation, second-order
reaction, 67
Automotive industry, operating
e f f i c i e n c i e s , 18
Automotive RIM, 4t
295296 REACTION INJECTION MOLDING
Β
Barbituric acid derivative(s),
formation, 128
Base-catalyzed polymerization of
lactam(s), 136
Baseball bats, f o a m - f i l l i ng
equipment, 264f,265f
Benzoyl chloride, effect on t i n
catalysts, 116
Bimodal d i s t r i b u t o r ( s ) , high,
rationale, 42
Bisacyllactam, structure, 142
Bis(4-morpholino)ethylene, 133
reaction with MDI, 129
Block copolymer(s)
nylon, 142-58
See also Nylon block copolymers
dynamic modulus curves, 147f
effect of polyol content
heat sag values, 149
moisture effect, 149
polyether effects on impact
strength/stiffness, 147f
prepolymer formation, 142
properties, 144-4 5
reaction exotherm, 156f
v i s c o s i t y comparison, 155f
phase mixing effects, 45
Body panel(s), polyurethane-RRIM,
thickness, 18
1,4-Butanediol, 68
n-Butanol effect, DBTDL, IR
spectra, 116
C
Calcined clay, 140
Caprolactam(s), 154
acyllactam-initlated
polymerization, 137f
anionic polymerization, 136-38
i n i t i a t i o n , 138
thermal, 137f
termination reaction, 136
polymerization, 135
preferred catalyst, 144
reaction with isocyanates, 138
Caprolactam magnesium bromide,
preferred catalyst, 144
Carbamoyl chloride, effect on t i n
catalysts, 116
CaSi03—See Wollastonite
C a t a l y s i s , 111
polyurethane elastomers, 45
Chopped Integral strands
heat sag effect, 234,235t
notched Izod impact strength,
effect, 232,233t
Chopped integral strands—Continued
packing fraction, 99f
reinforcement
f l e x u r a l modulus, 231t,232
surface quality, 229
Class A surface
d e f i n i t i o n , 229
obtaining, 21
Clogging effects, s o l i d f i l l e d
systems, avoidance, 266
Compression molding, estimated
c a p i t a l , 21t
Cone and plate viscometer(s)
annular, 100-102
displaced, 100
shear rate, highest attainable, 105
v i s c o s i t y determination, 102
Cone and plate viscometry, 100-105
Consumer application(s) 4,5t
physical
decay, temperature effects, 76-80
density and p l a s t i c i z e r
effects, 78
Crystalline aggregate(s),
formation, 81
CSG—See Chopped strand glass
Cure cycle, time reduction, 279
C y l i n d r i c a l mold, flow front
p r o f i l e s , 253f
D
DAO—See 1,4-Dlazo 2,2,2 octane
Dashboard—See Fascia
DBTDL—See D i b u t y l t i n dilaurate
Densitometer scans, MDI, 57,58f
Diazo 2,2,2 octane, catalysis of
isocyanate groups, 113t
D i b u t y l t i n dilaurate
catalysis of isocyanate groups, 113t
dissociation, l a u r i c acid
effects, 1l8f
interaction with carbamoyl chloride,
IR spectra, 119f
IR spectra, 115f
n-butanol effect, 1l6,117f
ligand exchange, 114-16
specific conductance, 117f
structure characteristics, 114
urethane reaction, catalysis
mechanism, 1l8f
D i f f e r e n t i a l scanning calorimetry
polyurethane
elastomers, 32,38,40f,4lf
urethane elastomers, 75,80
Diisocyanate(s), aromatic, RIM
elastomers, 81INDEX 297
Direct gate, 240f
Direct gating, 239
Displaced cone and plate, 100
DSC—See D i f f e r e n t i a l scanning
calorimetry
Dynamic mechanical spectroscopy,
polyurethane elastomers, 32
Ε
Economic 'advantage (s ), 15
Efficient mixing, achieving, 88
EG—See Ethylene glycol
Elastomer properties, hard
segments, 130t,131t
Enamine(s), r e a c t i v i t y , 126
Energy balance equation, 67
Engineering p l a s t i c ( s ) ,
development, 8t
Engineering rubber(s), features
Epoxy formulations, processing
equipment, 269,271
Epoxy RIM material(s), 9
Equipment, 259-78
flow diagram, 85f
operation, 84-89
special needs, 9
usage, 5t
Ethoxyacetylene, ketene aminals,
formation, 133
Ethylene g l y c o l , 56
External mold release, application
time, 216
F
Fan gate, 242
IKV version, 240-47
method, 241
narrow, 244f
