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Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite
Structure of bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite
Names
Preferred IUPAC name
3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane
Other names
Trade names
  • Irgafos 126 (BASF)
  • ADK Stab PEP 24 (Adeka)
  • Ultranox 626 (SI Group)
Identifiers
3D model (JSmol)
EC Number
  • 248-597-9
  • InChI=1S/C33H50O6P2/c1-29(2,3)23-13-15-27(25(17-23)31(7,8)9)38-40-34-19-33(20-35-40)21-36-41(37-22-33)39-28-16-14-24(30(4,5)6)18-26(28)32(10,11)12/h13-18H,19-22H2,1-12H3
    Key: InChIKey=AIBRSVLEQRWAEG-UHFFFAOYSA-N
  • O(P1OCC2(COP(OC3=C(C(C)(C)C)C=C(C(C)(C)C)C=C3)OC2)CO1)C4=C(C(C)(C)C)C=C(C(C)(C)C)C=C4
Properties
C33H50O6
Molar mass 542.757 g·mol−1
Appearance White solid
Density 1.166 at 20°C
Melting point 172–179 °C (342–354 °F; 445–452 K)
Boiling point 311 °C (592 °F; 584 K)
93.0 µg/L at 25°C
Hazards
GHS labelling:
GHS09: Environmental hazard
Warning
H410
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite is an organophosphite used as a polymer stabilizer in plastics. Like other phosphite antioxidants it primarily acts to remove hydroperoxides and is typically used in comination with hindered phenolic antioxidant such as it acts as pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).

Synthesis

[edit]

It is formed by reaction between phosphorous trichloride, pentaerythritol and 2,4-di-tert-butylphenol. The poor solubility of pentererythritol can be an issue and non-nuncleophilic amines are often used to promote the reaction.[1]

Properties and applications

[edit]

Compared to tris(2,4-di-tert-butylphenyl)phosphite (a common phosphite antioxidant) it has higher activity but lower stability against hydrolysis. Trace levels of amine bases are often added to commerical material to slow hydrolysis and increase storage life. [2] It's crystal stucture has been determined.[3] It is comparable with a wide range of plastics inclding polyolefin]s, engineering plastics and polyurethane fibers. It is an approved food contact material in the US.[4]

References

[edit]
  1. ^ Zhu, Yuliang; Liu, Xinyue; Tang, Ying; Xu, Kexin; Tang, Xin; Zhu, Longzhi; Xiong, Biquan (13 November 2024). "Recent Advances in the Synthesis of Commercially Available Phosphite Antioxidants". ChemistryOpen. doi:10.1002/open.202400135.
  2. ^ Papanastasiou, M.; McMahon, A.W.; Allen, N.S.; Doyle, A.M.; Johnson, B.J.; Keck-Antoine, K. (November 2006). "The hydrolysis mechanism of bis(2,4-di-tert-butyl)pentaerythritol diphosphite (Alkanox P24): An atmospheric pressure photoionisation mass spectrometric study". Polymer Degradation and Stability. 91 (11): 2675–2682. doi:10.1016/j.polymdegradstab.2006.04.023.
  3. ^ Barren, J. P.; Bryant, G. L.; Garbauskas, M. F.; Mahood, J. A. (15 August 1995). "Bis(2,4-di-tert-butylphenyl) Pentaerythritol Diphosphite". Acta Crystallographica Section C Crystal Structure Communications. 51 (8): 1636–1639. doi:10.1107/S0108270195000965.
  4. ^ "FDA broadens food contact approval for SI Group's Ultranox 626 antioxidant". Additives for Polymers. 2019 (9): 4–4. September 2019. doi:10.1016/S0306-3747(19)30174-5.


?

[edit]
General chemical structure of orthophthalates. (R and R' are general placeholders.)

Phthalates (US: /ˈθæleɪts/,[1] UK: /ˈθɑːleɪtsˌ ˈfθælɪts/[2][3]), or phthalate esters, are esters of phthalic acid. They are mainly used as plasticizers, i.e., substances added to plastics to increase their flexibility, transparency, durability, and longevity. They are used primarily to soften polyvinyl chloride (PVC).

Lower-molecular-weight phthalates, those derived from C3-C6 alcohols, are being gradually replaced in many products in the United States, Canada, and European Union over health concerns.[4][5] They are being replaced by high-molecular-weight phthalates (those with more than six carbons in their backbone, which gives them increased permanency and durability), as well as alternative plasticizers not based on phthalic anhydride. In 2010, the market was still dominated by high-phthalate plasticizers; however, due to legal provisions and growing environmental awareness and perceptions, producers are increasingly switching to non-phthalate plasticizers.[6] The legacy use of phthalate plasticizers has prevented manufacturers from using post-consumer recycled PVC since that recycled content would likely contain phthalates. Thus, many manufacturers have moved to use only virgin PVC in their products.[7][8][9] There are, however, efforts underway to collect post-consumer PVC for chemical recycling efforts that can remove legacy phthalates and create virgin-like PVC. Those efforts are focused on areas like healthcare where PVC makes up a significant amount of medical devices.[10]

Tables

[edit]
Title
Name Abbreviation Alcohol carbon number Molecular weight (g/mol) CAS No.
Dimethyl phthalate DMP 1 194.18 131-11-3
Diethyl phthalate DEP 2 222.24 84-66-2
Diallyl phthalate DAP 3 246.26 131-17-9
Di-n-propyl phthalate DPP 3 250.29 131-16-8
Di-n-butyl phthalate DBP 4 278.34 84-74-2
Diisobutyl phthalate DIBP 4 278.34 84-69-5
Di-2-methoxyethyl phthalate DMEP 3 282.29 117-82-8
Butyl cyclohexyl phthalate * BCP 4 – 6 304.38 84-64-0
Di-n-pentyl phthalate DNPP 5 306.4 131-18-0
Dicyclohexyl phthalate DCP 6 330.42 84-61-7
Butyl benzyl phthalate BBP 4 – 7 312.36 85-68-7
Di-n-hexyl phthalate DNHP 6 334.45 84-75-3
Diisohexyl phthalate DIHxP 6 334.45 146-50-9, 68515-50-4
Diisoheptyl phthalate* DIHpP 7 362.5 41451-28-9, 71888-89-6
Butyl decyl phthalate BDP 4 – 10 362.5 89-19-0
Dibutoxy ethyl phthalate DBEP 6 366.45 117-83-9
Di(2-ethylhexyl) phthalate DEHP, DOP 8 390.56 117-81-7
Di(n-octyl) phthalate DNOP 8 390.56 117-84-0
Diisooctyl phthalate DIOP 8 390.56 27554-26-3
n-Octyl n-decyl phthalate ODP 8 – 10 418.61 119-07-3
Diisononyl phthalate DINP 9 418.61 28553-12-0
Di(2-propylheptyl) phthalate DPHP 10 446.66 53306-54-0
Diisodecyl phthalate DIDP 10 446.66 26761-40-0
Diundecyl phthalate DUP 11 474.72 3648-20-2
Diisoundecyl phthalate DIUP 11 474.72 85507-79-5
Ditridecyl phthalate DTDP 13 530.82 119-06-2
Diisotridecyl phthalate DITP 13 530.82 68515-47-9


