Plasticizers: Types, Uses, Classification, Selection & Regulation

What are plasticizers?

Plasticizers are non-volatile organic substances (mainly liquids) added into a plastic or elastomer. They are also usually cheaper than other additives. They improve the following properties of the polymers:

Flexibility - Makes the product softer
Extensibility - Do not break easily at cold temperatures
Processability - Becomes easier and possible to process

Plasticizers increase the flow and thermoplasticity of a polymer. This is done by decreasing the viscosity of the polymer melt, Tg, Tm, and elastic modulus of the finished product. During this process, the fundamental chemical character of the plasticized material remains unaltered.

Plasticizers are most often used in Polyvinyl chloride. PVC plastic is the third largest polymer by volume after PP and PE. Unplasticized PVC (or rigid PVC) is used in pipes, siding, and window profiles. Whereas plasticized PVC (or flexible PVC) is used in automotive interior trim, cables, PVC films, flooring, roofing, wall coverings, etc.

Methods of plasticization

Plasticization is the process of making the final plastic product more flexible. By incorporating the right type and amount of plasticizer you can tweak your formulation. Hence, selecting the right plasticizer for a specific application is very critical to make the product softer. Plasticization can occur both internally and externally. Below is a pictorial representation of the types of plasticization.

Internal plasticization

A polymer can be internally plasticized by chemically modifying the polymer or monomer. This increases flexibility. It involves copolymerization of the monomers of the desired polymer (having high Tg) and that of the plasticizer (having low Tg) so that the plasticizer is an integral part of the polymer chain. The most used internal plasticizer monomers are:

Vinyl acetate
Vinylidene chloride

But this technique is limited: every copolymer is only suited to certain flexibility requirements

Also, the complexity of the reaction can lead to longer reaction times and increased costs. Internally plasticized materials show temperature dependence and dimensional instability at high temperatures.

External plasticization

This is the most commonly used method of plasticization. This is because low-cost liquid plasticizers give the formulator freedom in developing formulations. They range from semi-rigid to highly flexible depending on the quantity). Examples include esters formed from the reaction of acids or acid anhydrides with alcohols. There are two main groups of external plasticizers:

A primary plasticizer enhances elongation, softness and flexibility of polymer. They are highly compatible with polymers and can be added in large quantities. For example: up to 50% of vinyl gloves are made up of plasticizers, which make the PVC flexible and soft enough to wear.

A secondary plasticizer is one that typically cannot be used as the sole plasticizer in a plasticized polymer. Secondary plasticizers may have limited compatibility with the polymer and/or high volatility. They may or may not contain functional groups which allow them to solvate the polymer at processing temperatures. Secondary plasticizers are variously used for:
- Cost reduction
- Viscosity reduction
- Solvency enhancement
- Surface lubricity augmentation, and
- Low temperature property improvement
Extenders are a subset of secondary plasticizers. They are commonly employed with primary plasticizers to reduce costs in general purpose flexible PVC. They are mostly low-cost oils having limited compatibility in PVC. They are added to reduce cost and, in some cases, to improve fire resistance. Examples of extenders include:
- Naphthenic hydrocarbons
- Aliphatic hydrocarbons
- Chlorinated paraffins (fire resistance), and others

Select from a range of 1700+ commercially available plasticizers in our database

Ways to process plasticizers

Suspension PVC (S-PVC) process is the common method of manufacturing PVC. The PVC is obtained in the form of particles with sizes 50-200 microns. These particles are mixed with plasticizers & can be extruded in pellets. They are further used for processing via extrusion, calendaring, and injection molding. The processing equipment for this process is typically very expensive. It provides lower flexible PVC formula costs.

The incorporation of an external plasticizer in PVC polymer enhances its flexibility. Five distinct steps involved while adding plasticizers include:

STEP 1: Plasticizer is mixed with resin

STEP 2: Plasticizer penetrates and swells the resin particles

STEP 3: Polar groups in the PVC resin are freed from each other

STEP 4: Plasticizer polar groups interact with the polar groups on the PVC chain

STEP 5: PVC structure is re-established upon cooling with full retention of plasticizer

Loss of plasticizers/plasticizer exudation

The incompatibility between polymer and plasticizer can cause exudation. Several factors can lead to the migration of plasticizers including:

Temperature
Humidity
Mechanical stress, and
Weathering

The migration can happen out of plastic's surface, into or onto a substrate to which it is held in intimate contact. The loss of plasticizer can lead to less flexibility, embrittlement, and cracking.

What are the main types of plasticizers?

Plasticizers are classified based on their chemical composition. It is important to understand the influence of structural elements on the properties of plasticizers and their effect on base polymers. For example, the presence of elements like alcohols in a homologous series of phthalates, and adipates.

Different plasticizers affect different physical and chemical properties of materials. Thus, you need a particular plasticizer to change properties to meet end-user requirements.

