Handbook for the Chemical Analysis of Plastic and Polymer ...
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This article was downloaded by: 10.3.98.104On: 12 May 2022Access details: subscription numberPublisher: CRC PressInforma Ltd Registered in England and Wales Registered Number: 1072954 Registered office: 5 Howick Place, London SW1P 1WG, UK
Handbook for the Chemical Analysis of Plastic and PolymerAdditives
Bolgar Michael, Hubball Jack, Groeger Joseph, Meronek Susan
Crosslinking Compounds/Accelerators
Publication detailshttps://www.routledgehandbooks.com/doi/10.1201/b19124-4
Bolgar Michael, Hubball Jack, Groeger Joseph, Meronek SusanPublished online on: 25 Sep 2015
How to cite :- Bolgar Michael, Hubball Jack, Groeger Joseph, Meronek Susan. 25 Sep 2015,Crosslinking Compounds/Accelerators from: Handbook for the Chemical Analysis of Plastic and PolymerAdditives CRC PressAccessed on: 12 May 2022https://www.routledgehandbooks.com/doi/10.1201/b19124-4
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27
CHAPTER 3
Crosslinking Compounds/Accelerators
The chemical crosslinking process has its origins in the Goodyear process by which rubber wastransformed from a viscous form into a shape-retaining rubbery material through reaction withsulfur and heat. This 'vulcanizing' process promoted bonding between unsaturated end groups inthe natural rubber chains, thus forming 'crosslinks' between chains. With these crosslinks, therubber molecules were no longer subject to mutual slip, thus a molded object would permanentlyretain its shape while retaining elastomeric behavior.
Crosslinking is a major commercial process for elastomeric, thermoplastic, and liquid polymericmaterials. The approaches for crosslinking reaction imitation vary with the type of polymer, theend application, costs, and technical approach. Many crosslinking processed are thermallyinitiated. Heat exposure increases oxidation risk, while considerably boosting energyrequirements. The rate of crosslinking can be increased by careful technical development of aprocess and selection of organic compounds that function as cure accelerators. In some cases, therate of cure may be moderated with chemical retarding agents to control exothermic reactions andphysical stability.
Crosslinking of many commercial thermoplastics is conducted with reactive peroxides, includingdicumyl peroxide, benzoyl peroxide, and many others, all of which have different activationtemperatures. At the crosslinking initiation temperature, the peroxide decomposes and forms freeradicals that react with unsaturated end groups on the polymer chains, thus forming chemicalcrosslinks between chains. For thermoplastic addition, stability of the peroxides is increased forstorage and handling by incorporation into master batches that may include waxes, clay, fatty acids,or resins.
A wide range of liquid polymers are crosslinked with reactive peroxides, such as benzoyl peroxide,diacyl peroxide, and various peroxyesters and peroxyketals. These are used to crosslink acrylicresins for a wide range of applications. Since these peroxides are inherently unstable, they arereduced in concentration for safe storage and use by dilution with cyclohexane, diallyl phthalate, ordimethyl phthalate. These diluents must be understood from an analytical perspective for properrole and source identification.
Crosslinking of many thermoplastic polymers can be accomplished by addition of a vinyl silane. Inthis process, the vinyl silane is mixed into the polymer during extrusion. The heat energy grafts thesilane to the polymer chains. The component is then molded or extruded into the desired form.Following this, the crosslinking process is initiated by exposure to moisture and heat. With thisprocess, the processing temperature is reduced. Therefore, the polymer is not oxidized and thevinyl silane is not decomposed into a host of reaction products. Analytically, silane crosslinkinginitiators can be identified by the vinyl silane signature.
Ionizing radiation is used to crosslink a number of rubber and thermoplastic materials, particularlyfor applications where precise control of crosslinking density (the proportion of crosslinked to non-crosslinked chains in a given polymer) must be carefully controlled and where chemical purity is akey consideration. Polymers for biomedical applications are typically radiation crosslinked. Withthis process, an electron beam or gamma radiation source is used to provide ionizing energy.Crosslinking proceeds spontaneously if the polymer contains reactive end groups or if anunsaturated copolymer or unsaturated polymer additive is blended. For rubber compounds, diene
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Handbook for the Chemical Analysis of Plastic and Polymer Additives28
monomers are typically added to provide unsaturated bonds. From an analytical perspective,radiation-crosslinked polymers may contain few chemical signatures that indicate the curingprocess.