Fascia, RIM use, 15-17
Fiber glass reinforcements, i n
urethanes, 225-36
F i l l e d polyurethane(s), 95
F i l l i n g pattern method, 250-57
Film gating, 241
F i r - t r e e mixer, 249f
Fixture (s), 20t
Flaked glass, disadvantage, 228
Flow, pressure drop, 243
Foaming, use, 150
Fox's equation, 47
Free pour impingement mixing
head, 271,274
cross section, 275f
Fringed micelle c r y s t a l l i t e ( s ) ,
formation, 65-66
G
Gel permeation chromatography,
polyurethane elastomers, 32
Glass f i b e r ( s ) , 97-110
packing f r a c t i o n , 98-100
Glass fibe r s l u r r i e s , shear
thinning, 102
Glass flakes, 226
reinforcement, surface quality, 229
GPC—See Gel permeation chromatography
Growth, 5,15
H
Hagen-Poisseuille p r i n c i p l e , 251
Hammer-milled glass—See M i l l e d glass
fibers
and material type, 7t
chain extender, 54
content, d e f i n i t i o n , 29
percentage vs. elastomer
properties, 130t,131t
polyurethane elastomers, 27,28f
variations and use, 6
Hard segment polymer(s),
properties, 7t
HDI—See 1,6-Hexamethylene diisocyante
High-polydispersity r a t i o ( s ) ,
rationale, 42
High-shear RRIM viscometer, 105-8
HMG—See M i l l e d glass fibers
Hot process equipment, 272f
I
Impact strength, chopped integral
strands, 232
Impingement injection mixing, 238
Impingement mixing, 12f
equipment, 259-61
maximum operational pressure, 261
Reynolds number, 88
IMR—See Internal mold release, 22
Incompatible polyols, i n
polyurethanes, 86t
Industrial consumer
application(s), 4,5t
Injection molding, estimated
c a p i t a l , 21t
Interior trim foam, market usage, 4
Internal mold release, 22
agent, requirements, 217
economic advantages, 216
multiple stream, 222298 REACTION INJECTION MOLDING
Internal mold release—Continued
need, 216
nylon system, 157
RRIM, 23t
technology, 23
Intersegmented interactions,
absence, 47
Isocyanate(s)
electron density, 112
polarized complexes, formation, 113
reaction with caprolactams, 138
reaction with organotin
catalysts, 112
r e a c t i v i t y with alkenes, 126
Isocyanurate, urethane modified, 9
fiber length effects, 12t
J
J-car f a s c i a , molding with
IMR, 218,220
Κ
Ketene acetals
formation of ketene aminals, 133
structure, 128
Ketene aminal(s)
moisture effects, 127
preparation, 133
r e a c t i v i t y , 126
RIM polymerizations, 129-32
structure, 126
Ketene aminal-isocyanate(s), 125-34
specific reaction, 126-28
Krauss-Maffel head, 88
L
Lactam(s), base catalyzed
polymerization, 136
Lauryl lactam, 154
Loss tangent, polyurethanes, 93»94f
Low-pressure casting, 150
nylon systems, 160-61
M
Market(s), automotive, 3-4
MDI—See Modified diphenylmethane
4,4*-diisocyanate
M i l l e d glass f i b e r s , 226
bulk volume determination, 98
length requirement, 228
as reinforcement, flexural
modulus, 229,231t
tensile strength, effect, 232
Mineral reinforcement, 140
Mixing
efficiency
predicting, 260
achieving, 88
impingement, 238
Mixing head, 263f
free pour impingement, 271,274
cross section, 275f
i n d u s t r i a l application, 262
open molds, 274
small s i z e , 261-62
Modified diphenylmethane
4,41-diisocyanate
characteristics, 56
densitometer scans, 57,58f
d i f f e r e n t i a l scanning
calorimetry, 56
dynamic mechanical data, 56,63f
reaction, 129
X-ray d i f f r a c t i o n , 56 , 57,58f, 59f
Modified diphenylmethane
4,4,-diisocyanate/ethylene g l y c o l ,
X-ray d i f f r a c t i o n , 54,55f
Mold(s)
c y l i n d r i c a l , flow front
profiles, 253f
design, problems, 250
nylon systems, 159-60
M o l d f i l l i n g
a i r entrapment, 240f
avoiding, 245,247,257
f i l l i n g pattern method, 251
flow management, 239-47
island geometry, 245
polyurethane, 237-58
process, 11
Molecular weight determination,
polyurethane