Title
Name Abbreviation Alcohol carbon number Molecular weight (g/mol) CAS No. Applications Properties of concern for human health (ECHA classification) !
Dimethyl phthalate DMP 1 194.18 131-11-3 Cellulose acetate coatings, insect repellent Not class.
Diethyl phthalate DEP 2 222.24 84-66-2 Cellulose acetate coatings, perfumes & personal care products Under assessment as Endocrine Disrupting
Diallyl phthalate DAP 3 246.26 131-17-9 Forms vinyl ester resins Skin sensitising
Di-n-propyl phthalate DPP 3 250.29 131-16-8 Cellulose acetate & nitrocellulose coatings Not class.
Di-n-butyl phthalate DBP 4 278.34 84-74-2 Nitrocellulose coatings, cold-flex PVC Toxic to Reproduction, Endocrine Disrupting, Under assessment as Persistent, Bioaccumulative and Toxic
Diisobutyl phthalate DIBP 4 278.34 84-69-5 Nitrocellulose coatings, adhesives & Sealants, Inks and waxes Toxic to Reproduction, Endocrine Disrupting
Di-2-methoxyethyl phthalate DMEP 3 282.29 117-82-8 Cellulose acetate Toxic to Reproduction
Butyl cyclohexyl phthalate * BCP 4 – 6 304.38 84-64-0 specialist use?
Di-n-pentyl phthalate DNPP 5 306.4 131-18-0 Toxic to Reproduction
Dicyclohexyl phthalate DCP 6 330.42 84-61-7 Flooring, Toys Toxic to Reproduction, Endocrine Disrupting, Skin sensitising
Butyl benzyl phthalate BBP 4 – 7 312.36 85-68-7 Foamed vinyl (flooring), adhesives, sealants and coating products. Polyvinyl butyral Toxic to Reproduction, Endocrine Disrupting
Di-n-hexyl phthalate DNHP 6 334.45 84-75-3 Toxic to Reproduction
Diisohexyl phthalate DIHxP 6 334.45 146-50-9, Toxic to Reproduction
Diisoheptyl phthalate* DIHpP 7 362.5 41451-28-9, Toxic to Reproduction
Butyl decyl phthalate BDP 4 – 10 362.5 89-19-0 specialist use?
Dibutoxy ethyl phthalate DBEP 6 366.45 117-83-9
Di(2-ethylhexyl) phthalate DEHP, DOP 8 390.56 117-81-7 PVC generally Toxic to Reproduction, Endocrine Disrupting
Di(n-octyl) phthalate DNOP 8 390.56 117-84-0 Not classified but some uses restricted under REACH
Diisooctyl phthalate DIOP 8 390.56 27554-26-3 Toxic to Reproduction
n-Octyl n-decyl phthalate ODP 8 – 10 418.61 119-07-3
Diisononyl phthalate DINP 9 418.61 28553-12-0 Flooring, Wall coverings, Cladding and Roofing, Cables and wires, Film and sheet, Automotive , Tubes & Hoses, Coated Fabrics, Inks and waxes Not classified but some uses restricted under REACH
Di(2-propylheptyl) phthalate DPHP 10 446.66 53306-54-0 Flooring, Wall coverings, Cladding and Roofing, Cables and wires, Film and sheet, Automotive , Tubes & Hoses, Coated Fabrics Under assessment as Endocrine Disrupting
Diisodecyl phthalate DIDP 10 446.66 26761-40-0
Diundecyl phthalate DUP 11 474.72 3648-20-2
Diisoundecyl phthalate DIUP 11 474.72 85507-79-5 Cladding and Roofing, Cables and wires, Automotive Not class.
Ditridecyl phthalate DTDP 13 530.82 119-06-2
Diisotridecyl phthalate DITP 13 530.82 68515-47-9 Cables and wires, Automotive Not class.
Title
Name Abbreviation Structural formula Molecular weight (g/mol) CAS No.
Dimethyl phthalate DMP C6H4(COOCH3)2 194.18 131-11-3
Diethyl phthalate DEP C6H4(COOC2H5)2 222.24 84-66-2
Diallyl phthalate DAP C6H4(COOCH2CH=CH2)2 246.26 131-17-9
Di-n-propyl phthalate DPP C6H4[COO(CH2)2CH3]2 250.29 131-16-8
Di-n-butyl phthalate DBP C6H4[COO(CH2)3CH3]2 278.34 84-74-2
Diisobutyl phthalate DIBP C6H4[COOCH2CH(CH3)2]2 278.34 84-69-5
Butyl cyclohexyl phthalate * BCP CH3(CH2)3OOCC6H4COOC6H11 304.38 84-64-0
Di-n-pentyl phthalate DNPP C6H4[COO(CH2)4CH3]2 306.40 131-18-0
Dicyclohexyl phthalate DCP, DCHP C6H4[COOC6H11]2 330.42 84-61-7
Butyl benzyl phthalate BBP CH3(CH2)3OOCC6H4COOCH2C6H5 312.36 85-68-7
Di-n-hexyl phthalate DNHP C6H4[COO(CH2)5CH3]2 334.45 84-75-3
Diisohexyl phthalate DIHxP C6H4[COO(CH2)3CH(CH3)2]2 334.45 146-50-9
Diisoheptyl phthalate DIHpP C6H4[COO(CH2)4CH(CH3)2]2 362.50 41451-28-9
Butyl decyl phthalate BDP CH3(CH2)3OOCC6H4COO(CH2)9CH3 362.50 89-19-0
Dibutoxy ethyl phthalate DBEP C6H4[COO(CH2)2O(CH2)4CH3]2 366.45 117-83-9
Di(2-ethylhexyl) phthalate DEHP, DOP C6H4[COOCH2CH(C2H5)(CH2)3CH3]2 390.56 117-81-7
Di(n-octyl) phthalate DNOP C6H4[COO(CH2)7CH3]2 390.56 117-84-0
Diisooctyl phthalate DIOP C6H4[COO(CH2)5CH(CH3)2]2 390.56 27554-26-3
n-Octyl n-decyl phthalate ODP CH3(CH2)7OOCC6H4COO(CH2)9CH3 418.61 119-07-3
Diisononyl phthalate DINP C6H4[COO(CH2)6CH(CH3)2]2 418.61 28553-12-0
Di(2-propylheptyl) phthalate DPHP C6H4[COOCH2CH(CH2CH2CH3)(CH2)4CH3]2 446.66 53306-54-0
Diisodecyl phthalate DIDP C6H4[COO(CH2)7CH(CH3)2]2 446.66 26761-40-0
Diundecyl phthalate DUP C6H4[COO(CH2)10CH3]2 474.72 3648-20-2
Diisoundecyl phthalate DIUP C6H4[COO(CH2)8CH(CH3)2]2 474.72 85507-79-5
Ditridecyl phthalate DTDP C6H4[COO(CH2)12CH3]2 530.82 119-06-2
Diisotridecyl phthalate DITP C6H4[COO(CH2)10CH(CH3)2]2 530.82 68515-47-9

Bits

[edit]

The official definition of a plasticizer focuses on performance criteria, rather than specific descriptions of chemical and/or physical characteristics.

PVC is unique in its acceptance of large amounts of plastiseiser with gradual changes in physical properties from a rigid solid to a soft gel.

Plasticizers also lower the processing temperature and change many other physical and mechanical properties. For example, they lower the glass transition temperature, the Youngs modulus, and the melt viscosity.

PVC has excellent electrical insulation properties, making it ideal for cabling applications. Its good impact strength and weatherproof attributes make it ideal for construction products.

https://www.cdc.gov/biomonitoring/phthalates_factsheet.html https://www.plasticisers.org/wp-content/uploads/2016/10/Plasticisers_Factsheet_The-power-of-many.pdf

The mechanism by which phthalates and related compounds effect plasticization to polar polymers has been a subject of intense study since the 1960s. The mechanism is one of polar interactions between the polar centres of the phthalate molecule (the C=O functionality) and the positively charged areas of the vinyl chain, typically residing on the carbon atom of the carbon-chlorine bond. For this to be established, the polymer must be heated in the presence of the plasticizer, first above the Tg of the polymer and then into a melt state. This enables an intimate mix of polymer and plasticizer to be formed, and for these interactions to occur. When cooled, these interactions remain and the network of PVC chains cannot reform (as is present in unplasticized PVC, or PVC-U). The alkyl chains of the phthalate then screen the PVC chains from each other as well. They are blended within the plastic article as a result of the manufacturing process.[11]

Because they are not chemically bonded to the host plastics, phthalates are released from the plastic article by relatively gentle means. For example, they can be removed by heating or by extraction with organic solvents.

https://d1wqtxts1xzle7.cloudfront.net/54286173/PVC_handbook-with-cover-page-v2.pdf?Expires=1651146476&Signature=Fqe3oSwGSP7Im6q3-LKa0TGpb2FVjkexVSc4ceHr-X6ldnLuD5Y7awYbb0kUDuPZNmRp0HVakHFbcEe1UKXbUn7VVYSf0mRzqSQuunW8bqA3nCyR4VZjfufPAIqXRBFrtb99EAuOgNAOeOE7o7KhKhz31ro30n6xq3ByzygnsUb0kgJ9J-JAMu6HM9dX06uGX0CWflgqiXXeL1nkLKnK3WuGGHupPqG0yKwjChu8UwKHEnBTqsKTeisCXDWuUb8pZbLFMFu8FwcAF6l~ychp~39BUZ4-qRH6Sgis4K7QKC8JQMFxfphjY384Dwp~ns5CUHaQ7IrqQq4LonVXawH1xw__&Key-Pair-Id=APKAJLOHF5GGSLRBV4ZA

[12]

[13]

https://echa.europa.eu/documents/10162/17233/rest_ten_phthalates_screening_report_en.pdf/40a25f0b-01af-7c52-eea0-7f891dfa9ae4?t=1649839351089

1970 health risks https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1474854/pdf/envhper00501-0008.pdf

The phthalates have a clear syrupy liquid consistency and show low water solubility, high oil solubility, and low volatility.