Ultraviolet (UV) crosslinking of polymers is broadly used for many applications where heating isimpractical or damaging to the base polymer and where other forms of ionizing radiation may beharmful or excessively costly for the application. UV radiation can be used to decompose areactant that is blended into a polymer and the free radicals that result will form crosslinks in thepolymer. UV curing is used for a wide range of urethanes for cured-in-place coatings, for example.This method is also commonly used for acrylic composite dental restoratives. The crosslinkinginitiators used for this process must strongly absorb UV radiation and they must be stable and havelow volatility in the polymer prior to crosslinking initiation. Benzophenones are a major class oforganic compounds used for this process.
Rigid polymers such as epoxy and polyurethane are used in high volume for a wide range ofstructural, coating, electrical, and other applications. Epoxy formulations vary widely and thechemical signatures of cured resins will vary accordingly. Amine curing agents are the mostcommonly used for epoxy systems. The selection of the type of amine affects the rate of cure andalso impacts the end use of the crosslinked material. Amine-crosslinked epoxies have increasedmoisture sensitivity compared to those cured with aromatic isocyanates, for example. The aminecrosslinking agents include triethylenetetramine, ethylenediamine, diethyltriamine, cycloaliphaticamines, and others. Analytically, these amines might be identified through GC/MS analysis ofsolvent-extracted or thermally desorbed samples, particularly if unreacted amines remain.
Polyurethanes are also available with a wide range of crosslinking systems, some of which areextremely sensitive to UV exposure. One such curing agent is toluene diisocyanate.Hexamethylene diisocyanate is not subject to UV-induced degradation. As with epoxies, urethanesare highly crosslinked and analytical determination of the ingredients and extractible organicsrequires careful selection of methodology and knowledge of the polymer systems.
From an analytical perspective, the crosslinking materials and process should be well understood.A reactive peroxide, for example, will generally not be evident in the analysis of a polymercrosslinked with this material. This will be evident when not fully decomposed during a cureprocess, for example, and the presence of non-reacted peroxide may be a valuable indication of anunder-cure condition. Typically, the decomposition products of dicumyl peroxide are what will befound analytically. These include acetic acid, cumyl alcohol, acetophenone, and others. Heating ofmost thermoplastics to a level that initiates decomposition of the curing agent would also oxidizethe base polymer. It is therefore necessary to protect the polymer with an antioxidant. GC/MSanalysis of a typical peroxide-crosslinked polyethylene will reveal the peroxide decompositionproducts, an antioxidant, and no trace of the original peroxide.
Accelerators
The rate of crosslinking of commercial rubber products and a number of other thermosetting plasticcompounds can be accelerated by addition of a number of compounds identified as cureaccelerators. These are useful for increasing throughput in commercial processes, for locking intransient foam structures, and for controlling recovery in shape-retaining components. These arealso useful when a crosslinking agent must be used at the lowest possible temperature to preventdecomposition of the polymer. Accelerators may also enhance tensile properties and improve ageresistance of the final product. Cure accelerators are also known as crosslinking synergists.
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Crosslinking Compounds/Accelerators 29
Most accelerators are organic substances that contain either nitrogen or sulfur, or both. Typicalaccelerators include tetraisobutylthiuram disulfide, n-oxydiethylene thiocarbamyl-N-oxydiethylenesulfonamide, tetrabenzylthiuram disulfide, and others. They can be classed as either primary orsecondary accelerators and are often used in combination, depending on the desired final outcome.Crosslinking of many commercial thermoplastics is conducted with reactive peroxides, includingdicumyl peroxide, benzoyl peroxide, and many others, all of which have different activationtemperatures. At the crosslinking initiation temperature, the peroxide decomposes and forms freeradicals that react with the unsaturated end groups on the polymer chains, thus forming chemicalcrosslinks between chains For thermoplastic addition, stability of the peroxides is increased forstorage and handling by incorporation into master batches that may include waxes, clay, fatty acids,or resins.
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Handbook for the Chemical Analysis of Plastic and Polymer Additives30
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20
˚
C)
Water MeOH EtOH Acetone CH
2
Cl
2
Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
FormulaN
S
SH
Accelerator MBT, MBT/MG
Off-white to yellow powder
Stable under normal conditions of use.
