Acrylonitrile styrene acrylate

Last updated
Acrylonitrile styrene acrylate
ASA monomers Image.png
Monomers in ASA polymer
Identifiers
PubChem CID
Properties
C
18 H
23 N O
2
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Acrylonitrile styrene acrylate (ASA), also called acrylic styrene acrylonitrile, is an amorphous thermoplastic developed as an alternative to acrylonitrile butadiene styrene (ABS), that has improved weather resistance. It is an acrylate rubber-modified styrene acrylonitrile copolymer. It is used for general prototyping in 3D printing, where its UV resistance and mechanical properties make it an excellent material for use in fused filament fabrication printers, [1] particularly for outdoor applications. ASA is also widely used in the automotive industry. [2]

Contents

Properties

ASA is structurally very similar to ABS. The spherical particles of slightly crosslinked acrylate rubber (instead of butadiene rubber), functioning as an impact modifier, are chemically grafted with styrene-acrylonitrile copolymer chains, and embedded in styrene-acrylonitrile matrix. The acrylate rubber differs from the butadiene based rubber by absence of double bonds, which gives the material about ten times the weathering resistance and resistance to ultraviolet radiation of ABS, higher long-term heat resistance, and better chemical resistance. ASA is significantly more resistant to environmental stress cracking than ABS, especially to alcohols and many cleaning agents. n-Butyl acrylate rubber is usually used, but other esters can be encountered too, e.g. ethyl hexyl acrylate. ASA has lower glass transition temperature than ABS, 100 °C vs 105 °C, providing better low-temperature properties to the material. [3]

ASA has high outdoor weatherability; it retains gloss, color, and mechanical properties in outdoor exposure. It has good chemical and heat resistance, high gloss, good antistatic properties, and is tough and rigid. It is used in applications requiring weatherability, e.g. commercial siding, outside parts of vehicles, or outdoor furniture. [4]

ASA is compatible with some other plastics, namely polyvinyl chloride and polycarbonate. ASA-PVC compounds are in use. [4]

ASA can be processed by extrusion and coextrusion, thermoforming, injection molding, extrusion blow molding, and structural foam molding. [4]

ASA is mildly hygroscopic; drying may be necessary before processing. [4]

ASA exhibits low moulding shrinkage. [5]

ASA can be used as an additive to other polymers, when their heat distortion (resulting in deformed parts made of the material) has to be lowered. [6]

ASA can be coextruded with other polymers, so only the ASA layer is exposed to high temperature or weathering. ASA foils are used in in-mold decoration for forming e.g. car exterior panels. [6]

ASA can be welded to itself or to some other plastics. Ultrasonic welding can be used to join ASA to PVC, ABS, SAN, PMMA, and some others. [4]

ASA can be solvent-welded, using e.g. cyclohexane, 1,2-dichloroethane, methylene chloride, or 2-butanone. Such solvents can also join ASA with ABS and SAN. Solutions of ASA in these solvents can also be used as adhesives. [4]

ASA can be glued with cyanoacrylates; uncured resin can however cause stress cracking. ASA is compatible with acrylic-based adhesives. Anaerobic adhesives perform poorly with ASA. Epoxies and neoprene adhesives can be used for bonding ASA with woods and metals. [4]

ASA waste can be combined with sand for pavement structures. The dynamic modulus results showed that the ASA mixtures have improved high-temperature deformation resistance as compared to the asphalt mixtures. The ASA mixtures have excellent rutting resistance and moisture damage resistance. The tensile strength ratio of the ASA and asphalt mixture are all larger than 0.8 and therefore satisfy the Superpave specification. The average coefficient of permeability of the ASA mixture is 6–10 times higher than the asphalt mixture in the same air void level. The average aggregate loss percent of the ASA mixtures is 9.2–10.8 times higher than asphalt mixtures. Overall, sand and ASA plastic mixtures were found to be an adequate substitute for asphalt mixtures typically used for road surfaces. [7] ASA and sand can also be used in 3D printing and injection molding as a low-cost method of distributed recycling. [8]

Compared to polycarbonate, ASA has higher resistance to environmental stress cracking, and exhibits lower yellowing in outdoor applications. Compared to polypropylene, ASA has lower moulding shrinkage (0.5% vs 1.5%), higher stiffness, impact resistance, heat distortion temperature, and weatherability. [9]

