Handbook of Plasticizers

Front Cover
ChemTec Publishing, 2004 - Technology & Engineering - 687 pages
A comprehensive source providing theoretical, historical and up-to-date information on placticizers' physical and mechanical properties, action, behavior, uses, functions, mechanisms, effects on other materials, the environment, and more.
 

Contents

George Wypych
1
16001100 BC
2
decrease the glass transition temperature of the polymer the most typical reason for plastici
3
fire behavior most plasticizers generally increase susceptibility of material to burn drip d
4
polymeric plasticizer has sufficiently high molecular weight usually Mn is higher than 5000
5
George Wypych
7
Floor coverings wallpapers
8
The discussion in the next section is designed to find common features of plasticizers within the
9
reduce stiffness of polymer442
328
diisononyl phthalate455 in creep resistant plastisol477 and in antimicrobial gloves manufacture549
329
lower alkyl biphenyls553
330
55 phr in a laminated glazing unit547
331
affect fusion temperature484502504522
332
Incorporation of plasticizer in PVC system is expected to lead to an increased free volume Exper
333
The glass transition temperature Tg is the other fundamental quantity related to plasticization
335
Chapter 9 contains a broad discussion of steps of plasticization with special attention to PVC F
336

Property
10
Partition coefficient log Kow
11
It should be pointed out that properties of plasticizers make their selection very easy It was s
12
Property
13
Outstanding property
14
Property
15
Tensile strength 50 phr MPa
16
Each of these groups is still divided into two classes having chlorine concentration below or abo
17
Figure 26 shows that specific gravity of chloroparaffin is only slightly affected by paraffin ty
18
Heat of vaporization at 25oC Jg
20
If the polymer is not plasticized by energetic plasticizers solvents must be used in the process
21
Plasticizers are usually incorporated into energetic compositions as processing aids to improve t
22
Plasticizers require excellent physical compatibility and greater safety at elevated temperatures
23
These unsaturated acids can be epoxidized with the use of hydrogen peroxide or peracetic acid ac
24
TLVTWA 8 h OSHA mgm3
25
NFPA health
26
Figure 212 shows that polypropylene glycol performs in a typical way by reducing tensile strengt
27
NFPA flammability
28
Table 24 Typical characteristics of some crudes
29
Outstanding property
30
Viscosity at 25oC mPa s
32
Boiling point oC
33
NFPA reactivity
34
Highly recommended for these polymers
35
ClashBerg temperature 50 phr oC
36
Out of these three groups phthalates which are esters of orthophthalic acid are popular in f
37
Heat of vaporization at boiling point Jg
38
Figure 215 Loss of esters of phthalic acid and alcohols having different number of carbon atoms
39
Figure 217 shows influence of number of carbon atoms in alcohol on freezing temperature of plast
40
Dielectric constant Figure 219 refractive index Figure 220 specific gravity Figure 221
41
Figures 229231 show the mechanical performance of plasticized PVC containing 50 phr plasticize
42
This discussion shows that our knowledge of plasticizers is far from complete Even for wellstud
43
22181 Esters
44
Outstanding property
45
22182 Polybutenes
46
TLVTWA 8 h OSHA mgm3
48
Dielectric constant
49
Freezing point oC
50
Very small additions of sulfonamide plasticizer 025 to 2 phr were used with polycarbonate123
51
Property
52
Property
53
ClashBerg temperature 50 phr oC
54
22243 Carbon dioxide
55
Figure 236 shows that addition of this plasticizer to tetrafluoroethyleneperfluoroalkyl vinyl
56
22248 Multiring aromatic compounds
58
A biocompatible product may be plasticized by lipids158 Lipids were found to be compatible with
59
222413 Thioeters
60
Various other processes not discussed here lead to manufacture of acids required for production o
61
The structure at the upper left corner characterizes the main product The above technology shows
62
Figure 238 shows a stage of the production process of phthalates in which phthalic anhydride res
63
The reboilers are suppressedvaporization pumpthrough types with pumps 286 and 288 respecti
64
The quality of the plasticizer can be increased by removal of dissolved oxygen from a feed alcoho
65
Some examples of reactive plasticizers111162178183 internal plasticization184187 and polyme
66
In polyimide used for high temperature applications a plasticizer having very unusual structure i
67
9 Vames S Chem Week May 20 1998 p 3336
68
63 US Patent 4457791 1984
69
121 US Patent 4996284 1991
70
180 US Patent 4108926 1978
71
George Wypych
73
Twentyfive grams of a plasticizer is placed in 125 ml Erlenmeyer flask and 50 ml alcohol is adde
74
Shear thinning and thixotropic properties of nonNewtonian materials at the shear rate ranging fr
75
The effect of immersion of plastics in various liquids can be followed by weight change changes
76
Saybolt chromometer is used for determination of color of refined oils petroleum waxes and pharm
77
For lot uniformity and equivalence infrared analysis is performed to confirm the presence and th
78
Fogging test is done by placing the specimen in the beaker and covering it with a top cover The
79
Shore A softer materials and D harder materials durometers are used in ISO method129 The ind
80
A variety of manual and automatic instruments exists Also a number of calibration liquids can b
81
ISO standard122 specifies test for determination of migration of plasticizers from one material t