U
260 ˚C
Akrochem Corporation
C
7
H
5
S
2
N167.25
2-mercaptobenzothiazole
2-benzothiazolethiol; 2-benzothiazolylmercaptan; 2(3H)-benzothiazolethione
149-30-4DL64750002-MBT
180-182 ˚C
<0.1 2.0 10.0 U U
Used as a vulcanization accelerator for rubber mixes based on natural and synthetic rubbers and in the production of plastics and lacquers.
FDA approved 1998 for the following materials to be used in contact with food: adhesive preservatives, 21CFR175.105; a rubber accelerator (up to 1.5% of weight of rubber), 21CFR177.2600; in the synthesis of slimicides for use in paper/paper-board, 21CFR176.300; an adjuvant in the manufacture of foamed plastics, 21CFR178.3010. Listed in 40CFR136.1 and USEPA Method 640: The Determination of Mercaptobenzothiazole in Municipal and Industrial Wastewaters.
Does not biodegrade in river water in 8 weeks. Slightly susceptible to indirect photolysis. Medium to low mobility in soil, and marginal to no mobility in sediment. This substance may be hazardous to the environment; special attention should be given to fish. Log Pow value of 2.41 indicates a low potential to bioaccumulate.
Can be released as point source pollution during manufacture, transportation, and end use. Additionally, it may be released from manufactured products containing this material during the active life cycle of the products and/or upon disposal of the products.
A 2-year NTP study on rats indicates evidence of carcinogenic activity in rats gavaged with 750 mg/kg BW (male) and 375 mg/kg BW (female). No carcinogenic effect on bacteria and yeast cells.
Captax/Rotax (purified form)Perkacit
®
MBTThiotax
R.T. Vanderbilt CompanyAkzo Nobel Chemicals B.V.Solutia, Inc.
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Crosslinking Compounds/Accelerators 31
Mass Spectrum for
For Chromatogram See Appendix A -
Accelerator MBT, MBT/MG - PLAS-AC-001
PLAS-AC-001 - page 445
MW
=167
.25
m/z
Abu
ndan
ce
167
100
6923
108
15
6315
123
11
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Handbook for the Chemical Analysis of Plastic and Polymer Additives32
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20
˚
C)
Water MeOH EtOH Acetone CH
2
Cl
2
Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
White powder
Stable under normal conditions of use.
10-40
347.18 ˚C
Akrochem Corporation
C
3
H
6
N
2
S102.11
ethylene thiourea
2-imidazolidinethione; 2-imidazoline-2-thiol; 2-mercaptoimidazoline
96-45-7NI9625000ETU
203 ˚C
~2 10-40 <0.1 U U
ETU is used as an accelerator in the vulcanization of polychloroprene (Neoprene) and other elastomers; for coated fabrics, for epichlorohydrin, and for chlorosulfonated polyethylene rubbers. It is also an intermediate for antioxidants, insecticides, fungicides, dyes, pharmaceuticals, and synthetic resins.
FDA: Use of ETU as a food additive is prohibited. EPA (1995): Health Advisory for long-term exposure is 0.4 mg/L. Can be monitored in water by EPA Method 509 - Determination of Ethylene Thiourea (ETU) in Water Using Gas Chromatogra-phy with a Nitrogen-Phosphorus Detector. FAO/WHO (1993): ADI: 0.004 mg/kg BW.
ETU is a trace contaminant and metabolic degradation product of a widely used class of ethylene bisdithiocarbamate fungi-cides such as Maneb and Zineb. Half-life in H
2
O is 7–13 days. Octanol/water partition coefficient as log Pow: –0.66 (cal-
culated).
Can be released as point source pollution during manufacture. Additionally, it may be released from manufactured products containing this material during the active life cycle of the products and/or upon disposal of the products.
Ethylene thiourea is toxic and known to produce thyroid neoplasms (thyroid hyperplasia) in rats and liver neoplasms in mice following long-term administration; NIOSH: potential occupational carcinogen; NTP: Suspect carcinogen; OSHA: Possible suspect carcinogen. Acute oral toxicity (LD50): 1832 mg/kg [Rat].
Pennac
®
CRANocceler
®
22Soxinol
®
22Vulkacit
®
NPV/C
Pennwalt Corp.Ohuchi Shinko Co., Ltd.Sumitomo Chemical Co., Ltd.Lanxess Deutschland GmbH Ltd.