0 elastomers, 38,41f,42,43f
Ν
Narrow fan gate, 244f
NCO group—See Isocyanates
Nonautomotive market(s), 4
Nucleation, internal release
agents, 217
Nylon(s), v s . urethanes, 154-58
Nylon 6, 9,135-62
melting point, 135
particulate reinforcement, 140
RIM, 138-42
Nylon block copolymer(s), 142-58
adsorption effects, 151f
dynamic modulus curves, I47f
effect of polyol content, 145tINDEX 299
Nylon block copolymer(s)—Continued
heat resistance, 146,149
heat sag values, 149
heat sag/flexural modulus, 149t
immersion growth data, 153f
moisture effect, 149
molding processes, 150
morphology, 146
polyether effects on impact
strength/stiffness, 147f
prepolymer formation, 142
properties, 144-4 5
reactions, 142-44
exotherm, 156f
r e l a t i v e humidity effects, 152f
structure, 146
synthesis, 142
temperature modulus response, 149t
use of polyol rubber blocks 150
v i s c o s i t y comparison, 155
Nylon processing, equipment
Nylon system(s)
equipment requirements, 158-60
gel times, 1 54
injection rates, 157
internal mold release, 157
low-pressure casting, 160-61
molds, 159-60
monomers, 154
0
Open molds, mixing head, 274
Organic-silicone hybrid technology—
See Silicone-organic hybrid(s)
Organotin catalyst(s)
i n urethane systems, 111-21
reaction with isocyanates, 112-14
Orthoester(s), formation of ketene
aminals, 133
Ovens, hot process equipment, 273f
Ρ
Packing fraction
c a l c u l a t i o n , 98
chopped strand glass
reinforcement, 99f
as function of weight averages, 101f
P a i n t a b i l i t y , internal release
agents, 217
P a r t i c l e cone(s), d i f f i c u l t i e s , 100
Particulate reinforcement, 140
PC a l l o y
c a p i t a l , 22t
hourly labor cost, 20,21t
PEDA—See Polyether diamine
Phase separation
premature, 46
segmented polyurethane(s), 95
Phase-separation studies, 27-52
Phenyl-Isocyanate diadduct,
structure, 127
Physical cross-links
decay, temperature effects, 76-80
density and p l a s t i c i z e r effects, 78
Plant(s), t y p i c a l , 17
Plaque thickness, 89
P l a s t i c i z e r ( s ) , effect of
c r o s s - l i n k s , 76,79
Polyamide(s)
particulate reinforcement, 140
preparation, 129
solution derived, preparation, 133
Polyether, structure, 142
PolymerIzation
Polyol(s )
and polyurethanes, t e n s i l e
properties, 93t
characteristics, 30
high-shear rate data, 108
incompatible, i n polyurethanes, 86t
molecular weight Increases, 46
rheology, 97-110
Polyol rubber block (s), use i n nylon
block copolymers, 150
Polyurethane(s)
amine additive effects, 53-64
amorphous systems, 33
glass t r a n s i t i o n temperatures, 48t
block composition, 53
c r y s t a l l i n e systems, 45-47
d i f f e r e n t i a l scanning
calorimetry, 32,38,40f,4lf
dynamic mechanical spectra, 32,33
dynamic mechanical temperature
behavior, 93-95
f i l l e d , 95
f l e x u r a l modulus-temperature
behavior, 90,92f,93
foam molding, m o l d - f i l l i n g
operation, 255
gel permeation chromatography, 32
hard-segment composition, 27, 28f
incompatible polyols, 86t
mechanical properties, 33
m o l d f i l l i n g , 237-58
molecular weight
determination, 38,41f,42,43f
noncrystalline systems, 47-49
reinforced RIM
c a p i t a l , 22t
hourly labor costs, 211
thickness for body panels, 18300 REACTION INJECTION MOLDING
Polyurethane (s ) —Continued
RIM, 15-26
production, 29,32
segmented, phase separation, 95
tensile properties, 42,93t
tensile stress-strain, 90,91f
t r a n s i t i o n a l behavior, 93/f94f
u n f i l l e d , 89-90
wide angle X-ray
scattering, 32,38,39f
Premature phase separation, 46
Pressure recording, reinforced
RIM, 107f
Process efficiency, 18
Process energy cost comparison, 19t
Processing, s o l i d - f i l l e d
system, 262, 266-67
Productivity, I8t
PU—See Polyurethane(s)