82
Plasticizer testing is frequently done with polyvinylchloride PVC compositions In such cases r
83
There are no equivalent international standards for these methods
84
Preparation of pastes using planetary mixer is discussed in ISO standard162 The use of a dissolv
85
23
86
Standard specification for tricresyl phosphate contains requirements for apparent specific gravit
87
35
88
36
89
T1 T2 DT initial final and difference temperatures respectively
90
Karl Fischer titration75 is specified for use in plasticizers23 The method determines free and h
91
Nonvolatile matter is determined by placing material on a sample dish in an oven at an agreed te
92
40 ASTM D196901 Standard Specification for 2Ethylhexanol
93
Extraction
94
method
95
Determination of plasticizer absorption at room temperature
96
in work places by gas chromatography
97
George Wypych
99
clear instruction of sampling procedure should be available refer to Section 329 for the desc
100
after the car is empty pump is stopped the valves are closed in the car and then in the trans
101
Each part of the bulk handling system should be electrically grounded Swing joints should be equ
102
Plasticizers may be stored in drums but most frequently they are stored in bulk Figure 44 shows
103
Figure 44 shows the sloped bottom of a tank which helps to clean the tank from sediments and to
104
It is also advisable to transfer plasticizers through filters or have filters mounted on the circ
105
A Marcilla and M Beltrán
107
According to the lubricity theory the function of a plasticizer is to reduce intermolecular fric
108
Houwink7 emphasized the concept of the gliding planes which had been introduced years before by
109
Years later Aiken9 studied the results from the tensile creep test on plasticized PVC with diffe
110
As mentioned above the gel theory considers that the polymer structure is sustained by an intern
111
Moorshead17 proposed an empirical approach to explain the action of the plasticizers which is fo
112
The free volume theory originated some years later than the lubricity and the gel theories when
113
51
114
Some well established models that correlate free volume fraction to the glass transition temperat
115
As pointed out by Sears and Darby4 the free volume theory explains successfully at least qualit
116
When a small quantity of plasticizer is added many polymers tend to increase the number and size
117
55
118
Recently Mauritz and Storey proposed a free volume based theory that predicts plasticizer diffusi
119
7 Houwink R Proc XI Int Cong Pure Appl Chem London 1947 p 575583
120
Valery Yu Senichev and Vasiliy V Tereshatov
121
Phase equilibrium is the most general thermodynamic approach to evaluate the phase state of a com
122
If the temperature rises above TAc another incompatibility area may appear Such an area has bee
123
There are four areas in Figure 62 There is a singlephase liquid system above curve 2 area I
124
62
125
Nonpolar polymers can dissolve in polar solvents if their molecules have groups capable of polar
126
Rigid chains cannot move gradually because a great amount of energy is required to separate two r
127
It is convenient in practice to use semiempirical correlations of the mutual solubility of subst
128
The change of entropy DSid is calculated from the Gibbs equation obtained for mixing of ideal g
129
Trioctyl phosphate
130
The value of solubility parameter depends on the value of the evaporation enthalpy of a liquid at
131
612
132
616
133
As the structure of molecules becomes more complex the set of solvents is sharply narrowed down
134
Table 63 Molar attraction constants
135
621
136
Enonpolar nonpolar contributions to cohesion energy
137
The Riders approach was developed into the threedimensional dualistic model in which the equati
139
Thermodynamic stability prevents plasticizer exudation as the temperature changes under mechanic
140
629
141
631
142
As a rule entropy decreases during mixing but in some specific cases the magnitude of these chan
143
These effects are part of the solubility parameters concept This concept allows to predict compa
144
Overdosing stabilizer is a common error in material design This may done to increase processabil
146
As mentioned above the macromolecules develop into more extended conformations in a good solvent
147
The impact resistance is determined by absorption of the energy of formation of the free surface
148
34 V P Belousov A G Morachevskiy Heat properties of nonelectrolyte solutions Handbook Chemis
149
85 P M Rider J Appl Polymer Sci 25 2975 1980
150
George Wypych
151
D diffusion coefficient
152
Figure 71 Glass transition temperature Tg of PVC compositions containing various weight fract
153
73
154
DOP experiences fast a picosecond time scale brelaxations which might be libratory oscillat
155
These simple examples included only polymer and plasticizer In normal formulations many other co
156
74
157
1H NMR was used to study migration of two plasticizers di2ethylhexyl phthalate DEHP and tr
158
From the data presented so far it can be seen that there are three steps involved in the migrati
159
Diffusion into a liquid is described by equations 74 and 75 It is not likely that there wi
160
A thermodynamic equilibrium method is used to determine the equilibrium ratio of concentrations o
161
The network density of samples was estimated from the equilibrium compression modulus of samples
162