HN
NH
S
Accelerator ETU-22 PM
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Crosslinking Compounds/Accelerators 33
Mass Spectrum for
For Chromatogram See Appendix A -
32
34
36
38
40
42
44
46
48
50
52
54
56
58
60
62
64
66
68
70
72
74
76
78
80
82
84
86
88
90
92
94
96
98
10
01
02
10
41
06
10
81
10
11
205
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
m/z
-->
Ab
un
da
nce
Ave
rag
e o
f 1
5.8
88
to
16
.21
9 m
in.:
PL
AS
-AC
-00
2.D
10
2
45
73
42
59
10
44
77
05
17
55
31
00
61
Accelerator ETU-22 PM - PLAS-AC-002
PLAS-AC-002 - page 442
MW
=102
.16
m/z
Abu
ndan
ce
102
100
4521
7320
4220
597
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Handbook for the Chemical Analysis of Plastic and Polymer Additives34
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20
˚
C)
Water MeOH EtOH Acetone CH
2
Cl
2
Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
Accelerator BBTS
Cream to buff powder or pellets
Stable under normal conditions of use.
U
Not available
Akrochem Corporation
C
11
H
14
N
2
S
2
238.38
N-(1,1-dimethylethyl)-2-benzothiazolesulfenamide
N-(1,1-dimethylethyl)benzothiazolesulfenamide; benzothiazolyl-2-tert-butylsulfenamide; benzothiazyl-2-tert-butylsulfenamide
95-31-8DL6200000TBBS/BBS
105 ˚C
0.345 40-80 40-80 U U
TBBS is used as a vulcanization accelerator in NR, SBR, BR, and rubber blends. Normally used alone or with small quanti-ties of ultra accelerators in tire compounds or other industrial rubber products.
FDA approved 1998 for use as an accelerator in the manufacture of rubber material intended for use in all stages of produc-tion, processing, packaging, and transport of food: 21CFR177.2600.
TBBS does not ionize at environmental pHs, is not readily biodegradable, but hydrolyzes in less than 1 day at pH 9 or less. The identified hydrolysis products: mercaptobenzothiazole, di(benzothiazoyl2)disulfide, t-butylamine, and benzothiazoleare are non-volatile, with a low potential for bioaccumulation, and are not readily biodegradable. Indirect photo-oxidation by hydroxy radicals is predicted with a half-life estimated at 2.8 hours. Log Pow of 3.9 at room temperature.
Due to the vulcanization process, finished rubber products contain only small amounts of TBBS or synthesis by-products (benzothiazole, 2-mercaptbenzothiazole, and 2-mercaptobenzothiazole disulfide). Release to the environment of these chemicals may occur during the use of rubber products. Fugacity model (Mackay level III) data suggest that it would mostly distribute to soil (if released to the air or soil compartments) and to water (if released to the water compartment).
TBBS may be absorbed by the gastro-intestinal route, undergoing hydrolysis in vivo. Studies suggest that the hydrolysis products are toxic primarily to the liver and kidney. It was not found to be mutagenic in bacteria or in vitro mammalian gene mutation assays. It was not genotoxic in an in vivo mouse micronucleus assay. (LD50): >7940 mg/kg dermal [Rabbit]. It did induce chromosomal aberrations in mouse lymphoma cells in vitro with metabolic activation. Carcinogenicity not known.
Delac
®
NSPennac
®
TBBSPerkacit
®
TBBSSantocure
®
NS
Uniroyal Chemical Co.Pennwalt Corp.Akzo Nobel Chemicals BSolutia Inc.
N
S
S
HN
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Crosslinking Compounds/Accelerators 35
Mass Spectrum for
For Chromatogram See Appendix A -
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
230
235
240
245
250
05
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
m/z
-->
Abundance
Avera
ge o
f 13.8
92 to 1
3.9
08 m
in.: P
LA
S-A
C-0
03.D
182
223
57
238
149
108
166
69
122
63
82
154
135
90
102
51
96
190
75
140
117
206
127
159
171
176
113
PLAS-AC-003 - page 440
MW
=238
.38
m/z
Abu
ndan
ce
182
100
223
53
5752
238
39
149
35
Accelerator BBTS - PLAS-AC-003
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Handbook for the Chemical Analysis of Plastic and Polymer Additives36
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20
˚
C)
Water MeOH EtOH Acetone CH
2
Cl
2
Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
S
N
S
HN
Accelerator CBTS
White to tan powder
Stable under normal conditions of use.