Several chemical families of plasticizers are used for polymer modification. Among them, the most common are:

Phthalate Esters – Produced by esterification of phthalic anhydride or phthalic acid. Obtained by the oxidation of orthoxylene or naphthalene. Most commonly used phthalate plasticizers include:
1. DEHP: Low molecular weight ortho-phthalate. Still the world’s most widely used PVC plasticizer
2. DINP, DIDP: High molecular weight ortho-phthalates

Aliphatic dibasic acid Esters – These include chemicals such as glutarates, adipates, azelates and sebacates. Made from aliphatic dibasic acids such as adipic acid and alcohols.

Benzoate Esters – They are esterification products of benzoic acid and selected alcohols or diols.

Trimellitate Esters – Produced by esterification of trimellitic anhydride (TMA) and typically C8 – C10 alcohols.

Polyesters – Formed by the reaction of many combinations of dicarboxylic acids and difunctional alcohols.

Citrates – They are tetraesters, resulting from the reaction of one mole of citric acid with three moles of alcohol. Citric acid’s lone hydroxyl group is acetylated.

Bio-based Plasticizers – They are based on epoxidized soybean oil (ESBO), epoxidized linseed oil (ELO), castor oil, palm oil, other vegetable oils, starches, sugars etc.

Others – Includes phosphates, chlorinated paraffins, alkyl sulfonic acid esters, and more

Phthalate Plasticizers

Phthalates are produced by the esterification of phthalic anhydride. The phthalic anhydride is obtained by the oxidation of orthoxylene.

Dioctyl Terephthalate (DOTP, DEHT) Plasticizer Molecule

Phthalates appear colorless with a faint odor. They have limited solubility in water. But are miscible in many organic solvents (mineral oil etc.). Key benefits and limitations of phthalate plasticizers include:

Benefits	Limitations
They are the conventional choice as they resist extraction, evaporation and migration Phthalates offer durability, flexibility, weather resistance and are able to withstand high temperatures Phthalates are economical when compared to other plasticizers	In polymers like PVC, phthalates do not bind chemically and leach out of plastics, leading to their occurrence in the environment Some phthalate plasticizers can pose serious risks to health as they are carcinogens and/or developmental toxins Certain phthalates can accumulate at low levels in the human body

Sub-categories of phthalate plasticizers

Di-2-ethylhexyl-phthalate (DEHP)

Di-2-ethylhexyl-phthalate (DEHP) is a low molecular weight ortho-phthalate. It has a chemical formula of C₆H₄(C₈H₁₇COO)₂. It is produced by the esterification of phthalic anhydride with 2-ethyl-hexanol. It is a non-volatile, colorless, and odorless viscous liquid, soluble in oil, but not in water. Due to its low cost and generally good performance, DEHP is widely employed as a plasticizer in manufacturing articles made of PVC.

Melting point: −50°C
Boiling point: 250 - 257°C at 0.5 kPa

Structure of DEHP

DEHP offers good gelling, satisfactory electrical properties and helps to produce highly elastic compounds with reasonable cold strength. It displays fairly good flexibility at low temperatures and some resistance to high temperature.

However, DEHP is listed by the IARC as a human carcinogen. DEHP has been implicated as a hormone mimicker and as a developmental toxin in certain studies. In the EU, DEHP is considered an SVHC (substance of very high concern) under REACH legislation. It cannot be used in most products. It extracts readily into non-polar solvents (oils and fats in foods packed in PVC). Therefore, the US Food and Drug Administration (FDA) permits the use of DEHP-containing packaging only for foods that predominantly consist of water.

DEHP is used in applications, such as:

Manufacturing articles made of PVC, copolymers of vinyl chloride and vinyl acetate
Medical devices like catheter, tubing, etc.
In developing various formulations ranging from glassy compositions to soft and highly flexible materials
Use is decreasing due to concern about its effects on human health, but DEHP is still the most widely used plasticizer in the world

DEHP has been progressively deselected for technical reasons such as loss of performance over time, regulation, etc. It is also substituted by terephthalate plasticizers, DINP and DIDP.

Diisononyl phthalate (DINP)

Diisononyl phthalate (DINP) is a high molecular weight ortho-phthalate. Its chemical formula is C₂₆H₄₂O₄. It is produced by the esterification of phthalic anhydride with isononyl alcohol in a closed system. It is an almost colorless and odorless oily liquid. It is very slightly soluble in water. But soluble in alcohols, hexane, etc. It is miscible and compatible with all the monomeric plasticizers used in PVC compounding.

Melting point: −43°C (−45°F; 230 K)
Boiling point: 244-252°C at 0.7 kPa
Flash point: 221°C (c.c.)

Structure of DINP

Diisononyl phthalate offers flexibility and durability to vinyl products. It also provides good performance at both low and high temperatures. It is less volatile than DEHP. Its good solvency leads to good flexible PVC processing characteristics.