The volume distribution coefficient of the diffusant concentration is expressed as a ratio of a d
163
If the value of K1w slightly depends on the content of plasticizer in material it is possible to
164
54
166
Below 6 vol concentration of mineral oil in low molecular weight polystyrene the plasticizer was
167
This is a short summary of implications of theoretical findings in the area of diffusion and mobi
168
12 Nicolai T Brown W Macromolecules 29 No5 26th Feb1996 p1698704
169
George Wypych
171
Barium and strontium sulfates have the lowest oil absorption below 10 g per 100 filler Many co
172
Section 73 discusses migration of plasticizers with some references to simultaneous migration of
173
Silanes are added to some formulations to increase adhesion to substrates in contact Silane can
174
PVC foams are an interesting example of migrationcontrolled processes13 Several components cont
175
Figure 87 shows that the conversion of monomers in photopolymerization of PMMAacrylate increase
176
Figure 89 shows that the presence of dioctyl sebacate DOS increases the effectiveness of cross
177
A Marcilla JC García and M Beltrán
179
Steps one and two can take place at ambient temperatures after the plasticizer and PVC are mixed
180
Elastic and viscous modulus and complex viscosity are the magnitudes determined commonly by tempe
181
In respect to the effect of the plasticizer concentration the results vary from one author to an
182
Following the previous step or simultaneously plasticizer interacts with the rest of
183
Nakajima13 compared the results obtained by SEM and by rheology With more compatible plasticizer
184
The differential scanning calorimetry DSC is usually employed to measure the glass transition t
185
DSC has also been employed to establish the degree of fusion attained in plasticized PVC Potente
186
In the region of 1800 to 1650 cm1 the carbonyl group of plasticizer is observed A shift in thi
187
Thermogravimetric analysis has been widely employed to characterize polymers by their decompositi
188
Figure 99 shows the experimental and theoretical curves obtained by adding the thermographs of
189
Another remarkable aspect observed in Figures 911 and 912 is a splitting of the peak correspond
190
The first reaction corresponds to the plasticizer fraction which has not interacted with resin P
191
32 Marcilla A Beltrán M García J C Mang D J Vinyl Add Technol 1 1 10 1995
192
George wypych
193
101
194
Figure 103 shows the effect of the number of methylene groups in acid of diester Here also the
195
Figure 105 shows that the tensile strength of internally plasticized cellulose diacetate increas
196
Mechanical performance of material can also be influenced by the effect of the plasticizer on pol
197
Based on the definition of plasticization the elongation should increase with increase in the pla
198
Both time and temperature of fusion affect elongation of PVC plastificates as Figures 1011 and 1
199
Toughness stiffness ductility and modulus are all related to the tensile strength and the elon
200
Figure 1018 shows that impact strength of plasticized PVC increases with increase in the amount
201
The photorefractive materials combine photoconductivity and electrooptical properties They cons
202
Refractive indices of plasticizer and polymer are behind brilliance The closer are both indices
203
Trimellitate
204
Juan Carlos Garcia and Antonio Francisco Marcilla
205
However the temperature of maximum torque does not correspond with the temperature of complete f
206
Table 104 Viscosity of plasticized PVC compounds and plasticizers Adapted by permission fro
209
10441 Flow Properties
210
10442 Gelation and Fusion
211
o
212
10443 Recycling of PVC Plastisols
213
Table 105 Behavior of viscosity in Pas at a shear rate of 1 s1 for fresh and aged plastisol
214
The data in Table 106 show that
215
A new evidence supporting influence of increased mobility on ionic conductivity comes from work o
216
In some cases plasticizers may reduce ionic conductivity as for example in EPDM blends65 Dibuty
217
Ethylene glycol
218
The kinetic processes have some peculiarities around glass transition For example an upward shi
219
94
220
1017
221
1022
222
1027
223
Note that all of the above equations assume that the polymerplasticizer system is a singlephase
224
Butadienenitrile rubbers SKN18
225
Table 109 The glass transition temperatures of selected plasticizers
226
Dioctyl azelate
227
There are several fillers and inorganicorganic additives used in flame retarded materials and th
228
Figures 1035 and 1036 show smoke density and oxygen index for PVC plasticized with three differ
229
The effect of polymer blending on flammability was studied in combination of ABS one of the most
230
195
231
The exact kinetics of degradation of different plasticizers are not available It would be conven
232
It is wellestablished in organic chemistry that acids increase rates of halogen elimination The
233
Numerous studies were conducted by thermogravimetry166170173176179180 Several aspects impor
234
Considering that the differences between plasticizer loss and plastisol loss are very small compa
235
Figures 1045 and 1046 show that the effect of plasticizer concentration increase cannot be desc
236
In order to better understand these data the results of thermostability testing are compared wit
237
Spectral analysis of volatile products shows that pure plasticizer evaporates before thermal degr
238
Studies on PVC electrical cable recycling showed that only 2 wt plasticizer was lost during 18 y