S
Decomposes
C
13
H
16
N
2
S
2
264.41
N-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine
N-cyclohexyl-2-benzothioazole sulfenamide
95-33-0DL6250000CBTS
102 ˚C
0.002 U U U U
Delayed action sulfenamide accelerator for natural and synthetic rubbers. It provides better scorch resistance than thiazoles and can be accelerated by thiurams and dithiocarbamates to give shorter cure times. It can also be used as a retarder for ETU-cured polychloroprene and high thiuram cures.
Not FDA approved for food contact applications.
Not expected to be an environmental hazard.
Can be released as point source pollution during manufacture, transportation, and end use. Additionally, it may be released from manufactured products containing this material during the active life cycle of the products and/or upon disposal of the products.
LD50 (oral): 5300 mg/kg [Rat]LD50 (oral): >8000 mg/kg [Mouse]LD50 (dermal): >7490 mg/kg [Rabbit]Embryotoxic LD50 (intravenous): 32 mg/kg [Mice, Rodents]
Accelerator CBTSSantocure
Akrochem Corporation
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Crosslinking Compounds/Accelerators 37
Mass Spectrum for
For Chromatogram See Appendix A -
45
50
55
60
65
70
75
80
85
90
95
10
01
05
11
01
15
12
01
25
13
01
35
14
01
45
15
01
55
16
01
65
17
01
75
18
01
85
19
01
95
20
02
05
21
02
15
22
02
25
23
02
35
24
02
45
25
02
55
26
02
65
27
00
10
20
30
40
50
60
70
80
90
m/z
-->
Ab
un
da
nce
Ave
rag
e o
f 1
9.8
61
to
21
.75
0 m
in.:
PL
AS
-AC
00
7N
.D\d
ata
.ms
98
.1
16
7.0
10
8.0
18
2.0
55
.11
49
.06
9.0
22
1.0
12
2.0
26
4.1
13
6.0
81
.12
31
.11
75
.19
0.0
15
6.0
19
2.0
20
4.1
12
9.1
62
.0
Accelerator CBTS - PLAS-AC-007
PLAS-AC-007 - page 441
MW
=264
.41
m/z
Abu
ndan
ce
9810
0
167
78
168
17
108
16
264
7
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Handbook for the Chemical Analysis of Plastic and Polymer Additives38
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20
˚
C)
Water MeOH EtOH Acetone CH
2
Cl
2
Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
N
S S
S
S
N
Cure-Rite
®
IBT
Pale yellow to white powder
Stable under normal conditions
U
Not available
Noveon, Inc.
C
18
H
36
N
2
S
4
408.76
tetraisobutylthiuram disulfide
tetra(isobutyl)thioperoxydicarbamic acid
3064-73-1N/ATIBTD
70-73 ˚C
<0.01 U U U U
Used as an accelerator and vulcanizing agent in rubber (EPDM, SBR, Nitrile, and Natural). Especially useful when the for-mation of nitrosoamines is a concern.
FDA approved for use with rubber food-contact materials per 21CFR178.2010 and 178.3860.
Due to its low solubility in water and therefore the non-availability to species, this product is not expected to be toxic to aquatic organisms. Estimated log Kow value of 3.4 indicates a low to moderate potential to bioaccumulate.
Can be released as point source pollution during manufacture, transportation, and end use. Additionally, it may be released from manufactured products containing this material during the active life cycle of the products and/or upon disposal of the products.
Not listed as a carcinogen by IARC, NTP, ACGIH, or OSHA.
React-Rite
®
TIBTDWestco TIBTD
Resource Innovations, Inc.Western Reserve Chemical Corp.
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Crosslinking Compounds/Accelerators 39
Mass Spectrum for
For Chromatogram See Appendix A -
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
05
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
m/z
-->
Abundance
Avera
ge o
f 15.6
82 to 1
5.9
73 m
in.: P
LA
S-A
C-0
04.D
57
86
76
72
53
115
203
129
90
210
68
147
122
98
61
103
176
188
80
214
133
137
94
141
151
155
159
163
167
107
Cure-Rite
®
IBT - PLAS-AC-004
PLAS-AC-004 - page 447
MW
=408
.76
m/z
Abu
ndan
ce
5710
0
8677
7672
5540
5623
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Handbook for the Chemical Analysis of Plastic and Polymer Additives40
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20
˚C)Water MeOH EtOH Acetone CH2Cl2 Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
Activator OT Urea
White solid
Decomposes at 135 ˚C (MP)
~16
Decomposes 135 ˚C
Akrochem Corporation
CH4N2O60.07
urea
carbonyl diamide; carbamide; isourea
57-13-6YR6250000Not Identified
133-135 ˚C
>80 U U U U
Urea is used in the manufacture of urea-formaldehyde plastics, adhesives, polymers, synthetic fibers, dyes, etc.