DINP plasticizers are employed extensively in indoor and outdoor applications. Being less volatile, it is found effective in applications where products are exposed to relatively high temperatures and need more resistance to degradation. DINP helps vinyl products in the following ways:

It withstands many weather conditions.
It makes them water resistant.
It provides them with high thermal insulation and durability.

DINP is combined with PVC powder by flooring manufacturers to produce soft and flexible finished products.

Diisodecyl phthalate (DIDP)

Diisodecyl phthalate (DIDP) is a high molecular weight ortho-phthalate. Its chemical formula is C₂₈H₄₆O₄. It is a blend of compounds derived from the esterification of phthalic acid and isomeric decyl alcohols. It is a clear, colorless, and odorless liquid. It is soluble in most organic solvents but insoluble in water. DIDP is widely used in wire and cable formulations. It also manufactures automotive interior trims. They are also suitable for coatings for furnishings, cookware, pharmaceutical pills, food wrappers, and many other items.

Melting point: −50°C
Boiling point: 250–257°C at 0.5 kPa

Structure of DIDP

DIDP plasticizer increases the flexibility of the plastic/ plastic coating. They are more permanent (less volatile, less water extractable) than DINP. Its good heat stability and electric insulation make it a preferred choice for:

heat-resistant electrical cords,
car interiors, and
PVC flooring.

However, the branched alkyl chain structure of DIDP makes it susceptible to oxidation at higher temperatures which may lead to PVC degradation. It has a lower plasticizing efficiency than DOP. It needs to be used in higher concentrations to give an ideal plasticizing effect.

Dibutyl phthalate (DBP)

Dibutyl phthalate (DBP) is produced from n-butanol and isobutanol, respectively, which are the co products when 2-ethylhexanol is manufactured. It has a chemical formula of C₁₆H₂₂O₄. It is colorless to faint yellow in appearance. DBP is typically used in blends with other plasticizers as a solvency booster in flexible PVC compounds which have a low processing temperature requirement.

Melting point: −35°C (−31°F; 238 K)
Boiling point: 340°C (644°F; 613 K)
Flash point: 157°C (closed cup)

Structure of DBP

However, their low molecular weight makes them too volatile for most of the applications. It was found that the PVC glazing seals used as agricultural films gave off vapors of DBP. These were harmful to a certain variety of greenhouse crops.

Browse commercial grades of phthalate plasticizers in our database.

Other phthalates

Note that isoalkyl phthalates (e.g., DIOP, DIUP, DTDP) do not have a methyl branch on the penultimate carbon of the alkyl chain. For alkyl groups containing 6 or more carbons the “iso” prefix, by convention, simply means “branched”.

See structures in the following table.

Other Phthalate Plasticizers Used in Polymers

Butyl Benzyl Phthalate (C₁₉H₂₀O₄)

MP: -35°C (-31°F; 238 K)
BP: 370°C (698°F; 643 K)

It is an ester of phthalic acid, benzyl alcohol and n-butanol. This phthalate is frequently used as a plasticizer for vinyl foams, which are often used as vinyl floor coverings/ tiles and in the automotive industry.

Diisoheptyl phthalate (DIHP, C₂₂H₃₄O₄)

MP: -35°C (-31°F; 238 K)
BP: 370°C (698°F; 643 K)

Diisoheptyl phthalate consists of chemical compounds containing various isoheptyl esters of phthalic acid.

Dihexyl phthalate (DHP, C₆H₄(COOC₆H₁₃)₂)

MP: -28 to -27°C
BP: 350°C

Alkyl sidechains may contain some branching

Diisooctyl phthalate(DIOP, C₂₄H₃₈O₄)

MP: -28 to -27°C
BP: 350°C

It is a clear oily liquid with a slight odor and is denser and partially soluble in water. It is obtained by reaction of phthalic anhydride with iso- octanol in the presence of an acid catalyst.

Di-iso-undecyl phthalate (DIUP)

MP: -28 to -27°C
BP: 350°C

DIUP is a high molecular weight phthalate. Being nonvolatile, it is widely employed for high temperature applications like insulating heat resistant cables. DIUP is less susceptible to fogging than DEHP

Dimethyl phthalate (DMP, C₁₀H₁₀O₄)

MP: 2°C (36°F; 275 K)
BP: 283 to 284°C

DMP is a dimethyl ester of 1,2- benzenedicarboxylic acid. It is a colorless liquid with a slight aromatic odor

Diisotridecyl phthalate (DTDP, C₃₄H₅₈O₄)

MP: -28 to -27°C
BP: 350°C

DTDP is the highest weight dialkyl phthalate to be used as a plasticizer. It was widely used as a high temperature plasticizer for PVC until trimellitates came into existence. It needs high processing temperatures for compounding with PVC.