PVC has excellent electrical insulation properties, making it ideal for cabling applications. Its good impact strength and weatherproof attributes make it ideal for construction products (flooring, wall coverings), electrical (wire and cable jacketing), consumer goods (toys, footwear, etc.), packaging, transportation (inside and outside of vehicles), furnishings, and medical uses (tubing, blood bags)

[14]

Production

[edit]

Phthalates are produced industrially by the acid catalysed reaction of phthalic anhydride with excess alcohol. The synthesis of diethyl phthalate is illustrative of this:

The properties of the phthalate can be varied by changing the alcohol,[15] allowing for an almost limitless range of products, although only around 30 are, or have been, commercially important. Phthalate's share of the global plasticisers market has been decreasing since around 2000. Despite this the global production of phthalates has continued to rise. In 2015 total production of was around 5.5 million tonnes,[16] up from around 2.7 million tonnes in the 1980s.[17]. The reason for this has been the increasing size of the plasticiser market (a smaller slice of a much bigger pie), driven by increases in PVC production, which doubled between 2000 and 2020. The People’s Republic of China is the largest consumer, accounting for around 45% of all use. Europe and the United States together account for around 25% of use, with the remainder widely spread around the world.[16]

Common Phthalates
Commercially important compounds shown in bold
Name Abbreviation Alcohol carbon number Molecular weight (g/mol) CAS No. Properties of concern for human health (ECHA classification 2022)[18]
Dimethyl phthalate DMP 1 194.18 131-11-3
Diethyl phthalate DEP 2 222.24 84-66-2 Under assessment as Endocrine Disrupting
Diallyl phthalate DAP 3 246.26 131-17-9 Skin sensitising
Di-n-propyl phthalate DPP 3 250.29 131-16-8
Di-n-butyl phthalate DBP 4 278.34 84-74-2 Toxic to Reproduction, Endocrine Disrupting, Under assessment as PBT
Diisobutyl phthalate DIBP 4 278.34 84-69-5 Toxic to Reproduction, Endocrine Disrupting
Di-2-methoxyethyl phthalate DMEP 3 282.29 117-82-8 Toxic to Reproduction
Butyl cyclohexyl phthalate BCP 4 – 6 304.38 84-64-0
Di-n-pentyl phthalate DNPP 5 306.4 131-18-0 Toxic to Reproduction
Dicyclohexyl phthalate DCP 6 330.42 84-61-7 Toxic to Reproduction, Endocrine Disrupting, Skin sensitising
Butyl benzyl phthalate BBP 4 – 7 312.36 85-68-7 Toxic to Reproduction, Endocrine Disrupting
Di-n-hexyl phthalate DNHP 6 334.45 84-75-3 Toxic to Reproduction
Diisohexyl phthalate DIHxP 6 334.45 146-50-9, Toxic to Reproduction
Diisoheptyl phthalate DIHpP 7 362.5 41451-28-9 Toxic to Reproduction
Butyl decyl phthalate BDP 4 – 10 362.5 89-19-0
Dibutoxy ethyl phthalate DBEP 6 366.45 117-83-9
Di(2-ethylhexyl) phthalate DEHP, DOP 8 390.56 117-81-7 Toxic to Reproduction, Endocrine Disrupting
Di(n-octyl) phthalate DNOP 8 390.56 117-84-0 Not classified but some uses restriction
Diisooctyl phthalate DIOP 8 390.56 27554-26-3 Toxic to Reproduction
n-Octyl n-decyl phthalate ODP 8 – 10 418.61 119-07-3
Diisononyl phthalate DINP 9 418.61 28553-12-0 Not classified but some uses restrictions
Di(2-propylheptyl) phthalate DPHP 10 446.66 53306-54-0 Under assessment as Endocrine Disrupting
Diisodecyl phthalate DIDP 10 446.66 26761-40-0
Diundecyl phthalate DUP 11 474.72 3648-20-2
Diisoundecyl phthalate DIUP 11 474.72 85507-79-5
Ditridecyl phthalate DTDP 13 530.82 119-06-2
Diisotridecyl phthalate DITP 13 530.82 68515-47-9

Natural occurrence

[edit]

Various plants and microorganisms have been reported to naturally produce phthalate esters (endogenous phthalates).[19][20] Biosynthesis is believed to involved a modified Shikimate pathway[21][22] The extent of this natural production is not fully know, but it may create a background of phthalate pollution.

Uses

[edit]

PVC Plasticisers

[edit]
Plasticised PVC has excellent electrical insulation properties and is extensively used as sheathing for wires and cables.

Among the common plastics, PVC is unique in its acceptance of large amounts of plasticiser with gradual changes in physical properties from a rigid solid to a soft gel. Between 90-95% of all phthalates are used as plasticisers for the production of flexible PVC.[23][24] They were the first commercially important compounds for this role,[25] a historic advantage that has lead to them becoming firmly embedded in flexible PVC technology.[26] Compounds derived from alcohols with 7-13 carbon atoms occupy a privileged position as general purpose plasticisers, suitable for almost all flexible PVC applications.[27][26] Compounds larger than this have limited compatibility in PVC, with di(isotridecyl) phthalate representing the practical upper limit. Conversely, compounds derived from alcohols with 4-6 carbon atoms are too volatile to be used on their own, but have been used alongside other compounds as secondary plasticisers, where they improve low-temperature flexibility. Phthalates derived from alcohols with 1-3 carbon atoms are not used as plasticisers in PVC at all, due excessive fuming at processing temperatures.[26]

Historically DINP, DEHP, DIOP, DOTP and DIHP have been the most important phthalates, however many of these are now facing regulatory pressure and gradual phase-outs. Almost all phthalates derived from alcohols with 8 or fewer carbons are classed as toxic by ECHA. This includes Bis(2-ethylhexyl) phthalate (DEHP or DOT), which has long been the the most widely used phthalate, with commercial production dating back to the 1930's.[28][29] In the EU, the use of DEHP is restricted under REACH and it can only be used in specific cases if an authorisation has been granted; similar restrictions exist in many other jurisdictions. Despite this, the phase-out of DEHP is slow and it was still the most frequently used plasticizer in 2018, with an estimated global production of 3.24 million tonnes.[29] DINP and DIDP are used as a substitutes for DEHP in many applications, as they are not classified as hazardous.[30] Non-phthalate plastisizers are also being increasingly used.

Almost 90% of all plasticizers are used in PVC, giving this material improved flexibility and durability.[31] The majority is used in films and cable sheathing.[29] Flexible PVC can consist of over 85% phthalate by mass, however unplasticized PVC (UPVC) should not contain any.

PVC properties as a function of phthalate plasticizer level[32]
Plastisicer content (% DINP by weight) Specific gravity (20 °C) Shore hardness
(type A, 15 s)		 Flexural stiffness (Mpa) Tensile strength (Mpa) Elongation at break (%) Example applications
Rigid 0 1.4 900 41 <15 Unplasticized PVC (UPVC): window frames and sills, doors, rigid pipe
Semi-rigid 25 1.26 94 69 31 225 Vinyl flooring, flexible pipe, thin films (stretch wrap), advertising banners
Flexible 33 1.22 84 12 21 295 Wire and cable insulation, flexible pipe
Very Flexible 44 1.17 66 3.4 14 400 Boots and clothing, inflatables,
Extremely Flexible 86 1.02 < 10 Fishing lures (soft plastic bait), polymer clay, plastisol inks

Non-PVC Plasticisers

[edit]

Phthalates see use as plasticisers in various other polymers, with applications centred around coatings such as lacquers, vanishes and paints. The addition of phthalates imparts some flexibility to these materials, reducing their tendency to chip. Phthalates derived from alcohols with between 1-4 carbon atoms are used as plasticisers for cellulose-type plastics, such as cellulose acetate, nitrocellulose and cellulose acetate butyrate, with commonly encountered applications including nail polish. Most phthalates are also compatible with alkyds and acrylic resin, which are used in both oil and emulsion based paints.

Other polymer systems include polyvinyl butyral (particularly the forms used to make laminated glass), PVA and its co-polymers like PVCA. They are also compatible in nylon, polystyrene, polyurethanes, and certain rubbers; but their use in these is very limited.[33] Phthalates have also been used for producing plastic explosives such as Semtex.

Phthalates can plasticise ethyl cellulose, polyvinyl acetate phthalate (PVAP) and cellulose acetate phthalate (CAP), all of which are used to make enteric coatings for tablet and capsule medications. These coatings protect drugs from the acidity of the stomach, but allow their release and absorption in the intestines.