FDA approved 1998 for the following applications: in the manufacture of resin and polymer-based coatings in contact with food, 21CFR175:300; in the manufacture of cellophane for packaging food, 21CFR177.1200. EU (1990) determined urea acceptable for use in plastic materials in contact with foodstuffs. In 1993, a joint FAO/WHO Committee on food additives determined 3% urea in chewing gum is not toxic.
Although urea has generally low ecotoxicity to organisms, its well-documented indirect and long-term effects to the ecosys-tems, e.g., eutrophication, groundwater pollution, soil acidification, and ammonia emissions to air, should be considered. When released to soil, this material will hydrolyze into ammonium in a matter of days to several weeks. This material is not anticipated to bioaccumulate — it has a BCF <100.
Occupational and environmental exposure during production is possible due to accidental process breakdown and disorders in reactor operations, pumping cycles, evaporation, and crystallization processes; in maintenance, loading and unloading operations. Potential occupational exposure occurs via inhalation of aerosols from urea melt and hot saturated solutions, splashed to skin or eyes, or inhalation of dust.
No documented toxic effects at low doses. Chronic exposure is carcinogenic and mutagenic: 821 g/kg [Rat] and 394 g/kg [Mouse] for one year results in lymphomas and Hodgkin’s disease. Long-term toxicity: High doses affect cholinergic and bioenergetic processes and modify CNS structure. Acute oral toxicity (LD50): 14.3 g/kg BW [Rat], 11 g/kg [Mouse].
Supercel 3000Varioform II
H2N NH2
O
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Crosslinking Compounds/Accelerators 41
Mass Spectrum for
For Chromatogram See Appendix A -
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
05
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
m/z
-->
Abundance
Avera
ge o
f 10.0
81 to 1
0.3
95 m
in.: P
LA
S-A
C-0
05.D
44
60
43
42
41
45
61
Activator OT Urea - PLAS-AC-005
PLAS-AC-005 - page 446
MW
=60.
07
m/z
Abu
ndan
ce
4410
0
6065
4325
429
413
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Handbook for the Chemical Analysis of Plastic and Polymer Additives42
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20˚C)
Water MeOH EtOH Acetone CH2Cl2 Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
Zn
SS
S S NN
Accelerator EZ & EZ-SP
White powder
Stable under normal conditions of use.
U
Not available
Akrochem Corporation
C10H20N2S4 • Zn361.93
zinc diethyldithiocarbamate
bis(diethyldithiocarbamato)zinc; diethyldithiocarbamic acid, zinc salt; ethyl zimate
14324-55-1ZH0350000DEDTZ/ZDEC
178-181 ˚C
<0.1 U S S U
ZDEC is used in the following applications: as a fast primary or secondary vulcanization accelerator in NR, SBR, IIR, EPDM and for natural and synthetic latex; a stabilizer in butyl, butadiene, and urethane rubbers; an antioxidant in rubber-based adhesive systems; a stabilizer in cement; a heat stabilizer for polyethylene.
FDA approved 1998 for use as an accelerator in the manufacture of rubber material (up to 1.5% of weight of rubber) intended for use in all stages of production, processing, packaging, and transport of food: 21CFR177.2600. Regulated for use under 21CFR175.105 for components of adhesives.
Ecological impact not determined. Similar compounds show low to moderate biodegradability, but rapid hydrolysis under acidic conditions. Similar compounds are also determined to have low bioaccumulation potential and environmental persis-tence: 96 hour LC50 0.23 mg/L [Rainbow Trout], 0.40 mg/L [Bluegill Sunfish], 0.26 mg/L [Fathead Minnow], 48 hour EC50 0.44 mg/L [Daphnia Magna].
Migration of ZDEC into water after 3 days exposure at 20 ºC is 0.6 mg/L.
Not listed as a suspected carcinogen by NTP, IARC, or OSHA. Reactions with nitrosylating agents during vulcanization may yield suspected carcinogens such as nitrosamines. Studies of rats and mice gavaged with ZDEC yield no genotoxic or teratogenic effects. Long-term exposure to large doses may have neurodegenerative effects in addition to altering hydrolytic enzymes in the human brain. Acute oral (LD50): 3530 mg/kg [Rat]. Acute dermal (LD50): >3160 mg/kg [Rabbit].