Applications

Cost: Phthalates are used as PVC plasticizers since the earliest days of flexible PVC. These plasticizers are both inexpensive and effective. The collapse of oil prices began in 2015. This further reduced the price of petrochemicals, including phthalate esters. Some phthalate is replaced by notably bio-based products. These alternatives have seen increasing feedstock prices over time. This widens an already present cost differential.

Performance: Phthalate replacement products have processability and permanence limitations.

Supply: The worldwide plasticizer market is quite large, with over 7 million tons per year. There’s not enough manufacturing capacity to produce large volumes of phthalate replacements.
1. In electrical and electronic applications, they are used for insulating wires and cables.
2. Phthalate plasticizers are widely used in vinyl-based building materials. These include floorings and wall coverings. They provide them with flexibility and durability.

Regulations

2001-2006 – DINP and DIDP Are Safe for Use in Current Applications

The risk assessment results show that DINP and DIDP pose no risk to human health or the environment in any of their current applications.

2012 – Australia Risk Assessment Confirms DIDP & DINP Safe for Toys – NICNAS Report

The Australian Government Department of Health and Aging reported the following. The current exposures to DINP do not indicate a health concern for children even at the highest exposure levels. These exposures have no restrictions on the use of DINP in toys and child-care articles.

2013 – EC Confirms Safe Use of DINP and DIDP in all current consumer applications – EC Report

The European Commission (EC) has re-evaluated the restriction on plasticizers DINP and DIDP. They concluded that:

No unacceptable risk has been characterized for the uses of DINP and DIDP in articles that can be placed in the mouth.
The evaluation of potential substitutes has been less pertinent due to the absence of any further risks from the uses of DINP and DIDP.

2014 – US CHAP Lifted Ban on DIDP, DNOP and Prohibits >0.1% level of DINP in Child Care Products

U.S. Consumer Product Safety Commission (CPSC) established a Chronic Hazard Advisory Panel (CHAP). This panel studies and reviews the potential adverse effects of phthalates used in child care articles on children’s health. This was done under section 108 of the Consumer Product Safety Improvement Act of 2008:

Three types of phthalates (DEHP, DBP, BBP) are banned permanently in any amount greater than 0.1% in children’s toys and certain child care articles.
Three additional types of phthalates (DINP, DIDP, DNOP) were banned on an interim basis in any amount greater than 0.1%.

CHAP provided its report and recommended the following actions:

Permanent ban on DBP, BBP, and DEHP remains unchanged. Additionally, DIBP, DPENP, DHEXP, and DCHP at levels greater than 0.1% are to be added to the existing permanently prohibited list.
Interim Ban on DINP at levels greater than 0.1% in children’s toys and child care articles to be made permanent.
Current bans on DNOP and DIDP be lifted
Use DIOP on an interim basis until sufficient data are available. This was done to determine whether a permanent restriction is necessary.
No action on DMP, DEP, and DPHP at this time but it did encourage appropriate agencies to gather necessary exposure and hazard data. This was done to estimate total exposure to the phthalate alternatives and assess the potential health risks.

There were also efforts early in the Obama administration to further regulate phthalates. This took place under the authority of legislation passed in 1976, the Toxic Substances Control Act (See TSCA sec 5b). However, this was never done.

2017 – Danish EPA Proposal on DINP

Following the fourth re-submission in two years, the Danish EPA dossier proposed the classification of DINP as a reproductive agent. It was accepted by ECHA and the public consultation was initiated in April 2017. Through extensive prior testing, regulatory evaluations, and peer-reviewed published scientific reviews the scientific data does not support this classification proposal.

2018 – ECHA RAC Concludes DINP Requires No Classification – ECHA News

ECHA’s Risk Assessment Committee (RAC) has concluded that Di-isononyl phthalate (DINP) does not warrant classification for reprotoxic effects under the EU’s Classification, Labelling and Packaging (CLP) regulation.

RAC undertook a stringent hazard assessment following the rules of the CLP regulation, with the conclusion that, given the lack of evidence of adverse effects, classification is not required. Amongst prior regulatory assessments, the ECHA evaluation of new scientific evidence – endorsed by the European Commission in 2014 – concluded that DINP can be safely used in all current applications. All relevant data are included in the DINP REACH registration dossiers, which were updated in 2015 and 2016.

Criteria for Phthalate Replacement

The choice of phthalate replacement is usually based on several criteria like:

Cost
Expected exposure conditions of finished product during its service life. These include compatibility, outdoor weatherability, low-temperature flexibility, etc.
Processing condition limitations like low processing temperatures or high processing rates

The type of plasticizers which can be used to overcome these issues are listed below.