History

In the 1960s, James A. Herbig and Ival O. Salyer of Monsanto were the first to attempt to make what would become ASA using butyl acrylate as the rubber phase. This work was then refined by Hans-Werner Otto and Hans Peter Siebel of BASF using a copolymer of butyl acrylate with butadiene for the rubber phase. [10]

Production

ASA can be made by either a reaction process of all three monomers (styrene, acrylonitrile, acrylic ester) or a graft process, although the graft process is the typical method. A grafted acrylic ester elastomer is introduced during the copolymerization of styrene and acrylonitrile. The elastomer is introduced as a powder. [11]

As of 2003, there were only few large manufacturers of ASA; e.g. BASF, General Electric, Bayer, Miele, Hitachi, and LG Chem. The production process is similar to ABS, but it has some key differences and difficulties. The annual demand around 2003 was about 1-5% of ABS. [9]

Applications

ASA/PC (polycarbonate) blends have been prepared and are commercially available. [12] [13]

In the Fused Filament Fabrication 3-D printing process, the ASA filament is used to fabricate 3-D printed parts, which above all must absorb a certain amount of impact and impact energy without breaking. [14] Substantial effort has been focused on 3D printing parameter optimization by many methods [15] including with the Taguchi methods to enable ASA to be used for high-end applications. [16]

ASA with compounds of silver, rendering its surface antimicrobial by the silver's oligodynamic effect, was introduced to the market in 2008. [6]

3D printed ASA can be used for absorbers for water desalination. [17]

Related Research Articles

<span class="mw-page-title-main">Petrochemical</span> Chemical product derived from petroleum

Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.

<span class="mw-page-title-main">Polystyrene</span> Polymer resin widely used in packaging

Polystyrene (PS) is a synthetic polymer made from monomers of the aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. It is an inexpensive resin per unit weight. It is a poor barrier to air and water vapor and has a relatively low melting point. Polystyrene is one of the most widely used plastics, with the scale of its production being several million tonnes per year. Polystyrene is naturally transparent, but can be colored with colorants. Uses include protective packaging, containers, lids, bottles, trays, tumblers, disposable cutlery, in the making of models, and as an alternative material for phonograph records.

<span class="mw-page-title-main">Thermoplastic</span> Plastic that softens with heat and hardens on cooling

A thermoplastic, or thermosoftening plastic, is any plastic polymer material that becomes pliable or moldable at a certain elevated temperature and solidifies upon cooling.

<span class="mw-page-title-main">Acrylonitrile butadiene styrene</span> Thermoset polymer

Acrylonitrile butadiene styrene (ABS) (chemical formula (C8H8)x·​(C4H6)y·​(C3H3N)z ) is a common thermoplastic polymer. Its glass transition temperature is approximately 105 °C (221 °F). ABS is amorphous and therefore has no true melting point.

Acrylonitrile is an organic compound with the formula CH2CHCN and the structure H2C=CH−C≡N. It is a colorless, volatile liquid. It has a pungent odor of garlic or onions. Its molecular structure consists of a vinyl group linked to a nitrile. It is an important monomer for the manufacture of useful plastics such as polyacrylonitrile. It is reactive and toxic at low doses.

<span class="mw-page-title-main">Styrene-butadiene</span> Synthetic rubber polymer

Styrene-butadiene or styrene-butadiene rubber (SBR) describe families of synthetic rubbers derived from styrene and butadiene. These materials have good abrasion resistance and good aging stability when protected by additives. In 2012, more than 5.4 million tonnes of SBR were processed worldwide. About 50% of car tires are made from various types of SBR. The styrene/butadiene ratio influences the properties of the polymer: with high styrene content, the rubbers are harder and less rubbery. SBR is not to be confused with the thermoplastic elastomer, styrene-butadiene block copolymer, although being derived from the same monomers.

<span class="mw-page-title-main">Copolymer</span> Polymer derived from more than one species of monomer

In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are sometimes called bipolymers. Those obtained from three and four monomers are called terpolymers and quaterpolymers, respectively. Copolymers can be characterized by a variety of techniques such as NMR spectroscopy and size-exclusion chromatography to determine the molecular size, weight, properties, and composition of the material.