Other uses

[edit]

Relatively minor amounts of some phthalates are used in non-plasticizer applications. Phthalates find use in personal-care items such as eye shadow, moisturizer, nail polish, liquid soap, and hair spray.[34][35][36] Low molecular weight phthalate like dimethyl phthalate and diethyl phthalate are used as fixatives for perfumes.[37] Dimethyl phthalate has been also used as an insect repellent and is especially useful against ixodid ticks responsible for Lyme disease.[38] and species of mosquitoes such as Anopheles stephensi, Culex pipeins and Ades aegypti.[39][40][41]

Diallyl phthalate is used to prepare vinyl ester resins with excellent electrical insulation properties and is used to manufacture of electronic parts.Alkyds are sometimes classes as phthalates, as they meet the technical definition, being polymeric esters of phthalic acid however their properties and applications are very different.

History

[edit]

The development of cellulose nitrate plastic in 1846 led to the patent of castor oil in 1856 for use as the first plasticizer. In 1870, camphor became the more favored plasticizer for cellulose nitrate. Phthalates were first introduced in the 1920s and quickly replaced the volatile and odorous camphor. Polyvinyl chloride (PVC)

Waldo Semon and the B.F. Goodrich Company developed a method in 1926 to plasticize PVC by blending it with various additives,[42] with the use of dibutyl phthalate patented in 1933.[43]

In February 2009, the Joint Research Centre (JRC) of the European Commission published a review of methods to measure phthalates in food.[44]

In 2021, a study looked for phthalates in 64 fast food items. Phthalate DnBP was detected in 81 percent of the samples, while DEHP was found in 70 percent. Diethylhexyl terephthalate (DEHT), the main alternative to DEHP, was detected in 86%.[45]

Alternatives

[edit]
Market trend in decreasing use of low orthophthalates including DEHP

Being inexpensive, nontoxic (in an acute sense), colorless, noncorrosive, biodegradable, and with easily tuned physical properties, phthalate esters are nearly ideal plasticizers. Among the numerous alternative plasticizers are Dioctyl terephthalate (DEHT) (a terephthalate isomeric with DEHP) and 1,2-Cyclohexane dicarboxylic acid diisononyl ester (a hydrogenated version of DINP).

Many bio-based plasticizers based on vegetable oil have been developed. It is a ready substitute for dioctyl phthalate.[46]

Health effects

[edit]
Toy dolls manufactured in China and seized by U.S. Customs and Border Protection in 2013 due to high phthalate levels

A study in the peer-reviewed journal Environmental Pollution published October 12, 2021 found that high phthalate levels are weakly correlated with a greater risk of dying from any cause and with a stronger correlation to dying from heart problems, but the calculated hazard ratios were below 2 in both cases. The study estimated that phthalates may contribute to 91,000–107,000 premature deaths each year among people aged 55–64 in the United States.[47]

Prevalence and human exposure

[edit]

Due to the ubiquity of plasticized plastics, the majority of people are exposed to some level of phthalates. For example, most Americans tested by the Centers for Disease Control and Prevention have metabolites of multiple phthalates in their urine.[48] In studies of rodents exposed to certain phthalates, high doses have been shown to change hormone levels and cause birth defects.[49]

Endocrine disruption

[edit]
Further information: Endocrine disruptor § Phthalates

Phthalates enter the bloodstream and disrupt sex hormone production, interfering with sexual development in infants and sexual behaviour in adults. Levels of phthalates have been dose-dependently linked to reduced anogenital distance[50] decreased sexual desire and satisfaction in women,[51] and malformed genital development in rats.

Phthalates act by mimicking the female hormone estrogen, which in turn inhibits production of the male hormone testosterone. As such, phthalates are considered to be endocrine disruptors[52][53][54]—a substance that interferes with the normal hormonal mechanisms that allow a biological organism to interact with its environment, and has sparked demands to ban or restrict its use in baby toys.[52]

Endocrine disruptors exhibit numerous behaviors that can make studying them a challenge. There can be a lag between when someone is exposed to an endocrine disruptor and any symptoms manifesting themselves–in particular fetal and early childhood exposure may have consequences later in adulthood.[52][55] Many studies refer to this period of fetal and postnatal development as particularly important to development, but studying this is difficult; it is obviously a huge challenge to measure endocrine disruptor exposure during fetal development and then decades later diagnosing any health problems. Additionally, endocrine disruptor exposure can transmit epigenetically to one's offspring without them being directly exposed to the endocrine disruptors.[56] Finally, particularly low levels of exposure may still have significant effects, and exposure to multiple endocrine disruptors across a variety of compounds (not just phthalates) may synergistically combine to cause a greater effect.[52][55] Evaluating the actual effects of a specific compound such as a particular phthalate requires examining cumulative exposure across multiple compounds, rather than evaluating one compound in isolation.[55]

A widespread concern about phthalate exposure is the possibility (though not conclusive) that it is the cause of a worldwide drop in male fertility.[57][58][59] Studies have shown that phthalates cause abnormalities in the reproductive systems of animals,[60] with the greatest effects when the animal is exposed during gestation and immediately thereafter.[61] Numerous studies on adult male humans show the similar result that phthalate exposure correlates with worsening metrics of male fertility, such as semen quality, the quantity of damaged DNA in sperm, decreased sperm motility, decreased semen volume, and other metrics.[53][61][62] Phthalates causing harm to the male reproductive system is plausible,[63] and continues to be researched.

The effect of phthalates on the female reproductive system is also not fully understood yet. Current studies indicate phthalates have negative effects on folliculogenesis and steroidogenesis.[64]

Early research also shows phthalate exposure may be associated with diabetes and insulin resistance, breast cancer, obesity,[65] metabolic disorders, and immune function.[54]

There are possible (though not conclusive) associations between phthalate exposure and adverse child neurodevelopment,[66][67] including the development of ADHD and autistic behaviors and lower cognitive and motor development.[68] Most common associations found in medical reports link the phthalates exposure to hyperactivity, aggression, and other adverse behaviors.[68] Some studies have found the childhood exposure to be as early as in utero.[69]

In many cases, there are studies that show connections between phthalates and these negative outcomes, as well as studies that show no connection; this is likely due to the research challenges outlined above, and when resolved, could show that phthalate exposure does not cause health effects, or even that they have a much greater effect than currently predicted.[55] In all cases, larger studies are needed to demonstrate incontrovertibly what effect phthalate exposure has on human health.

A Nature Reviews Endocrinology review paper from 2017[55] gives some advice for avoiding exposure to phthalates for concerned people; while they make pains to state that there is no evidence that shows this advice will positively affect one's health, they suggest (1) eating a balanced diet to avoid ingesting too many endocrine disruptors from a single source, (2) eliminating canned or packaged food in order to limit ingestion of DEHP phthalates leached from plastics, and (3) eliminating use of any personal product such as moisturizer, perfume, or cosmetics that contain phthalates.[55] Eliminating personal products containing phthalates can be particularly difficult or impossible due to some countries such as the United States not requiring them to be disclosed in a list of ingredients.[70]

Endocannabinoid system disruption

[edit]

Phthalates block CB1 as allosteric antagonists.[71]

Other effects

[edit]

There may be a link between the obesity epidemic and endocrine disruption and metabolic interference. Studies conducted on mice exposed to phthalates in utero did not result in metabolic disorder in adults.[72] However, "in a national cross-section of U.S. men, concentrations of several prevalent phthalate metabolites showed statistically significant correlations with abnormal obesity and insulin resistance."[72] Mono-ethylhexyl-phthalate (MEHP), a metabolite of DEHP, has been found to interact with all three peroxisome proliferator-activated receptors (PPARs).[72] PPARs are members of the nuclear receptor superfamily. The author of the study stated "The roles of PPARs in lipid and carbohydrate metabolism raise the question of their activation by a sub-class of pollutants, tentatively named metabolic disrupters."[72] Phthalates belong to this class of metabolic disruptors. It is a possibility that, over many years of exposure to these metabolic disruptors, they are able to deregulate complex metabolic pathways in a subtle manner.[72]

Large amounts of specific phthalates fed to rodents have been shown to damage their liver and testes,[49] and initial rodent studies also indicated hepatocarcinogenicity. Following this result, di(2-ethylhexyl) phthalate was listed as a possible carcinogen by IARC, EC, and WHO. Later studies on primates showed that the mechanism is specific to rodents; humans are resistant to the effect.[73] The carcinogen classification was subsequently withdrawn.