Criteria for Phthalate Replacement	Examples of Alternative Plasticizers
Cost	Ring saturated phthalates DOTP Certain vegetable oil derivatives (e.g., ESBO)
Compatibility	Benzoates/dibenzoates Alkyl sulfonic acid esters Trimellitates
Outdoor weatherability	Trimellitates Alkyl sulfonic acid esters (depending on severity of expected service life)
Low temperature flexibility	Esters of aliphatic dibasic acids Some vegetable oil derivatives (e.g., acetylated monoglyceride esters, monoesters of fatty acids)
Plasticizer solvency	Benzoates/dibenzoates Some vegetable oil derivatives (e.g., acetylated monoglyceride esters, monoesters of fatty acids) TXIB
Flame retardancy	Phosphate esters (only)
High temperature service	Trimellitates Some vegetable oil derivatives (e.g., Dow Ecolibrium products)
Low plastisol viscosity	Benzoate esters (not dibenzoates) TXIB Esters of aliphatic dibasic acids
Solvent extraction resistance	Polyesters
Hydrolysis resistance	Alkyl sulfonic acid esters

Which alternative plasticizer should you select?

Terephthalate plasticizers

Terephthalate esters, particularly di-2-ethylhexyl terephthalate, are the most popular replacements for DEHP. They are less compatible with PVC. But their low cost and long history as commercial plasticizers are their most attractive features.

Dialkyl terephthalates with sidechains containing:

More than 8 carbon atoms have limited compatibility with PVC.
Fewer than 8 carbon atoms have volatility issues.

Cost	Low
Compatibility with the PVC polymer	Fair
Outdoor weatherability	Fair
Low temperature flexibility	Good
Plasticizer solvency	Fair to Good
Bio-based content	Typically None
Flame retardancy	Poor
High temperature service	Fair
Low plastisol viscosity	Good
Solvent extraction resistance	Poor
Hydrolysis resistance	Fair

Adipates

In PVC applications, adipates offer enhanced low-temperature properties. This is in comparison to phthalates of similar alkyl chain length. They are more volatile and exhibit poorer fusion and compatibility with PVC. This means they possess higher migration rates.

They are expensive relative to some other alternative plasticizers.
Generally used in blends with higher phthalates to deliver optimum plasticizing properties.

Polymeric plasticizers are typically made from aliphatic dibasic acids such as adipic acid and diols. They are primarily valued for their permanence. These plasticizers are generally classified as polyesters, not adipates.

Many have low solvency for PVC and high viscosity. Both these factors can make processing f-PVC compounds difficult.
Many have poor low-temperature properties and may be sensitive to moisture.

Check out the table below for the benefits of polymeric plasticizers.

Cost	Moderately High
Compatibility with the PVC polymer	Fair to Good
Outdoor weatherability	Fair to poor
Low temperature flexibility	Good
Plasticizer solvency	Fair
Bio-based content	None
Flame retardancy	Poor
High temperature service	Fair to poor
Low plastisol viscosity	Good
Solvent extraction resistance	Fair to good
Hydrolysis resistance	Fair

Benzoates

Benzoate and dibenzoate esters are highly solvating plasticizers for PVC. Because of their high volatility, monobenzoates are typically used only as:

solvency boosting or
viscosity depressing additives in flexible PVC.

Dibenzoate plasticizers are valued primarily for their strong solvency. But they are defensive against phthalate plasticizers. This is because of reduced low-temperature flexibility and poor plastisol viscosity characteristics. Both plasticizers are often used in blends with other plasticizers.

Benzoates also act as processing aids. They offer optimum performance in PVC and other thermoplastic polymers. Many applications use benzoates as part of a plasticizer blend. This is done to diminish the challenges faced during processing.
They display:

good UV stability,
excellent stain resistance,
good oil extraction resistance as well as
high solvating power.

Low molecular weight gives these plasticizers processing advantages by lowering the processing temperatures. However, benzoates are highly volatile in nature. There are many unique chemistries with differentiated performance. Benzoates (especially dibenzoates) are used in some flexible PVC flooring (resilient flooring).

Some common benefits and limitations of benzoate/dibenzoate esters can be found in the table below.

Cost	Moderate
Compatibility with the PVC polymer	Good
Outdoor weatherability	Poor to Good
Low temperature flexibility	Poor to Good
Plasticizer solvency	Excellent
Bio-based content	Typically none
Flame retardancy	Poor
Low plastisol viscosity	Poor to good
Solvent extraction resistance	Poor to fair
Hydrolysis resistance	Fair

Citrates

Citrate esters are used in many f-PVC toys. They are valued because:

They are “natural” products that may have partial to high bio-based content. This depends on how they are made.
They are non-toxic and provide heat and light stability.
They have some direct and indirect food additive clearances in PVC.
They offer good performance and excellent flexibility at low temperatures.

However, citrate plasticizers are highly volatile and a significant amount is lost due to this property. Citrates lack permanency. Hence, they are not employed in resilient applications like cables, flooring, or roofing. They induce more fogging in film applications.