PU-RIM—See Polyurethane (s)
Q
Quartz, 140
R
Reinforced RIM, 11
automotive, 4t
flow rate, 105
internal mold release, 23t
pipe diagram, 23Of
pressure recording, 107f
volume recording, 107f
Reinforced RIM viscometer
correction factors, 106,108
high shear, 105-8
Resin transfer molding, 150
Reynolds number, calculating, 260
RIM
basic p r i n c i p l e , 226
cycle, 2l4,215f
equipment, 259^-78
flow diagram, 268f
low capacity, 267,269
medium capacity, 267,269
estimated c a p i t a l , 21t
hourly labor cost, 20
process, 227f
processing, parameters used, 89t
RIM-polyurethane(s), reaction
systems, 84
Rotational casting, 150,154
RRIM—See Reinforced RIM
Rubber
injection temperature and rubber
sheet thickness, 284
state of cure, 279-91
i n storage bulb, 282-84
Rubber—Continued
temperature p r o f i l e s , 279-91
thermal properties, 282t
Rubber vulcanization
injection temperature and state of
cure, 286
mathematical treatment, 280
midplane temperature, 284t
as function of enthalpy, 288t
numerical calculation, 281
rubber sheet thickness effect, 285f
state of cure and cure time, 286t
by sulfur , 280
S
Second-order reaction
adiabatic, 67
Arrhenius equation 67
Sheet-molding compound(s)
c a p i t a l , 22t
hourly labor cost, 20,21t
tooling/fixtures, 20
Silicone(s)
internal mold release
technology, 213-24
tailormade, IMR agents, 219f
Silicone-organic hybrid(s)
internal mold release, 218-21
agents, 221-22
p a i n t a b i l i t y problems, 218
S102—See Quartz
SMC—See Sheet-molding compound(s)
S o l i d - f i l l e d systems
efficient mixing, 266
processing, 262,266-67
Solvation effect, on d i b u t y l t i n
dilaurate, 116
Sprue gate, 242,249f
problems, 247
Storage bulb, temperature i n rubber
vulcanization, 282-84
Straight-line dependence, effect of
RIM composition, 74,76
Stress-strain, t e n s i l e ,
polyurethanes, 90,91f
Structure-property relationship(s),
polyurethane, 53-64,83-96
Τ
Tensile elongation at break, with
reinforcement, 234
Tensile elongation values, with
reinforcement, 235
Tensile properties, polyurethane
elastomers, 42INDEX 301
Tensile strength data, with
reinforcement, 233t
Thin section moldings, flow
management, 240f
Tin catalyst(s)
a c t i v i t y , hydrolyzable chlorine
effects, 116,120
r o l e i n isocyanate polarization, 114
Tool(s), 20t
Torsion pendulum data,
polyurethanes, 93,94f
T r i e t h y l orthoacetate, 128
Trim waste, 18-19
Truncated vs. annular cones, 101f
U
u n f i l l e d polyurethane(s), 89-90
Urethane(s)
adiabatic reactor data, 71-73
adiabatic temperature vs. r i g i d
segments, 73f
components, 69t
c r o s s - l i n k s , temperature effects, 70
DSC, 75,80
fiber glass reinforcements, 225-36
milled glass, 228
gel times, 154
morphology, 65-82
physical properties, 70
p l a s t i c i z e r modification, 69,74t
raw materials, 16
use for auto parts, 226
v i s c o s i t y comparison, 155f
vs. nylon, 154-58
Urethane-modifled isocyanurate, fiber
length effects, 12t
Urethane reaction(s)
adiabatic reaction k i n e t i c s , 68
c a t a l y s i s , mechanism, 111
d i b u t y l t i n dilaurate, catalysis
mechanism, 1l8f
noncatalyzed, 113
organotin c a t a l y s i s , 111-21
Urethane segmented block
copolymer(s), 5
Urethane structural foam, market
usage, 5t
V
vinylamine(s), r e a c t i v i t y , 126
Viscometry, cone and plate, 100-105
V i s c o s i t y , equation, 102
Volum recording reinforced RIM 107f
W
Wide angle X-ray scattering, 32
polyurethane elastomers, 38,39f
Wollastonite, 140
X
X-ray scattering
modified diphenylmethane
4,4»-diisocyanate, 5 7 , 5 8 f , 5 9 f
wide angle, polyurethane
elastomers, 32,38,39f
Production by Meg Marshall
Indexing by Deborah Corson
Jacket design by Pamela Lewis
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