Handbook of PlasticizersA 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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Common terms and phrases
adhesives adipate alcohol Appl applications ASTM benzyl phthalate biodegradable blend Butyl benzyl phthalate cellulose Chem chemical chlorinated cizer coatings coefficient compatibility components composition compounds concentration of plasticizer copolymer crosslinked decrease degradation DEHP determined di-(2-ethylhexyl dibutyl phthalate dibutyl sebacate diethyl phthalate diethylene glycol diffusion diisodecyl diisodecyl phthalate diisononyl phthalate dioctyl EFFECT OF PLASTICIZERS elastomer epoxidized ester exposure Figure film flame retarding formulation fraction free volume gelation glass transition temperature glycol dibenzoate heat house dust improvement increase indoor interaction liquid Marcilla material method migration mixture modulus molding molecular weight molecules number of carbon paraffinic particles Patent phase plasticized PVC plasticizer plasticizer concentration plastisols polar polyester polymer polymeric polyurethane properties resin rubber samples sebacate shows solubility parameter solvent stabilizer surface tensile strength thermal ticizer tion toxicity Toxicol tributyl citrate tricresyl phosphate trimellitate vapor viscosity volatile