239
Plasticizer types and their different concentrations do not perform in the same manner More vola
240
Studies of the effect of plasticizers on PVC film stability were conducted using samples cast fro
241
Polycarbonate
242
Diethyl phthalate used as a plasticizer in cellulose acetate films was found to be completely deg
243
effect of conditions timetemperature on crystallization
244
Crystallinity of polyethylene oxide plasticized with DOP in the concentration range from 0 to 25
245
Studies on structure of plasticized materials suggest presence of various forms PVC is believed
246
Material staining is a complicated process caused by either migration of a staining agent or extr
247
Vasiliy V Tereshatov Valery Yu Senichev
248
Change in modulus of swollen elastomers depends on the chemical structure and volume fraction of
249
1033
250
The calculations using Eq 1033 show that irrespective of polymer and plasticizer nature when
251
Change in elastic properties of SPU1 SPU2 SPU5 SPU6 on swelling was studied on samples swo
252
Figure 1063 Calculated and experimental stressstrain at the stretching rate of 028 s1 a an
253
The change of viscoelastic behavior of crosslinked elastomers on swelling depends on polymer phys
254
Dogadkin et al284 found a strong influence of polymer structure on stressstrain behavior of swo
255
Dependences of tensile strength sk at maximum stress on swelling ratio q calculated for the
256
Hardening of some polymers in the presence of small amounts of plasticizer is also observed287 T
257
To eliminate the irreversible change of elastomer superstructure caused by direct contact of samp
258
Let us assume that the ideal chemical network has no physical interactions Such a network instan
259
Comparison of results of calculations Figure 1075 with experimental data for samples of PBU an
260
At lower deformation rate 28x103 s1 the density of physical network decreases in addition t
261
The densities of chemical network of PEU and PBU are the same neV0x 012 kmolm3 A lesser
262
Influence of plasticizers which are proton acceptors on deformation properties of SPU with variou
263
DOS
264
The above examples show that a simple explanation using free volume theory only applies to cases
265
1 Bohnert T Stanhope B Gruszecki K Pitman S Elsworth V Antec 2000 Conference proceedings
266
50 HarkinJones E M A Rotational molding of reactive plastics Ph D Tesis Dept of Mechanical and
267
103 Fujito H Kishimoto A J Phys Chem 28 547 1958
268
155 US Patent 5430108
269
204 Brebu M Vasile C Antonie S R Chiriac M Precup M Yang J Roy C Polym Deg Stab 67 No
270
252 Fras I Boudeulle M Cassagnau P Michel A Polymer 39 No20 1998 p477383
271
p29858
272
George Wypych
273
No studies are thus far available that propose the mechanism of action of plasticizers in any of
274
Acrylic binders in waterbased paints must have filmforming properties at the temperatures of pa
275
application of wet film I
276
9
277
In pressure sensitive roofing tape the plasticizer imparts a resiliency and gives a permanent ta
278
sulfolane 2345tetrahydrothiophene11dioxane37
279
In many instances polymers are in contact with liquids that penetrate their structure This proce
280
Figure 113 shows that the addition of citrate plasticizer decreases the glass transition tempera
281
235158
282
6074
283
improvement of solvent resistance73
284
In one application73 plasticizer was used to improve processability and to take advantage of anti
285
When exposed to heat CPVC produces substantial quantities of HCl which is a volatile product of
286
high levels of plasticizer white oil were used to produce crystal gels from linear SEBS copol
287
providing reactive sites for grafting UV absorber80
288
Most commercial glues such as the popular Crazy Glue do not use plasticizers These glues are bas
289
polyisobutylene the most frequently used nonmigrating plasticizer of EPDM compositions10611
290
For these reasons plasticizers are not used to modify mechanical properties of the final product
291
EVA is an internally plasticized copolymer used to plasticize or to reduce the amount of plastici
292
dioctyl phthalate in the plasticization of polymethylmethacrylate ionomer144147150 polypheny
293
There is a strong electrostatic interaction between the ionic groups of sulfonated syndiotactic p
294
Plasticization of polystyrenebisobutylenebstyrene ionomer by 2ethylhexylp dimethylaminob
295
Two rates of the tensile strength decrease are seen from Figure 1116 The slow initial decrease
296
dispersion aid for solid additives161
297
Nbutylbenzenesulfonamide from zero up to stoichiometric equivalent of amide units182 1 to 5
299
The type of plasticizer used here is less critical although it should have good compatibility bo
300
providing viscosity control219220221
302
Polycarbonates are one of a class of polymers in which small additions of plasticizer cause subst
303
up to 15 wt of glycol249
304
melt viscosity adjustment239 and gel viscosity reduction248
305
Pentaerythritotetrabenzoate ester Benzoflex S552 was used to plasticize polyarylene etherpo
306
6080 parts of paraffin wax to prepare surface modified film by plasticizer extraction261268
307
dioctyl phthalate273
308
increasing free volume273277
309
Carbon black 12
310
1060 wt diethylene glycol dibenzoate and dimethyl phthalate296
311
The crystallization rate and the range of temperatures at which crystallization may occur depend
312
1525 wt308
313