Environmental impact

[edit]

Phthalates are easily released into the environment. In general, they do not persist due to rapid biodegradation, photodegradation, and anaerobic degradation. Outdoor air concentrations are higher in urban and suburban areas than in rural and remote areas.[74] They also pose no acute toxicity.[36]

Because of their volatility, DEP and DMP are present in higher concentrations in air in comparison with the heavier and less volatile DEHP. Higher air temperatures result in higher concentrations of phthalates in the air. PVC flooring leads to higher concentrations of BBP and DEHP, which are more prevalent in dust.[74] A 2012 Swedish study of children found that phthalates from PVC flooring were taken up into their bodies, showing that children can ingest phthalates not only from food but also by breathing and through the skin.[75]

Diet is believed to be the main source of DEHP and other phthalates in the general population. Fatty foods such as milk, butter, and meats are a major source. Studies show that exposure to phthalates is greater from ingestion of certain foods, rather than exposure via water bottles as is most often first thought of with plastic chemicals.[76] Low-molecular-weight phthalates such as DEP, DBP, BBzP may be dermally absorbed. Inhalational exposure is also significant with the more volatile phthalates.[77]

Another study, conducted between 2003 and 2010 analysing data from 9,000 individuals, found that those who reported that they had eaten at a fast food restaurant had much higher levels of two separate phthalates—DEHP and DiNP—in their urine samples. Even small consumption of fast food caused higher presence of phthalates. "People who reported eating only a little fast food had DEHP levels that were 15.5 percent higher and DiNP levels that were 25 percent higher than those who said they had eaten none. For people who reported eating a sizable amount, the increase was 24 percent and 39 percent, respectively."[78]

In a 2008 Bulgarian study, higher dust concentrations of DEHP were found in homes of children with asthma and allergies, compared with healthy children's homes.[79] The author of the study stated, "The concentration of DEHP was found to be significantly associated with wheezing in the last 12 months as reported by the parents."[79] Phthalates were found in almost every sampled home in Bulgaria. The same study found that DEHP, BBzP, and DnOP were in significantly higher concentrations in dust samples collected in homes where polishing agents were used. Data on flooring materials was collected, but there was not a significant difference in concentrations between homes where no polish was used that have balatum (PVC or linoleum) flooring and homes with wood. High frequency of dusting did decrease the concentration.[79]

In general, children's exposure to phthalates is greater than that of adults. In a 1990s Canadian study that modeled ambient exposures, it was estimated that daily exposure to DEHP was 9 μg/kg bodyweight/day in infants, 19 μg/kg bodyweight/day in toddlers, 14 μg/kg bodyweight/day in children, and 6 μg/kg bodyweight/day in adults.[77] Infants and toddlers are at the greatest risk of exposure, because of their mouthing behavior. Body-care products containing phthalates are a source of exposure for infants. The authors of a 2008 study "observed that reported use of infant lotion, infant powder, and infant shampoo were associated with increased infant urine concentrations of [phthalate metabolites], and this association is strongest in younger infants. These findings suggest that dermal exposures may contribute significantly to phthalate body burden in this population." Although they did not examine health outcomes, they noted that "Young infants are more vulnerable to the potential adverse effects of phthalates given their increased dosage per unit body surface area, metabolic capabilities, and developing endocrine and reproductive systems."[80]

Infants and hospitalized children are particularly susceptible to phthalate exposure. Medical devices and tubing may contain 20–40% Di(2-ethylhexyl) phthalate (DEHP) by weight, which "easily leach out of tubing when heated (as with warm saline / blood)".[81] Several medical devices contain phthalates including, but not limited to, IV tubing, gloves, nasogastric tubes, and respiratory tubing. The Food and Drug Administration did an extensive risk assessment of phthalates in the medical setting and found that neonates may be exposed to five times greater than the allowed daily tolerable intake. This finding led to the conclusion by the FDA that, "[c]hildren undergoing certain medical procedures may represent a population at increased risk for the effects of DEHP".[81]

In 2008, the Danish Environmental Protection Agency (EPA) found a variety of phthalates in erasers and warned of health risks when children regularly suck and chew on them. The European Commission Scientific Committee on Health and Environmental Risks (SCHER), however, considers that, even in the case when children bite off pieces from erasers and swallow them, it is unlikely that this exposure leads to health consequences.[82]

Phthalates are also found in medications, where they are used as inactive ingredients in producing enteric coatings. It is not known how many medications are made using phthalates, but some include omeprazole, didanosine, mesalamine, and theophylline. A recent study found that urinary concentrations of monobutyl phthalate, the DBP metabolite, of Asacol (a particular formulation of mesalamine) users was 50 times higher than the mean of nonusers.[83] The study showed that exposures from phthalate-containing medications can far exceed population levels from other sources.[83] DBP in medications raises concern about health risks due to the high level of exposures associated with taking these medications, especially in vulnerable segments of the population, including pregnant women and children.[83]

In 2008, the United States National Research Council recommended that the cumulative effects of phthalates and other antiandrogens be investigated. It criticized U.S. EPA guidances, which stipulate that, when examining cumulative effects, the chemicals examined should have similar mechanisms of action or similar structures, as too restrictive. It recommended instead that the effects of chemicals that cause similar adverse outcomes should be examined cumulatively.[84] Thus, the effect of phthalates should be examined together with other antiandrogens, which otherwise may have been excluded because their mechanisms or structure are different.

[edit]

Canada

[edit]

In 1994, a Health Canada assessment found that DEHP and another phthalate product, B79P, were harmful to human health. The Canadian federal government responded by banning their use in cosmetics and restricting their use in other applications.[85]

A more recent assessment in 2017 found that B79P and DEHP may cause environmental damage. As of 2019, regulations to protect the environment against DEHP and B79P have not yet been put into place.[86]

European Union

[edit]
Update on non-classified plasticisers and the European REACH Candidate Classification including pending authorisation

The use of some phthalates has been restricted in the European Union for use in children's toys since 1999.[87] DEHP, BBP, and DBP are restricted for all toys; DINP, DIDP, and DNOP are restricted only in toys that can be taken into the mouth. The restriction states that the amount of these phthalates may not be greater than 0.1% mass percent of the plasticized part of the toy.

Generally, the high molecular weight phthalates DINP, DIDP, and DPHP have been registered under REACH and have demonstrated their safety for use in current applications. They are not classified for any health or environmental effects.

The low molecular weight products BBP, DEHP, DIBP, and DBP were added to the Candidate list of Substances for Authorisation under REACH in 2008-9, and added to the Authorisation list, Annex XIV, in 2012.[4] This means that from February 2015 they are not allowed to be produced in the EU unless authorisation has been granted for a specific use, however they may still be imported in consumer products.[88] The creation of an Annex XV dossier, which could ban the import of products containing these chemicals, was being prepared jointly by the ECHA and Danish authorities, and expected to be submitted by April 2016.[89]

In 2006 the Dutch office of Greenpeace UK sought to encourage the European Union to ban sex toys that contained phthalates.[90]

United States

[edit]

During August 2008, the United States Congress passed and President George W. Bush signed the Consumer Product Safety Improvement Act (CPSIA), which became public law 110-314.[91] Section 108 of that law specified that as of February 10, 2009, "it shall be unlawful for any person to manufacture for sale, offer for sale, distribute in commerce, or import into the United States any children's toy or child care article that contains concentrations of more than 0.1 percent of" DEHP, DBP, or BBP and "it shall be unlawful for any person to manufacture for sale, offer for sale, distribute in commerce, or import into the United States any children's toy that can be placed in a child's mouth or child care article that contains concentrations of more than 0.1 percent of" DINP, DIDP, DnOP. Furthermore, the law requires the establishment of a permanent review board to determine the safety of other phthalates. Prior to this legislation, the Consumer Product Safety Commission had determined that voluntary withdrawals of DEHP and diisononyl phthalate (DINP) from teethers, pacifiers, and rattles had eliminated the risk to children, and advised against enacting a phthalate ban.[92]

In another development in 1986, California voters approved an initiative to address their growing concerns about exposure to toxic chemicals. That initiative became the Safe Drinking Water and Toxic Enforcement Act of 1986, better known by its original name of Proposition 65.[93] In December 2013 DINP was listed as a chemical "known to the State of California to cause cancer"[94] This means that, starting December 2014, companies with ten or more employees manufacturing, distributing or selling the product(s) containing DINP are required to provide a clear and reasonable warning for that product. The California Office of Environmental Health Hazard Assessment, charged with maintaining the Proposition 65 list and enforcing its provisions, has implemented a "No Significant Risk Level" of 146 μg/day for DINP.[95]

Identification in plastics

[edit]
Some "Type 3" plastics contain PVC.[96]

Phthalates are used in some, but not all, PVC formulations, and there are no specific labeling requirements for phthalates. PVC plastics are typically used for various containers and hard packaging, medical tubing and bags, and are labeled "Type 3". However, the presence of phthalates rather than other plasticizers is not marked on PVC items. Only unplasticized PVC (uPVC), which is mainly used as a hard construction material, has no plasticizers. If a more accurate test is needed, chemical analysis, for example by gas chromatography or liquid chromatography, can establish the presence of phthalates.