Citrates/Citric acid esters are used to plasticize vinyl resins in toys, medical devices, and pacifiers for infants. Being FDA-approved, citrates find uses in food packaging film applications and pharmaceutical preparations. They are compatible with polymers like PVC, PVA, PVB, and polypropylene. Esters of citric acid are also used as foam inhibitors. Some typical features of citrates are mentioned in the table below.

Cost	High
Compatibility with the PVC polymer	Fair
Outdoor weatherability	Fair to poor
Low temperature flexibility	Fair to Good
Plasticizer solvency	Fair
Bio-based content	None to High
Flame retardancy	Poor
High temperature service	Poor to Fair
Low plastisol viscosity	Poor to Fair
Solvent extraction resistance	Fair
Hydrolysis resistance	Poor to Fair

Phosphates

Phosphate ester plasticizers are used primarily to impart flame retardancy to f-PVC. Some phosphate plasticizers are also used to improve UV light (outdoor weatherability). They are not typically used as primary plasticizers for PVC.

Triaryl and alkyl diaryl phosphates are the most important category of flame-retardant phosphate plasticizers used with PVC. They specifically achieve flame retardancy and/or low smoke generation. Phosphates are primary plasticizers for PVC. They can be utilized as sole plasticizers or in a cost-optimized blend.

Triaryl phosphates show excellent flame retardancy with low volatility. However, they have poorer low-temperature flexibility.
Alkyl diaryl phosphate esters have good low-temperature flexibility. But are more volatile and offer poorer flame retardancy than the triaryl esters.

Some phosphates have cited approval in food and medical device regulations.

Cost	High
Compatibility with the PVC polymer	Good
Outdoor weatherability	Fair to Good
Low temperature flexibility	Poor to Fair
Plasticizer solvency	Good
Bio-based content	None
Flame retardancy	Good
High temperature service	Fair
Low plastisol viscosity	Good
Solvent extraction resistance	Poor
Hydrolysis resistance	Fair

Chlorinated paraffins

Chlorinated paraffins are obtained by the chlorination of hydrocarbons. They consist of 30-70% chlorine. They act as flame retardants due to the presence of chlorine.

They have low volatility.
They offer high chemical stability and moisture resistance.
They are thermally unstable. This limits their applications to processing temperatures (within 175°C).

Therefore, for higher processing temperatures, the addition of other stabilizers is required. Higher the chlorine content, weaker the plasticizing effect of chlorinated paraffin for PVC.

Ring saturated variants of phthalate esters (e.g. DINCH)

Plasticizers like DINCH (di-isononyl ester of cyclohexane-1,2-dioc acid) look like phthalates. They do not have any (proven) adverse effects on human health.

They have relatively low solvating strength for PVC.
Their compatibility with PVC is defensive to that of their phthalate analogs.

Higher MW versions of ring-saturated dialkyl phthalates are increasingly incompatible with PVC.

Cost	Moderate
Compatibility with the PVC polymer	Fair
Outdoor weatherability	Fair
Low temperature flexibility	Good
Plasticizer solvency	Fair
Bio-based content	None
Flame retardancy	Poor
High temperature service	Poor
Low plastisol viscosity	Good
Solvent extraction resistance	Poor
Hydrolysis resistance	Fair

Alkyl sulfonic acid esters

Alkyl sulfonic acid esters are valued for their chemical and hydrolysis resistance. They are promoted as general-purpose plasticizers. There are relatively few manufacturers of these products.

Cost	Moderate
Compatibility with the PVC polymer	Good
Outdoor weatherability	Good
Low temperature flexibility	Fair
Plasticizer solvency	Good
Bio-based content	Typically None
Flame retardancy	Poor
High temperature service	Fair (DEHP like)
Low plastisol viscosity	Good
Solvent extraction resistance	Poor
Hydrolysis resistance	Good

Aliphatic dibasic acid esters

Aliphatic dibasic acid esters are primarily used for good low-temperature properties. They impart these properties to flexible PVC compounds. They are very efficient plasticizers and many are effective plastisol viscosity depressants. Some may have bio-based content. Drawbacks are their relatively poor compatibility with PVC and relatively low solvating strength.

Cost	Moderate
Compatibility with the PVC polymer	Fair
Outdoor weatherability	Poor to Fair
Low temperature flexibility	Excellent
Plasticizer solvency	Fair
Bio-based content	Typically None
Flame retardancy	Poor
High temperature service	Poor
Low plastisol viscosity	Excellent
Solvent extraction resistance	Poor
Hydrolysis resistance	Fair

In this category, the most commonly used plasticizers are:

Di-2-ethylhexyl sebacate (DOS)
Di-2-ethylhexyl azelate (DOZ)
Di-isodecyl sebacate (DIDS)

Polyol-carboxylic acid esters

Cost	Moderately High
Compatibility with the PVC polymer	Good
Low temperature flexibility	Good
Plasticizer solvency	Good
Flame retardancy	Poor
High temperature service	Fair to Good
Low plastisol viscosity	Fair to Poor
Solvent extraction resistance	Poor

Trimellitates

Trimellitic anhydride (TMA) is a tri-carboxylic acid. It is similar in structure to phthalic anhydride or acid. Trimellitate esters are used primarily because of their:

low volatility and
high permanence.