increasing ductility of this normally quite brittle polymer299301
314
improvement of the tear resistance311
315
Plasticizers are used in polymethylmethacrylate in very specific cases only PMMA ionomers are th
316
paraffinic naphthenic and aromatic processing oils in automotive weatherseals335
317
PolyNvinyl carbazole PVK is a glassy polymer which easily fails by a cracking fracture Plas
318
111
319
344
320
dimethyl diethyl dipropyl dibutyl diheptyl dioctyl and diisodecyl phthalates in optical s
321
isooctyl benzyl phthalate Santicizer 261 in caulks sealants378379 and a bridge joint const
322
Polyvinylacetate in a partially saponified form may perform function of its own plasticizer389 I
323
dipropylene glycol dibenzoate 10 to 15 phr392
324
polyethylene glycol in a blend with methylcellulose397 in pharmaceutical tablets coating compo
325
1 wt402 05 to 3 wt405 1 to 3 wt407 20 wt409 01 to 5 wt410 05 to 5 wt41
326
Soy lecithin 03 to 05
327
Figure 1151 shows that there is a considerable difference in the peak temperatures of storage an
337
Microcrystalline properties of the plasticized PVC depend on the PVC type plasticizer type and c
338
Introduction of a plasticizer causes separation of PVC chains relative to the concentration of th
339
Figure 1161 shows principles of diffusivity of plasticizers Diffusion coefficient k comes fro
340
Plasma treatment is currently exploited as a potential solution to migration problem The action
341
Equation 118 shows that shrinkage depends on the initial plasticizer content and its loss The
342
nbutyryl trinhexyl citrate 6
343
532
344
PVC Formolon 40 244
345
Packaging films with controlled transmission of CO2 and O2 are produced from plasticized polyviny
346
The change of PU properties as a result of the plasticization process does not always correspond
347
Values of the glass transition temperature of plasticizers obtained by the DSC method at a low he
348
Figure 1166 shows the dependence of the glass transition temperature Tgs of the SPU soft phase
349
The traditional views on plasticization of polymers are based on results of studying the single p
350
TCP holds an intermediate place in respect of its influence on the formation of microdispersion h
351
A partial or complete dissolution of the urethaneurea hard blocks of a high glass transition tem
352
It is clear from curves Figure 1170 that the greatest decrease in strength sk is observed fo
353
To lower hardness of polyurethane requires plasticizer capable to dissolve hard blocks of polymer
354
Addition of water to process mixture reduces processing viscosity but does not affect the glass t
355
8 wt6502025 phr648 375 phr640
356
650
357
tripropylene glycol monoethyl ether in cosmetic compositions661
358
dilution and expansion of rubber network675
359
Potassium hydroxide 5
360
683
361
Dihydroquinoline derivative 03
362
glycerol ester in a biodegradable material720
363
525 wt740
364
Figure 1176 shows that the glass transition temperature of starch films plasticized with glyceri
365
Polyethylene vinyl alcohol 304
366
27 US Patent 5707737
367
84 US Patent 5952423
368
138 Thermoplastic Processing Products Specialty Products Vinnolit VK 801 Vinnolit GmbH Co KG
369
190 Angelopoulos M Saraf R MacDiarmid A G Zheng W Feng J Epstein A J Antec 97 Volume II
370
248 US Patent 6403685
371
307 Labrecque L V Kumar R A Dave V Gross R A McCarthy S P J Appl Polym Sci 66 No8
372
p11808
373
417 US Patent 5879920
374
No9 Sept1999 p52731
375
523 Chee K K Eur Polym J 31 No2 Feb1995 p1559
376
579 US Patent 5726229
377
634 US Patent 6011011
378
693 US Patent 6242553
379
George Wypych
381
The observed behaviors seem to suggest that additions of DOP to the system lead to its distributi
382
This behavior can be expected from systems in which entropic factors can be neglected ABSPMMA b
383
The previous section suggests that the presence of another polymer in most cases is not likely to
384
Figures 121 and 122 show the effect of plasticizer addition on glass transition temperatures of
385
Studies on electrical conductivity suggest possible interaction between each component polymer an
386
Addition of polyethylene glycol PEG molecular weight of 400 daltons to polyvinylalcoholmet
387
General assessment of studies on plasticizers use in polymer blends shows that a large amount of
388
George Wypych
389
acetyl triethyl citrate in hydrophilic adhesives for medications76 and in biodegradable composi
390
Hotmelts
391
up to 5 wt13
392
8 to 16 wt of pressure sensitive adhesives18 and 15 to 20 wt in hyd
393
improved adhesion to unreactive and slowtocure metal substrates polyester plasticizer24
394
Disadvantages
395
In some products for medical dental drug and food contact applications the so called toxico
396
Calcium carbonate fine 2300
397
49
398
An average large aircraft needs more than a million fasteners made from a ferrous alloy These we
399
ethylene vinyl acetate copolymers for low fogging interior products129
400
Advantages
401
sodium salt of sulfonated phenylene formaldehyde158
402
too large a concentration of superplasticizer may prevent hydration and thus destroy binding ab
403
Plasticizers thicken the cementitious material and add lubrication to make it flow They are used
404
Practically any plasticizer suitable for plasticization of polyvinylchloride is used in fabricati
405
lower fusion and gelation temperatures178
406
cracking after some plasticizer was lost183
407
Bariumzinc stabilizer 15
408
5 wt in composition for strenghtening nails184 10 wt in a skin perm