Polyethylene terephthalate (PET, PETE, Terylene, Dacron) is the main substance used to package bottled water and many sodas. Products containing PETE are labeled "Type 1" (with a "1" in the recycle triangle). Although the word "phthalate" appears in the name, PETE does not use phthalates as plasticizers. The terephthalate polymer PETE and the phthalate ester plasticizers are chemically different substances.[97] Despite this, however, a number of studies have found phthalates such as DEHP in bottled water and soda.[98] One hypothesis is that these may have been introduced during plastic recycling.[98]

See also

[edit]

References

[edit]
  1. ^ "ACC Addresses Phthalates Safety" on YouTube: video of Steve Risotto of the American Chemistry Council, uploaded by user AmericanChemistry on 23 October 2009, retrieved 23 December 2011.
  2. ^ "phthalate". Oxford English Dictionary (Online ed.). Oxford University Press. (Subscription or participating institution membership required.)
  3. ^ "phthalate" in Collins English Dictionary
  4. ^ a b L 44, 18 February 2011 Regulation (EU) No 143/2011 of 17 February 2011 amending Annex XIV to Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals ('REACH')
  5. ^ "Phthalates | Assessing and Managing Chemicals Under TSCA". www.epa.gov. 2015-09-21. Retrieved 2017-04-07.
  6. ^ "Plasticizers – Study: Market, Analysis, Trends". Ceresana.
  7. ^ Helm D (2014). "The Greening of LVT: Mannington, Armstrong, Tarkett and others". Floor Daily.
  8. ^ "Interface Resilient Vinyl Flooring and Sustainability".
  9. ^ "Allura LVT".
  10. ^ Hansen OG (March 2020). "Make no mistake: PVC-based medical devices are fit for recycling". Plastics Today.
  11. ^ Wilkes CE, Summers JW, Daniels CA, Berard M (2005-01-01). PVC handbook. Hanser. ISBN 978-3446227149. OCLC 488962111.
  12. ^ Schwedler, Gerda; Rucic, Enrico; Lange, Rosa; Conrad, André; Koch, Holger M.; Pälmke, Claudia; Brüning, Thomas; Schulz, Christine; Schmied-Tobies, Maria I.H.; Daniels, Anja; Kolossa-Gehring, Marike (April 2020). "Phthalate metabolites in urine of children and adolescents in Germany. Human biomonitoring results of the German Environmental Survey GerES V, 2014–2017". International Journal of Hygiene and Environmental Health. 225: 113444. doi:10.1016/j.ijheh.2019.113444.
  13. ^ Kasper-Sonnenberg, Monika; Koch, Holger M.; Apel, Petra; Rüther, Maria; Pälmke, Claudia; Brüning, Thomas; Kolossa-Gehring, Marike (September 2019). "Time trend of exposure to the phthalate plasticizer substitute DINCH in Germany from 1999 to 2017: Biomonitoring data on young adults from the Environmental Specimen Bank (ESB)". International Journal of Hygiene and Environmental Health. 222 (8): 1084–1092. doi:10.1016/j.ijheh.2019.07.011.
  14. ^ Meeker JD, Sathyanarayana S, Swan SH (July 2009). "Phthalates and other additives in plastics: human exposure and associated health outcomes". Philosophical Transactions of the Royal Society of London. Series B, Biological Sciences. 364 (1526): 2097–2113. doi:10.1098/rstb.2008.0268. PMC 2873014. PMID 19528058.
  15. ^ Krauskopf, L. G. (September 1993). "Plasticizer structure/performance relationships". Journal of Vinyl and Additive Technology. 15 (3): 140–147. doi:10.1002/vnl.730150306.
  16. ^ a b Holland, Mike (6 June 2018). "Socio-economic assessment of phthalates". Organisation for Economic Co-operation and Development: 15. doi:10.1787/a38a0e34-en.
  17. ^ "TR 019 – An Assessment of Occurrence and Effects of Dialkyl-o-Phthalates in the Environment" (PDF). ECETOC. 29.05.1985. {{cite web}}: Check date values in: |date= (help)
  18. ^ "Search for Chemicals - ECHA". echa.europa.eu. European Chemicals Agency. Retrieved 9 June 2022. Enter CAS No's to validate manually
  19. ^ Zhang, Huawei; Hua, Yi; Chen, Jianwei; Li, Xiuting; Bai, Xuelian; Wang, Hong (3 July 2018). "Organism-derived phthalate derivatives as bioactive natural products". Journal of Environmental Science and Health, Part C. 36 (3): 125–144. doi:10.1080/10590501.2018.1490512.
  20. ^ Roy, Raj Narayan (2 October 2020). "Bioactive natural derivatives of phthalate ester". Critical Reviews in Biotechnology. 40 (7): 913–929. doi:10.1080/07388551.2020.1789838.
  21. ^ Tian, Congkui; Ni, Jinren; Chang, Fang; Liu, Sitong; Xu, Nan; Sun, Weiling; Xie, Yuan; Guo, Yongzhao; Ma, Yanrong; Yang, Zhenxing; Dang, Chenyuan; Huang, Yuefei; Tian, Zhexian; Wang, Yiping (April 2016). "Bio-Source of di-n-butyl phthalate production by filamentous fungi". Scientific Reports. 6 (1): 19791. doi:10.1038/srep19791.
  22. ^ Enikeev, A. G.; Semenov, A. A.; Permyakov, A. V.; Sokolova, N. A.; Gamburg, K. Z.; Dudareva, L. V. (May 2019). "Biosynthesis of Ortho-Phtalic Acid Esters in Plant and Cell Cultures". Applied Biochemistry and Microbiology. 55 (3): 294–297. doi:10.1134/S0003683819020066.
  23. ^ Latini, Giuseppe; De Felice, Claudio; Verrotti, Alberto (November 2004). "Plasticizers, infant nutrition and reproductive health". Reproductive Toxicology. 19 (1): 27–33. doi:10.1016/j.reprotox.2004.05.011.
  24. ^ Bi, Mengyan; Liu, Wei; Luan, Xiaoyu; Li, Muyang; Liu, Min; Liu, Wenqiu; Cui, Zhaojie (19 October 2021). "Production, Use, and Fate of Phthalic Acid Esters for Polyvinyl Chloride Products in China". Environmental Science & Technology. 55 (20): 13980–13989. doi:10.1021/acs.est.1c02374.
  25. ^ Semon, Waldo L.; Stahl, G. Allan (April 1981). "History of Vinyl Chloride Polymers". Journal of Macromolecular Science: Part A - Chemistry. 15 (6): 1263–1278. doi:10.1080/00222338108066464.
  26. ^ a b c Krauskopf, Leonard G. (2009). "3.13 Plasticizers". Plastics additives handbook (6. ed.). Munich: Carl Hanser Verlag. pp. 485–511. ISBN 978-3-446-40801-2.
  27. ^ Godwin, Allen (July 26, 2010). "Uses of Phthalates and Other Plasticizers" (PDF). U.S. Consumer Product Safety Commission (https://www.cpsc.gov/). ExxonMobil Chemical Company. Retrieved 19 May 2022. {{cite web}}: External link in |website= (help)
  28. ^ IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans Volume 29: Some industrial chemicals and dyestuffs (PDF). [Lyon]: International Agency for Research on Cancer. 1982. p. 271. ISBN 978-92-832-1229-4.
  29. ^ a b c "Market Report Plasticizers: Industry Analysis|Market Research". www.ceresana.com. Retrieved 19 May 2022.
  30. ^ Ventrice P, Ventrice D, Russo E, De Sarro G (July 2013). "Phthalates: European regulation, chemistry, pharmacokinetic and related toxicity". Environmental Toxicology and Pharmacology. 36 (1): 88–96. doi:10.1016/j.etap.2013.03.014. PMID 23603460.
  31. ^ David F. Cadogan and Christopher J. Howick "Plasticizers" in Ullmann's Encyclopedia of Industrial Chemistry 2000, Wiley-VCH, Weinheim. doi:10.1002/14356007.a20_439
  32. ^ Krauskopf, L. G. (2009). Plastics additives handbook (6. ed.). Munich: Carl Hanser Verlag. p. 495. ISBN 978-3-446-40801-2.
  33. ^ Cadogan, David F.; Howick, Christopher J. (15 June 2000). "Plasticizers". Ullmann's Encyclopedia of Industrial Chemistry. 27: 613–614. doi:10.1002/14356007.a20_439.
  34. ^ Koo, Hyun Jung; Lee, Byung Mu (December 2004). "ESTIMATED EXPOSURE TO PHTHALATES IN COSMETICS AND RISK ASSESSMENT". Journal of Toxicology and Environmental Health, Part A. 67 (23–24): 1901–1914. doi:10.1080/15287390490513300.