EthasanPerkacit® ZDECSoxinol® EZVulcacure
Solutia, Inc.Akzo Nobel Chemicals B.V.Sumitomo Chemical Co., Ltd.Alco Oil and Chemical Corp.
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Crosslinking Compounds/Accelerators 43
Mass Spectrum for
For Chromatogram See Appendix A -
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
05
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
m/z
-->
Abundance
Avera
ge o
f 26.7
09 to 2
6.7
43 m
in.: P
LA
S-A
C-0
06.D
116
360
88
60
72
148
44
212
244
331
271
283
184
97
299
155
168
123
352
367
104
175
203
79
219
232
130
255
139
Accelerator EZ & EZ-SP - PLAS-AC-006
PLAS-AC-006 - page 443
MW
=361
.93
m/z
Abu
ndan
ce
116
100
360
68
8855
362
51
6044
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Handbook for the Chemical Analysis of Plastic and Polymer Additives44
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20˚C)
Water MeOH EtOH Acetone CH2Cl2 Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
N, N'-Diethylthiourea
White semi-transparent crystals
Stable under normal conditions of use.
S
169 ˚C
C5H12N2S132.23
1,3-diethylthiourea
1,3-diethyl-2-thiourea; N,N'-diethylthiocarbamide
105-55-5YS9800000DETU
68-71 ˚C
3.8 S S U U
Accelerator for mercaptan-modified chloroprene rubber. Stabilizer for natural, nitrile-butadiene, styrene-butadiene, and chloroprene rubbers. Found in adhesives, animal repellent, cements, condoms, cosmetic applicators, disinfectants, fungi-cides, gloves, leather shoes, rubber in undergarments, tires and tubes, soaps and shampoos.
Regulated for use under 21 CFR §177.2600 Rubber Articles Intended for Repeated Use in Food Contact.
If released to soil, biodegradation of N,N-diethylthiourea may be an important removal process. Because of the estimated low Koc value in soil, N,N-diethylthiourea may rapidly leach in soil. The volatilization of N,N-diethylthiourea from moist soil is not expected to be an important removal process. Neither photolysis nor hydrolysis are expected to be important in water. BCF = 2.
The release of N,N-diethylthiourea in the environment is expected to occur during waste disposal from its production and use.
Oral (LD50): = 316 mg/kg [Rat]Oral (TDLo): = 11 gm/kg/2Y-C [Rat]Tumorigenic - Carcinogenic by RTECS criteria; Endocrine - thyroid tumors Mutation in mammalian somatic cells (mouse lymphocyte) = 1500 mg/LBacteria: Phytobacterium phosphoreum: 761.0 mg/L; 15 minute Microtox test: No data available.
Accelerator DETUThiate® HWestco DETUPennzone E
Akrochem CorporationRT VanderbiltWestern Reserve Chemical
NH
NH
S
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Crosslinking Compounds/Accelerators 45
Mass Spectrum for
For Chromatogram See Appendix A -
N, N'-Diethylthiourea - PLAS-AX-103
PLAS-AX-103 - page 444
MW
=132
.23
m/z
Abu
ndan
ce
132
100
6038
7119
131
15
133
8
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Handbook for the Chemical Analysis of Plastic and Polymer Additives46
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20˚C)
Water MeOH EtOH Acetone CH2Cl2 Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
1,3-Diphenyl-2-thiourea
White powder
Stable under normal conditions of use.
S
348-350 ˚C
C13H12N2S228.31
1,3-di(phenyl)thiourea
N,N'-diphenylthiocarbamide
102-08-9FE1225000DPTU
152-155 ˚C
<0.01 S S U U
Used as a primary or secondary vulcanization accelerator.
Regulated for use under the following sections of 21 CFR: §177.2600 Rubber Articles Intended for Repeated Use in Food Contact§175.105 Components of Adhesives
Level III Fugacity Model: Mass Amount (%) Half-Life (h) Emissions (kg/h) Air 0.0975 3.01 1000 Water 17 900 1000 Soil 82.2 1.8e+003 1000 Sediment 0.626 8.1e+003 0 Persistence Time: 1.17e+003 h
Can be released as point source pollution during manufacture, transportation, and end use. Additionally, it may be released from manufactured products containing this material during the active life cycle of the products and/or upon disposal of the products.