409
185
410
201
411
375 phr in dental cements for temporary prosthesis231
412
triisononyl trimellitate in low smoke compositions289
413
capability to transport holes selected plasticizers important in photorefractive polymer syst
414
dioctyl adipate in low temperature heat shrinkable film for labels349 and in transparent antibl
415
11 phr in optical films335 5 to 15 wt in UV absorbing films336 12 wt i
416
migration of DOP from materials used for medical applications342
417
12 wt in coatings of nutritional
418
low molecular plasticizers such as di2ethylhexyl adipate and di2ethylhexyl phthalate r
419
A study of the daily intake of di2 ethylhexyl adipate conducted in 1987 in UK estimated maxim
420
Soya lecithin 633
421
Epoxidized soybean oil 24
422
paraffinic oil in rubber compositions449 in molded synthetic compositions457 in extruded prod
423
PVC blending resin 30
424
20 to 25 wt in a synthetic rawhide lace492 and 80 phr in foot massaging
425
Disadvantages
426
224methyl12pentanediol diisobutyrate Texanol TXIB in nonfluorescent inks522 in fluore
427
elimination of cracking and blistering542
428
Lactic acid 07
429
40 wt in blood contacting applications567 and 30 to 40 wt in blo
430
Only a few surface layers can interact with a living system such as blood From a study including
431
Figure 1312 confirms suggestions based on studies reported in Figure 1310 Increased amount of
432
polyethylene glycol in osmotic membranes606
433
C7 to C11 phthalate Palatinol 711 in chipresistant vibrationdamping automotive coatings668
434
25 to 35 wt in selflevelling compositions for automotive industry640
435
plasticizer does not change the water content of hydrogel materials but changes their swell fac
436
glycerin in pushfit capsules700701703704706707 in sustained release compositions726 in
437
31 to 35 wt of dry composition in edible coatings718 and 75 to 10 in dex
438
formation of acid resistant protective coating which disintegrates at pH4740
439
Figure 1313 shows that the glass transition temperature of ethyl cellulose decreases along with
440
triphenyl phosphate in plasticization of triacetyl cellulose754755
441
Disadvantages
442
Internal lubricant calcium stearate 0413
443
helps to obtain surface tack in adhesive tapes783788
444
CaCO3 50
445
improves between layer adhesion807
446
A Marcilla JC García and M Beltrán
447
IARC decided to extend the studies on mice to other mammals including humans Although DOP provo
448
In the late 1990s the migration of plasticizers mainly phthalates from toys has given rise to
449
Finally in December 1999 the European Union decided to ban the commercialization of flexible PV
450
Alkyl sulfonic acid ester
451
Disadvantages
452
good heat aging characteristics849
453
866
454
Ammonium octamolybdate flame retardant 10
455
23 US Patent 6403685
456
83 US Patent 5948853
457
142 US Patent 6119807
458
198 US Patent 6254876
459
258 US Patent 6421035
460
318 US Patent 6194071
461
377 US Patent 5688455
462
431 Colletti T A Renshaw J T Schaefer R E J Vinyl Additive Technol 4 No4 Dec1998 p2339
463
489 US Patent 6461392
464
549 US Patent 6103781
465
606 US Patent 6491949
466
666 US Patent 6172132
467
723 US Patent 6410054
468
783 US Patent 6120869
469
835 Official Journal of the European Communities L 31546 9121999
470
George Wypych
471
Plasticizers have influence on all listed properties Heat stability can be improved by selection
472
Stretching plasticized polymer is the most important feature of blow molding process It is impor
473
Three problems with outcome of blow molding are related to rheology including sharkskin die swe
474
Thickness control is very important because thickness of the produced film can be as small as 00
475
The type and the concentration of plasticizers affects melt rheology which is responsible for ad
476
Figure 144 shows an installation for coil coating23 In section 1 the metallic substrate mate
477
Numerous defects may occur in the presence of plasticizers or are caused by the selection of the
478
The heating means 11 in the pressing plate may be achieved by first providing a heat insulating
479
transparent frosted material is produced in a smooth mold45 The material is composed of a mixt
480
Plasticizers are directly used for production of the plasticizer dispersions which may have high
481
The colorant composition is prepared by blending the organophilic clay and plasticizer and millin
482
In processes illustrated on these figures plasticizers are required for final product performanc
483
controlled immersion speed gives time to release air and wet form surface
484
In another invention83 a claim is made that fogging occurs because of the lack of a proper mixin
485
The majority of extrusion processes use already compounded materials in the form of dry blends or
486
Figure 1412 shows continuous production of chewing gum95 Each component of the formulation has
487
Figures 1411 to 1414 show different approaches to introduction of plasticizers which in some pr
488
Some typical faults are observed during extrusion which are related to plasticizers These includ
489
In most cases of injection molding the raw material for molding is in the form of a solid which
490
Use of plasticizer affected the quality of steering wheels119 The plasticizer migrated to the su
491
M Beltrán J C Garcia and A Marcilla
492
The rotational molding process was developed in the 1940s but its initial evolution was hindered
493