  35. ^ Hubinger, JC; Havery, DC (March 2006). "Analysis of consumer cosmetic products for phthalate esters". Journal of cosmetic science. 57 (2): 127–37. PMID 16688376.
  36. ^ a b Peter M. Lorz, Friedrich K. Towae, Walter Enke, Rudolf Jäckh, Naresh Bhargava, Wolfgang Hillesheim "Phthalic Acid and Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry, 2007, Wiley-VCH, Weinheim. doi:10.1002/14356007.a20_181.pub2
  37. ^ Al-Saleh, Iman; Elkhatib, Rola (January 2016). "Screening of phthalate esters in 47 branded perfumes". Environmental Science and Pollution Research. 23 (1): 455–468. doi:10.1007/s11356-015-5267-z. PMID 26310707. S2CID 22840018.
  38. ^ Brown, Margaret; Hebert, Adelaide A. (1997-02-01). "Insect repellents: An overview". Journal of the American Academy of Dermatology. 36 (2): 243–249. doi:10.1016/S0190-9622(97)70289-5. ISSN 0190-9622. PMID 9039177.
  39. ^ Karunamoorthi K, Sabesan S (May 2010). "Laboratory evaluation of dimethyl phthalate treated wristbands against three predominant mosquito (Diptera: Culicidae) vectors of disease". European Review for Medical and Pharmacological Sciences. 14 (5): 443–448. PMID 20556923.
  40. ^ Nathan, Sengottayan Senthil; Kalaivani, Kandaswamy; Murugan, Kadarkarai (October 2005). "Effects of neem limonoids on the malaria vector Anopheles stephensi Liston (Diptera: Culicidae)". Acta Tropica. 96 (1): 47–55. doi:10.1016/j.actatropica.2005.07.002. ISSN 0001-706X. PMID 16112073.
  41. ^ Kalyanasundaram, Muthuswami; Mathew, Nisha (2006-05-01). "N,N-Diethyl Phenylacetamide (DEPA): A Safe and Effective Repellent for Personal Protection Against Hematophagous Arthropods". Journal of Medical Entomology. 43 (3): 518–525. doi:10.1603/0022-2585(2006)43[518:NPDASA]2.0.CO;2. PMID 16739410.
  42. ^ Semon, Waldo L.; Stahl, G. Allan (April 1981). "History of Vinyl Chloride Polymers". Journal of Macromolecular Science: Part A - Chemistry. 15 (6): 1263–1278. doi:10.1080/00222338108066464.
  43. ^ US 1929453, Waldo Semon, "Synthetic rubber-like composition and method of making same", published 1933-10-10, assigned to B.F. Goodrich 
  44. ^ Methods for the determination of phthalates in food, (PDF) European Commission, Joint Research Centre Archived 20 July 2011 at the Wayback Machine
  45. ^ Edwards L, McCray NL, VanNoy BN, Yau A, Geller RJ, Adamkiewicz G, Zota AR (October 2021). "Phthalate and novel plasticizer concentrations in food items from U.S. fast food chains: a preliminary analysis". Journal of Exposure Science & Environmental Epidemiology. doi:10.1038/s41370-021-00392-8. PMID 34702987.
  46. ^ "Bio-based plasticizer". University of Minnesota. Archived from the original on 6 April 2012. Retrieved 7 October 2011.
  47. ^ LaMotte S (12 October 2021). "Synthetic chemical in consumer products linked to early death, study finds". CNN. Retrieved 2021-10-12.{{cite web}}: CS1 maint: url-status (link)
  48. ^ Pthalates Fact Sheet (PDF) (Report). Centers for Disease Control and Prevention. November 2009.
  49. ^ a b Third National Report on Human Exposure to Environmental Chemicals, (PDF) U.S. CDC, July 2005. Archived 1 April 2007 at the Wayback Machine
  50. ^ Swan SH, Main KM, Liu F, Stewart SL, Kruse RL, Calafat AM, et al. (Study for Future Families Research Team) (August 2005). "Decrease in anogenital distance among male infants with prenatal phthalate exposure". Environmental Health Perspectives. 113 (8): 1056–1061. doi:10.1289/ehp.8100. PMC 1280349. PMID 16079079.
  51. ^ Barrett ES, Parlett LE, Wang C, Drobnis EZ, Redmon JB, Swan SH (November 2014). "Environmental exposure to di-2-ethylhexyl phthalate is associated with low interest in sexual activity in premenopausal women". Hormones and Behavior. 66 (5): 787–792. doi:10.1016/j.yhbeh.2014.10.003. PMC 5035677. PMID 25448532.
  52. ^ a b c d Diamanti-Kandarakis E, Bourguignon JP, Giudice LC, Hauser R, Prins GS, Soto AM, et al. (June 2009). "Endocrine-disrupting chemicals: an Endocrine Society scientific statement". Endocrine Reviews. 30 (4): 293–342. doi:10.1210/er.2009-0002. PMC 2726844. PMID 19502515.
  53. ^ a b Zamkowska D, Karwacka A, Jurewicz J, Radwan M (July 2018). "Environmental exposure to non-persistent endocrine disrupting chemicals and semen quality: An overview of the current epidemiological evidence". International Journal of Occupational Medicine and Environmental Health. 31 (4): 377–414. doi:10.13075/ijomeh.1896.01195. PMID 30160090.
  54. ^ a b Bansal A, Henao-Mejia J, Simmons RA (January 2018). "Immune System: An Emerging Player in Mediating Effects of Endocrine Disruptors on Metabolic Health". Endocrinology. 159 (1): 32–45. doi:10.1210/en.2017-00882. PMC 5761609. PMID 29145569.
  55. ^ a b c d e f Braun JM (March 2017). "Early-life exposure to EDCs: role in childhood obesity and neurodevelopment". Nature Reviews. Endocrinology. 13 (3): 161–173. doi:10.1038/nrendo.2016.186. PMC 5322271. PMID 27857130.
  56. ^ Anway MD, Cupp AS, Uzumcu M, Skinner MK (June 2005). "Epigenetic transgenerational actions of endocrine disruptors and male fertility". Science. 308 (5727): 1466–1469. Bibcode:2005Sci...308.1466A. doi:10.1126/science.1108190. PMID 15933200. S2CID 236588.
  57. ^ Halpern DN (2018-09-04). "What Happens If We Hit Sperm Count Zero?". GQ. Retrieved 15 November 2018.
  58. ^ Belluz J (2018-09-17). "Sperm counts are falling. This isn't the reproductive apocalypse — yet". Vox. Retrieved 15 November 2018.
  59. ^ Salam M (2018-01-20). "Sperm Count in Western Men Has Dropped Over 50 Percent Since 1973, Paper Finds". The New York Times. ISSN 0362-4331. Retrieved 15 November 2018.
  60. ^ Hauser R, Calafat AM (November 2005). "Phthalates and human health". Occupational and Environmental Medicine. 62 (11): 806–818. doi:10.1136/oem.2004.017590. PMC 1740925. PMID 16234408.
  61. ^ a b Lyche JL, Gutleb AC, Bergman A, Eriksen GS, Murk AJ, Ropstad E, et al. (April 2009). "Reproductive and developmental toxicity of phthalates". Journal of Toxicology and Environmental Health Part B: Critical Reviews. 12 (4): 225–249. doi:10.1080/10937400903094091. PMID 20183522. S2CID 28086323.
  62. ^ Jurewicz J, Hanke W (June 2011). "Exposure to phthalates: reproductive outcome and children health. A review of epidemiological studies". International Journal of Occupational Medicine and Environmental Health. 24 (2): 115–141. doi:10.2478/s13382-011-0022-2. PMID 21594692.
  63. ^ Albert O, Jégou B (March 2014). "A critical assessment of the endocrine susceptibility of the human testis to phthalates from fetal life to adulthood". Human Reproduction Update. 20 (2): 231–249. doi:10.1093/humupd/dmt050. PMID 24077978.
  64. ^ Hannon PR, Flaws JA (2015-02-02). "The effects of phthalates on the ovary". Frontiers in Endocrinology. 6: 8. doi:10.3389/fendo.2015.00008. PMC 4313599. PMID 25699018.
  65. ^ Giulivo M, Lopez de Alda M, Capri E, Barceló D (November 2016). "Human exposure to endocrine disrupting compounds: Their role in reproductive systems, metabolic syndrome and breast cancer. A review". Environmental Research. 151: 251–264. Bibcode:2016ER....151..251G. doi:10.1016/j.envres.2016.07.011. PMID 27504873.