Commercial trimellitic anhydride is a starting material for trimellitate manufacture. It contains very small amount of phthalic anhydride. So, trimellitate plasticizers are not “phthalate alternatives”. Hence, they can't be judged as phthalate-free plasticizers. This is because traces of phthalates have been found in them.

These plasticizers have better extraction resistance and good processability when compared to phthalates. Trimellitates are employed in PVC compounds like:

high-temperature-rated wire insulation,
gaskets, and
some parts for automobile interiors.

Mentioned in the below table are some benefits of these plasticizers.

Cost	Moderately High
Compatibility with the PVC polymer	Good
Outdoor weatherability	Fair to Good
Low temperature flexibility	Fair to Good
Plasticizer solvency	Fair
Bio-based content	Typically none
Flame retardancy	Poor
High temperature service	Excellent
Low plastisol viscosity	Poor
Solvent extraction resistance	Fair
Hydrolysis resistance	Fair

Polymeric plasticizers

Many have low solvency for PVC and high viscosity. Both these factors can make processing f-PVC compounds difficult.
Many have poor low-temperature properties and may be sensitive to moisture.

Check out the table below for the benefits of polymeric plasticizers.

Cost	High
Compatibility with the PVC polymer	Good
Outdoor weatherability	Fair to Poor
Low temperature flexibility	Fair to Poor
Plasticizer solvency	Fair
Bio-based content	Typically None
Flame retardancy	Poor
High temperature service	Fair to Good
Low plastisol viscosity	Poor
Solvent extraction resistance	Fair to Good
Hydrolysis resistance	Fair to Good

Biobased plasticizers

As we shift to sustainable ingredients, bio-based plasticizers continue to gain further importance. They can be used as a phthalate alternative. They also lower our dependence on fossil fuel-based feedstock. The common feedstock for this class of plasticizers is mentioned below.

As the name says, biobased plasticizers are majorly based on:

Epoxidized soybean oil (ESBO)
Epoxidized linseed oil (ELO)
Castor oil
Palm oil
Other Vegetable oils
Starches
Sugars (including isosorbide esters)
others

Few more plasticizers are based on renewably sourced isosorbides and alkanoic acids. Isosorbide diesters are a non-toxic alternative to phthalates. They offer promising properties to PVC.

Being naturally/renewable sourced, bio-based plasticizers are sometimes easily approved for:

food contact and medical applications
toys and teething products for infants
wire insulation & jacketing
household & consumer goods
flooring and carpet backing
other building & construction end-use applications

Below mentioned are benefits of vegetable oil derivatives – epoxides. Chemically, epoxy plasticizers are esters which contain one or more epoxidized double bonds. Examples include epoxidized soybean oil (ESBO) and epoxidized linseed oil (ELO). Oxidation of an olefinic double bond to an oxirane structure leads to the formation of epoxy groups. The presence of an epoxy group helps these plasticizers to improve heat stability of the manufactured PVC articles. At higher concentrations epoxy plasticizers sometimes develop incompatibility with PVC.

Cost	Moderate to very high
Compatibility with the PVC polymer	Fair to Good
Outdoor weatherability	Fair
Low temperature flexibility	Poor (triglyceride esters of fatty acids) to good
Plasticizer solvency	Poor (triglyceride esters of fatty acids) to good
Bio-based content	Typically high
Flame retardancy	Poor
High temperature service	Good (triglycerides)
Low plastisol viscosity	Poor (triglycleride esters) to good
Solvent extraction resistance	Poor
Hydrolysis resistance	Fair

Vegetable oil derivatives are the most widely used natural product type plasticizers. Products consisting of triglyceride esters of unsaturated fatty acids (e.g., soybean oil, linseed oil) in which the double bonds in the fatty acid residues have typically been epoxidized have been commercial products for decades. Drawbacks include low solvating strength, high viscosities, and poor low-temperature properties.