The rotational molding process as shown in Figure 1418 is quite a simple process Probably bec
494
Heating cooling and the system to produce the molds motion are very similar in all machines The
495
Sintering and densification do not take place during rotational molding of liquid polymers Minim
496
Table 142 Types abbreviations and manufacturer of plasticizers employed
497
The shape of the curves shown Figure 1427 is very important in the process described above Th
498
The temperature of gelation T20 is another factor which affects standard deviation of wall part
499
The selection of variables ensures a good thickness uniformity in moldings but there are also ot
500
roll mills and internal mixers
501
tangential and intermeshing Banbury mixers are the most p
502
The mixing process in the rubber industry usually begins with mastication which is to obtain suit
503
Figure 1432 shows a schematic diagram of line for continuous production of rigid containers for
504
Figure 1434 shows hot roll coating equipment capable of coating web substrates with melted polym
505
In addition to web coating by wet materials organosols or plastisols coated material may underg
506
Electric devices may contain only a few conductive wires separated by insulating layers of plasti
507
14 US Patent 4985104 1991
508
73 US Patent 4219514 1980
509
127 US Patent 5142004 1992
510
186 US Patent 5017259 1991
511
George Wypych
513
Seventytwo toys from seventeen countries were analyzed by GCMS for the composition of phthalate
514
Plasticizers are not chemically bound in most cases thus they can be separated by either extract
515
Sublimation and evaporation are zeroorder processes Under isothermal conditions the rate of mas
516
Migration measurement is complicated by the presence of additional media into which the plasticiz
517
A large number of analytical methods are used to study plasticized materials Most methods such
518
Fourier transform infrared FTIR is used in plasticizer containing systems A special cell was c
519
Positron annihilation spectroscopy was used to determine free volume in plasticized PVC Figure 1
520
36 Paroli R M Delgado A H Polym Mater Sci Eng 75 2 1996 p6970
521
George Wypych
523
Diffusion of gases occurs as a result of redistribution of a free volume within the matrix Gas t
525
1612
526
1614
527
Figure 1152 shows that the final gelation temperature of phthalates increases with the number of
528
T0 temperature at which the rate of the first step a D b is at maximum
529
V3 viscosity at stage d fusion
530
Søren Thor Larsen
531
The last decades have witnessed an enormous increase in the number of subjects suffering from air
532
Immunotoxicology may be defined as the scientific discipline concerning the adverse effects of xe
533
Recently a matched casecontrol study in a cohort of 3754 newborns in Oslo Norway showed an in
534
Table 1711 Adjuvant and immunosuppressive effects of some phthalates and monophthalates Afte
535
Phthalates are assessed to be more powerful adjuvants than monophthalates as phthalates were abl
536
Allergy to phthalates themselves has only been reported in a limited number of case stories One
537
As the adjuvant effect varied with the chemical structure of the phthalates this suggests that p
538
Ruth A Roberts
539
17223 Chemical carcinogenesis
540
The more we understand about how nongenotoxic carcinogens cause cancer in rodents the more sophi
541
PPARa activation is responsible for the pleiotropic effects of PPs seen in rodents such as enzyme
542
Since the rodent effects of PPs are mediated via PPARa and humans appear to be nonresponsive to
543
1 Doull J Cattley R Elcombe C Lake B Swenberg J Wilkinson C Williams G van Gamert M Regul
544
Janet Y UriuAdams1 and Carl L Keen12
545
Phthalates are a group of phthalic acid diester compounds with straight or branch chain alcohols
546
When DEHP is given to mice during pregnancy fetal toxicity is observed including embryo or fetal
547
Other studies confirm that large doses of BBP typically greater than 1000 mg BBP kgday advers
548
Alterations in zinc metabolism can also occur when an acute phase response is triggered by a wide
549
In this scenario as a consequence of the maternal acute phase response there is a marked increa
550
The direct toxicity of several of the compounds used in the acutephase response experiments has
551
The acute phase response can also induce changes in other nutrients in addition to zinc For exam
552
That a suboptimal diet can influence pregnancy outcome is now well established Maternal micronut
553
21 Lake BG Toxicol Lett 8283 673 1995
554
458 NIH Publication No 973374
555
118 Rink L Kirchner H Int Arch Allergy Immunol 111 199 1996
556
Stephanie R MilesRichardson
557
The primary route of human exposure to phthalates is oral Food and foodstuffs are considered the
558
17431 Children
559
Although the largest source of phthalate exposure for the general public may be from DEHP the mo
560
17432 Women
561
DEHP is considered a suitable plasticizer to use in medical devices and procedures because of phy
562
In some cases occupational exposures to phthalates have been associated with adverse health effec
563
Expert Panel conclusions are summarized in Table 1742 Since primates showed no testis effects
564
When considering public health implications it is necessary to consider populations who are most
565
1 Steiner I Scharf L Fiala F Washuttl J Food Addit Contam 15 812817 1998
566
489527 2002
567
Werner Butte
568
VVOC very volatile organic compounds and VOC volatile organic compounds are transitory and pr