  66. ^ Factor-Litvak P, Insel B, Calafat AM, Liu X, Perera F, Rauh VA, Whyatt RM (10 December 2014). "Persistent Associations between Maternal Prenatal Exposure to Phthalates on Child IQ at Age 7 Years". PLOS ONE. 9 (12): e114003. Bibcode:2014PLoSO...9k4003F. doi:10.1371/journal.pone.0114003. PMC 4262205. PMID 25493564.
  67. ^ Balalian AA, Whyatt RM, Liu X, Insel BJ, Rauh VA, Herbstman J, Factor-Litvak P (April 2019). "Prenatal and childhood exposure to phthalates and motor skills at age 11 years". Environmental Research. 171: 416–427. Bibcode:2019ER....171..416B. doi:10.1016/j.envres.2019.01.046. PMC 6814270. PMID 30731329.
  68. ^ a b Engel SM, Patisaul HB, Brody C, Hauser R, Zota AR, Bennet DH, et al. (April 2021). "Neurotoxicity of Ortho-Phthalates: Recommendations for Critical Policy Reforms to Protect Brain Development in Children". American Journal of Public Health. 111 (4): 687–695. doi:10.2105/AJPH.2020.306014. PMC 7958063. PMID 33600256.
  69. ^ Factor-Litvak P, Insel B, Calafat AM, Liu X, Perera F, Rauh VA, Whyatt RM (2014-12-10). "Persistent Associations between Maternal Prenatal Exposure to Phthalates on Child IQ at Age 7 Years". PLOS ONE. 9 (12): e114003. Bibcode:2014PLoSO...9k4003F. doi:10.1371/journal.pone.0114003. PMC 4262205. PMID 25493564.
  70. ^ Dodson RE, Nishioka M, Standley LJ, Perovich LJ, Brody JG, Rudel RA (July 2012). "Endocrine disruptors and asthma-associated chemicals in consumer products". Environmental Health Perspectives. 120 (7): 935–943. doi:10.1289/ehp.1104052. PMC 3404651. PMID 22398195.
  71. ^ McPartland JM, Guy GW, Di Marzo V (12 March 2014). "Care and feeding of the endocannabinoid system: a systematic review of potential clinical interventions that upregulate the endocannabinoid system". PLOS ONE. 9 (3): e89566. Bibcode:2014PLoSO...989566M. doi:10.1371/journal.pone.0089566. PMC 3951193. PMID 24622769.
  72. ^ a b c d e Desvergne B, Feige JN, Casals-Casas C (May 2009). "PPAR-mediated activity of phthalates: A link to the obesity epidemic?". Molecular and Cellular Endocrinology. 304 (1–2): 43–48. doi:10.1016/j.mce.2009.02.017. PMID 19433246. S2CID 12880759.
  73. ^ "Chronic Hazard Advisory on Diisononyl Phthalate" (PDF). 2001. p. 87. Archived from the original (PDF) on 2008-10-05. Retrieved 2009-01-31. Human risk is therefore seen as negligible
  74. ^ a b Rudel RA, Perovich LJ (January 2009). "Endocrine disrupting chemicals in indoor and outdoor air". Atmospheric Environment. 43 (1): 170–181. Bibcode:2009AtmEn..43..170R. doi:10.1016/j.atmosenv.2008.09.025. PMC 2677823. PMID 20047015.
  75. ^ Carlstedt F, Jönsson BA, Bornehag CG (February 2013). "PVC flooring is related to human uptake of phthalates in infants". Indoor Air. 23 (1): 32–39. doi:10.1111/j.1600-0668.2012.00788.x. PMID 22563949.
  76. ^ Erythropel HC, Maric M, Nicell JA, Leask RL, Yargeau V (December 2014). "Leaching of the plasticizer di(2-ethylhexyl)phthalate (DEHP) from plastic containers and the question of human exposure". Applied Microbiology and Biotechnology. 98 (24): 9967–9981. doi:10.1007/s00253-014-6183-8. PMID 25376446. S2CID 11715151.
  77. ^ a b Heudorf U, Mersch-Sundermann V, Angerer J (October 2007). "Phthalates: toxicology and exposure". International Journal of Hygiene and Environmental Health. 210 (5): 623–634. doi:10.1016/j.ijheh.2007.07.011. PMID 17889607.
  78. ^ Zota AR, Phillips CA, Mitro SD (October 2016). "Recent Fast Food Consumption and Bisphenol A and Phthalates Exposures among the U.S. Population in NHANES, 2003-2010". Environmental Health Perspectives. 124 (10): 1521–1528. doi:10.1289/ehp.1510803. PMC 5047792. PMID 27072648.
  79. ^ a b c Kolarik B, Bornehag CG, Naydenov K, Sundell J, Stavova P, Nielsen OF (December 2008). "The concentrations of phthalates in settled dust in Bulgarian homes in relation to building characteristic and cleaning habits in the family". Atmospheric Environment. 42 (37): 8553–8559. Bibcode:2008AtmEn..42.8553K. doi:10.1016/j.atmosenv.2008.08.028.
  80. ^ Sathyanarayana S, Karr CJ, Lozano P, Brown E, Calafat AM, Liu F, Swan SH (February 2008). "Baby care products: possible sources of infant phthalate exposure". Pediatrics. 121 (2): e260–e268. doi:10.1542/peds.2006-3766. PMID 18245401. S2CID 22218732.
  81. ^ a b Sathyanarayana S (February 2008). "Phthalates and children's health". Current Problems in Pediatric and Adolescent Health Care. 38 (2): 34–49. doi:10.1016/j.cppeds.2007.11.001. PMID 18237855.
  82. ^ Opinion on phthalates in school supplies (PDF) (Report). Scientific Committee on Health and Environmental Risks, European Commission. 17 October 2008.
  83. ^ a b c Hernández-Díaz S, Mitchell AA, Kelley KE, Calafat AM, Hauser R (February 2009). "Medications as a potential source of exposure to phthalates in the U.S. population". Environmental Health Perspectives. 117 (2): 185–189. doi:10.1289/ehp.11766. PMC 2649218. PMID 19270786.
  84. ^ National Research Council (US) Committee on the Health Risks of Phthalates (2008-12-18). Phthalates and Cumulative Risk Assessment: The Tasks Ahead. National Research Council. doi:10.17226/12528. ISBN 9780309128414. PMID 25009926.
  85. ^ "Phthalates". Government of Canada. 6 October 2017. Retrieved 11 July 2019.
  86. ^ "Phthalate Substance Grouping – information sheet". canada.ca. Government of Canada. 12 March 2017. Retrieved 11 July 2019.
  87. ^ Commission Decision of 7 December 1999 adopting measures prohibiting the placing on the market of toys and childcare articles intended to be placed in the mouth by children under three years of age made of soft PVC containing one or more of the substances di-iso-nonyl phthalate (DINP), di(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), di-iso-decyl phthalate (DIDP), di-n-octyl phthalate (DNOP), and butylbenzyl phthalate (BBP)
  88. ^ "Echa and Denmark to prepare phthalates restriction".
  89. ^ "Registry of Intentions - ECHA".
  90. ^ Ms. KFT Retrieved 22 December 2014 Archived 15 September 2014 at archive.today
  91. ^ GovTrack.us. "H.R. 4040--110th Congress (2007): Consumer Product Safety Improvement Act of 2008, GovTrack.us (database of federal legislation). Retrieved 14 August 2009.
  92. ^ Public Concern, Not Science, Prompts Plastics Ban by Jon Hamilton, NPR.
  93. ^ "OEHHA Proposition 65: Proposition 65 in Plain Language!". ca.gov.
  94. ^ "OEHHA Proposition 65 (2013) Diisononyl Phthalate (DINP) listed". ca.gov.
  95. ^ "Current Proposition 65 No Significant Risk Levels (NSRLs) Maximum Allowable Dose Levels (MADLs)". California Office of Environmental Health Hazard Assessment. October 1, 2021. Retrieved March 23, 2022.{{cite web}}: CS1 maint: url-status (link)
  96. ^ "Types of Plastic - I-Cycle". www2.illinois.gov. Retrieved 2022-03-23.
  97. ^ "Learn the Facts About Food Packaging and Phthalates". Plasticsmythbuster.org. Archived from the original on 6 July 2009. Retrieved 2013-09-23.
  98. ^ a b Sax L (April 2010). "Polyethylene terephthalate may yield endocrine disruptors". Environmental Health Perspectives. 118 (4): 445–448. doi:10.1289/ehp.0901253. PMC 2854718. PMID 20368129.

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