Other vegetable oil derivatives (e.g., monoesters made from vegetable oil-derived fatty acids or acetylated monoglycerides derived from vegetable oils) may have:

better solvency
compatibility
low-temperature properties
high volatility

Already know which plasticizer you need? Browse for commercial grades here:

Adipates	Hydrocarbons	Polyesters
Benzoates	Orthophthalates, HMW	Sebacates
Chlorinated Paraffins	Orthophthalates, LMW	Terephthalates
Citrates	Other Esters	Trimellitates
Epoxidized Oils	Phosphates

Comparing Different Alternative Plasticizers

Property	Terephthalates	Adipates	Benzoates	Citrates	Phosphate	Trimellitates
Cost	Low	Moderately high	Moderate	Fair	High	Moderately High
Compatibility with the PVC polymer	Fair	Fair to Good	Good	Fair to Poor	Good	Good
Outdoor weatherability	Fair	Fair to Poor	Poor to Good	Fair to Good	Fair to Good	Fair to Good
Low temperature flexibility	Good	Good	Poor to Good	Fair to Good	Poor to Fair	Fair to Good
Plasticizer solvency	Fair to Good	Fair	Excellent	Fair	Good	Fair
Bio-based content	Typically none	None	Typically none	None to High	None	Typically none
Flame retardancy	Poor	Poor	Poor	Poor	Good	Poor
High temperature service	Fair	Fair to Poor	-	Poor to Fair	Fair	Excellent
Low plastisol viscosity	Good	Good	Poor to Good	Poor to Fair	Good	Poor
Solvent extraction resistance	Poor	Fair to Good	Poor to Fair	Fair	Poor	Fair
Hydrolysis resistance	Fair	Fair	Fair	Poor to Fair	Fair	Fair

Property	Ring Saturated Phthalate Esers	Alkyl Sulfonic Acid Esters	Aliphatic Dibasic Acid Esters	Polyol-Carboxylic Acid Esters	Polymeric Plasticizers	Biobased Plasticizers
Cost	Moderate	Moderate	Moderate	Moderately High	High	Moderate to Very High
Compatibility with the PVC polymer	Fair	Good	Fair	Good	Good	Fair to Good
Outdoor weatherability	Fair	Good	Poor to Fair	-	Fair to Poor	Fair
Low temperature flexibility	Good	Fair	Excellent	Good	Fair to Poor	Poor (triglyceride esters of fatty acids) to Good
Plasticizer solvency	Fair	Good	Fair	Good	Fair	Poor (triglyceride esters of fatty acids) to Good
Bio-based content	None	Typically None	Typically None	-	Typically None	Typically High
Flame retardancy	Poor	Poor	Poor	Poor	Poor	Poor
High temperature service	Poor	Fair (DEHP like)	Poor	Fair to Good	Fair to Good	Good (triglycerides)
Low plastisol viscosity	Good	Good	Excellent	Fair to Poor	Poor	Poor (triglyceride esters of fatty acids) to Good
Solvent extraction resistance	Poor	Poor	Poor	Poor	Fair to Good	Poor
Hydrolysis resistance	Fair	Good	Fair	-	Fair to Good	Fair

Points to Consider while Selecting Plasticizers

While selecting a general-purpose plasticizer for PVC, the main attributes to be checked are:

Regulatory clearance – Safe for use and Safe in use
Good compatibility
Cost effective
UV resistant
Long service life and sustainable-favorable LCA
High permanency thermally stable

Among them, regulation is an important decision factor while selecting plasticizers. In recent years, there has been a lot of discussion on phthalate plasticizers. But in fact, not all phthalates are prohibited. For example, the use of phthalate plasticizers in plasticized PVC is neither prohibited in the US (federal and state legislation) nor the EU in any plasticized PVC product.

Phthalates Used for Childcare Products

We have already discussed recent regulatory status w.r.t phthalate plasticizers in child care articles. There are also federal regulations (not laws) for plasticizers.

Only certain plasticizers are preapproved by the Food and Drug Administration for use in flexible PVC products used in various food contact applications (See USFDA Code of Federal Regulations Title 21, Part 177, Indirect Food Additives – Polymers)
Likewise, flexible PVC medical devices may (and often do) contain phthalate plasticizers (flexible PVC I.V. tubing, blood bags and examination gloves most often contain DEHP) if the finished product meets certification requirements

California Proposition 65 listed

On a state level, certain phthalate plasticizers are California Proposition 65 listed. This listing means that a chemical “is known by the State of California to cause cancer, birth defects or reproductive harm”.

It does not prohibit the use of the listed chemical or items containing the chemical in the State of California.
It does not create a labeling requirement for items containing the Proposition 65 listed chemical.

If it can be demonstrated that a flexible PVC product containing (Proposition 65 listed) DEHP plasticizer, for example, cannot expose a consumer to more than the maximum acceptable daily limit of DEHP (established by the state of California), no labeling is required in California.

Plasticizers in Europe

In the EU, there is a more systematic approach to chemical regulation. Under the REACH protocol for evaluating chemicals used in commerce, certain phthalates have been effectively banned from manufacture, importation, and usage. For example: DEHP -the world’s most widely used plasticizer that has been banned. Certain other high-volume phthalates including DINP and DIDP have been fully approved for use in all their current applications.

Plasticizers Regulatory Status
Source: ExxonMobil
(Click on Image to Enlarge)

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