Oral (LD50): 50 mg/kg [Rat]Intraperitoneal (LD50): 1 gm/kg [Rat]Intraperitoneal (LD50): 500 mg/kg [Mouse]
Accelerator Thio #1Vulkacit CAWestco DPTU
AkrochemLanxessWestern Reserve Chemical
HN
HN
S
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Crosslinking Compounds/Accelerators 47
Mass Spectrum for
For Chromatogram See Appendix A -
1,3-Diphenyl-2-thiourea - PLAS-AC-008
PLAS-AC-008 - page 449
MW
=228
.31
m/z
Abu
ndan
ce
135
100
7755
5122
5012
136
9
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Handbook for the Chemical Analysis of Plastic and Polymer Additives48
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20˚C)
Water MeOH EtOH Acetone CH2Cl2 Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
Dipentamethylenethiuram Tetrasulfide
Light yellow to gray powder
Stable under normal conditions of use.
U
510 ˚C
C12H20N2S6
384.70
1,1'-(tetrathiodicarbonothioyl)-bis-piperidine
120-54-7TN4221000DPTT
115 ˚C
<0.01 U S U U
This compound is used as primary or secondary accelerator or sulfur donor for both natural rubber and synthetic.
Regulated for use in articles in contact with food as specified under FDA §175.105, §175.300, §177.1210 (indirect food contact).
Contains no hazardous air pollutants or ozone depleting substances. It is also not listed under the US Clean Water Act Prior-ity Pollutant List.
Can be released as point source pollution during manufacture, transportation, and end use. Additionally, it may be released from manufactured products containing this material during the active life cycle of the products and/or upon disposal of the products.
Oral (LD50): > 2000 mg/kg [Rat]
Westco DPTTTetrone A
Western Reserve Chemical
N S
S
S
S
S N
S
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Crosslinking Compounds/Accelerators 49
Mass Spectrum for
For Chromatogram See Appendix A -
Dipentamethylenethiuram Tetrasulfide - PLAS-AC-009
PLAS-AC-009 - page 450
MW
=384
.70
m/z
Abu
ndan
ce
384
100
140
94
152
91
283
81
218
80
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Handbook for the Chemical Analysis of Plastic and Polymer Additives50
Brand Names & Manufacturers
Physical Properties
Application, Regulatory & Environmental Information
Appearance
StabilitySolubility(g/100mL 20˚C)
Water MeOH EtOH Acetone CH2Cl2 Hexane
Melting Point Boiling Point
Molecular Weight
CAS Number
RTECS Number
Abbreviation
Application
Regulatory Information
Environmental Impact
Point of Release
Toxicological Data
Chemical Name
Synonyms
Formula
NH
NH
NH
1,3-Di-o-tolylguanidine
White powder
Stable under normal conditions of use.
S
N/A
C15H17N3
239.32
1,2-bis(2-methylphenyl)guanidine
Di-o-tolylguanidine
97-39-2MF1400000DOTG
175 - 178 ºC
<0.01 S S U U
Seldom used alone, commonly used with thiazoles, thiurams, dithiocarbamates, and sulfenamides to promote its activity as an accelerant. Mainly used in processing thick rubber products, tread rubber, breaker rubber, and rubber roll cover.
Regulated for use under the following sections of 21 CFR: §177.2600 Rubber Articles Intended for Repeated Use in Food Contact§175.105 Components of Adhesives§178.3120 Animal Glue
Contains no hazardous air pollutants or ozone-depleting substances. It is also not listed under the US Clean Water Act Pri-ority Pollutant List.
Can be released as point source pollution during manufacture, transportation, and end use. Additionally, it may be released from manufactured products containing this material during the active life cycle of the products and/or upon disposal of the products.
LD50 Oral - Mammal - 120 mg/kgLD50 Oral Rat 56 mg/kg
Accelerator DOTGDOTGSovchem® DOTGVANAX® DOTG
TimeliallWestern Reserve ChemicalSovereign Chemical CompanyRT Vanderbilt
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4-4
Crosslinking Compounds/Accelerators 51
Mass Spectrum for
For Chromatogram See Appendix A -
1,3-Di-o-tolylguanidine - PLAS-AC-010
PLAS-AC-010 - page 451
MW
=239
.32
m/z
Abu
ndan
ce
107
100
106
42
239
31
9120
224
14
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