569
DBP and BBP are fastfusing plasticizers for PVC They are mostly used in combination with DEHP
570
PVC utilizes 85 of the total production of phthalate plasticizers with DEHP being the most impor
571
TCEP production in Germany has been discontinued in 19979 TCEP is no longer used in soft foams f
572
DBP
573
Data from Germany Japan and Sweden are available for indoor air concentrations of organophosphat
574
Highest concentrations of contaminants including plasticizers in air were reported for test chamb
575
Detection limits for phthalates eg BBP and DBP in floor dust may reach 0001 mgkg38 and ab
576
DEP
577
TCPP
578
Discontinued use or the replacement of one plasticizer by another may result in downward or upwar
579
DEHP is the longchain phthalate ester examined most extensively and hundreds of publications on
580
Chemicals that give rise to toxic endpoints other than cancer and gene mutations are often referr
581
Gaseous plasticizers are evenly dispersed in the air In the case of inhalation the anatomy and
582
Table 1758 Daily indoor intake of some plasticizers phthalatesorganophosphates calculated o
583
Regarding concentrations of plasticizers in material of human origin blood serum urine body f
584
It must be emphasized that the reference values have no uniform character and relate to the refer
585
1 Environment and Health Research for Europe Background Document to the Third Ministerial Confer
586
World Health Organization Geneva 1990
587
63 Macher JM Indoor Air 11 99 2001
588
99 Kohn MC Parham F Masten SA Portier CJ Shelby MD Brock JW Needham LL Environ Health
589
William R Roy
591
The US Environmental Protection Agency EPA maintains the Toxic Chemical Release Inventory1 T
592
Diethyl phthalate
593
Table 184 Summary of plasticizer concentrations detected in surfacewater samples
594
Dinbutyl phthalate
595
Di2ethylhexyl phthalate
596
Dinbutyl phthalate
597
The solubility of 21 of the plasticizers in water at 25oC ranges from about 01 mgL to 4000 mg
598
Henrys Law constants were compiled for the 23 plasticizers Table 189 However all of these va
599
The actual rate of volatilization of plasticizers from water apparently has not been experimental
600
The disappearance of a plasticizer from water can be the result of a number of abiotic and biotic
601
Table 1811 Summary of biodegradation halflives in days or potential to biodegrade of the 23
602
The adsorption of four different plasticizers by river sediment is illustrated in Figure 182 Th
603
104
604
Table 1813 Summary of vapor pressures mm Hg at 25oC of the 23 plasticizers and references
605
100 days
606
Table 1815 Amount of primary loss of parent compound biodegradation of nine phthalates after
607
Analogous to the partitioning of dissolved plasticizers from water to soil and sediments another
608
Table 1817 Summary of octanolwater partition coefficients of the 23 plasticizersa
609
Diisobutyl phthalate
610
The extent and rate of the degradation of vaporphase plasticizers by hydroxyl radicals has not b
611
1 Toxic Release Inventory National Library of Medicine Online Available at
612
2 Kohli J Ryan J F Afghan B K Phthalate esters in the aquatic environment In Analysis of Trace
613
George Wypych
615
This very useful regulation after more than a quarter century of practice does not give sufficie
616
78400
617
33703081
618
Di2ethylhexyl phthalate
619
Some reports of expert panels were already released81216 Table 195 gives a summary of conclus
620
Recommended Exposure Limits REL are set by the National Institute for Occupational Safety and H
621
workers must be able to escape such an environment without suffering permanent health damage
622
MRLs are based on noncancer health effects only Oral MRLs are expressed as daily human doses in
623
Drinking water protection is based on the Safe Drinking Water Act which authorizes EPA to develo
624
On the other hand the EPA Toxic Release Inventory shows that large quantities of plasticizers we
625
Table 1910 Plasticizers permitted as indirect additives to food33
626
1771210
627
European Union Directive contains only references to a few materials which may play a role of pla
628
December 2000
629
George Wypych
631
The National Institute for Occupational Safety and Health believes that protective clothing shoul
632
Breakthrough time is another measure of glove fitness for this purpose This parameter measures t
633
Table 201 gives general guidance regarding the applicability of different glove materials for di
634
The selection of a respirator general suggestions for its use the adsorption capacity of filter
635
The pressure drop in the filter depends on its design Chemical cartridges used for plasticizer a
636
Under conditions of use it is important to predict how long a particular cartridge will last unde
637
APF 2000 any suppliedair respirator that has a full facepiece and is ope
638
George Wypych
639
The above described process is an inprocess recovery of raw materials which are used for produc
640
The method of this invention utilizes a unit 10 comprising a supply and high pressure spray sys
641
Figure 215 Process of recovery of plasticizer from PVC fullscale installation 1 reactor 2 bu
642
It is evident from the above that a mixture of plasticizers and stabilizers is obtained from this
643
The gaseous products can be fed to an adsorption apparatus and the hydrochloric acid obtained ca
644

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