<span class="mw-page-title-main">Polybutadiene</span> Type of synthetic rubber formed from the polymerization of butadiene

Polybutadiene [butadiene rubber BR] is a synthetic rubber. Polybutadiene rubber is a polymer formed from the polymerization of the monomer 1,3-butadiene. Polybutadiene has a high resistance to wear and is used especially in the manufacture of tires, which consumes about 70% of the production. Another 25% is used as an additive to improve the toughness of plastics such as polystyrene and acrylonitrile butadiene styrene (ABS). Polybutadiene rubber accounted for about a quarter of total global consumption of synthetic rubbers in 2012. It is also used to manufacture golf balls, various elastic objects and to coat or encapsulate electronic assemblies, offering high electrical resistivity. Polybutadiene is typically crosslinked with sulphur, however, it has also been shown that it can be UV cured when bis-benzophenone additives are incorporated into the formulation.

<span class="mw-page-title-main">Engineering plastic</span> Plastics often used for making mechanical parts

Engineering plastics are a group of plastic materials that have better mechanical and/or thermal properties than the more widely used commodity plastics.

Nitrile rubber, also known as nitrile butadiene rubber, NBR, Buna-N, and acrylonitrile butadiene rubber, is a synthetic rubber derived from acrylonitrile (ACN) and butadiene. Trade names include Perbunan, Nipol, Krynac and Europrene. This rubber is unusual in being resistant to oil, fuel, and other chemicals.

Kraton is the trade name given to a number of high-performance elastomers manufactured by Kraton Polymers, and used as synthetic replacements for rubber. Kraton polymers offer many of the properties of natural rubber, such as flexibility, high traction, and sealing abilities, but with increased resistance to heat, weathering, and chemicals.

<span class="mw-page-title-main">Hot-melt adhesive</span> Glue applied by heating

Hot-melt adhesive (HMA), also known as hot glue, is a form of thermoplastic adhesive that is commonly sold as solid cylindrical sticks of various diameters designed to be applied using a hot glue gun. The gun uses a continuous-duty heating element to melt the plastic glue, which the user pushes through the gun either with a mechanical trigger mechanism on the gun, or with direct finger pressure. The glue squeezed out of the heated nozzle is initially hot enough to burn and even blister skin. The glue is sticky when hot, and solidifies in a few seconds to one minute. Hot-melt adhesives can also be applied by dipping or spraying, and are popular with hobbyists and crafters both for affixing and as an inexpensive alternative to resin casting.

<span class="mw-page-title-main">Acrylate polymer</span> Group of polymers prepared from acrylate monomers

An acrylate polymer is any of a group of polymers prepared from acrylate monomers. These plastics are noted for their transparency, resistance to breakage, and elasticity.

Thermoplastic elastomers (TPE), sometimes referred to as thermoplastic rubbers (TPR), are a class of copolymers or a physical mix of polymers that consist of materials with both thermoplastic and elastomeric properties.

Membrane roofing is a type of roofing system for buildings, RV's, Ponds and in some cases tanks. It is used to create a watertight covering to protect the interior of a building. Membrane roofs are most commonly made from synthetic rubber, thermoplastic, or modified bitumen. Membrane roofs are most commonly used in commercial application, though they are becoming increasingly common in residential application.

In materials science, a polymer blend, or polymer mixture, is a member of a class of materials analogous to metal alloys, in which at least two polymers are blended together to create a new material with different physical properties.

Rubber toughening is a process in which rubber nanoparticles are interspersed within a polymer matrix to increase the mechanical robustness, or toughness, of the material. By "toughening" a polymer it is meant that the ability of the polymeric substance to absorb energy and plastically deform without fracture is increased. Considering the significant advantages in mechanical properties that rubber toughening offers, most major thermoplastics are available in rubber-toughened versions; for many engineering applications, material toughness is a deciding factor in final material selection.

INEOS Styrolution is a global styrenics supplier and is headquartered in Germany. It is a subcompany of INEOS and provides styrenics applications for many everyday products across a broad range of industries, including automotive, electronics, household, construction, healthcare, packaging and toys/sports/leisure.

<span class="mw-page-title-main">Graft polymer</span> Polymer with a backbone of one composite and random branches of another composite

In polymer chemistry, graft polymers are segmented copolymers with a linear backbone of one composite and randomly distributed branches of another composite. The picture labeled "graft polymer" shows how grafted chains of species B are covalently bonded to polymer species A. Although the side chains are structurally distinct from the main chain, the individual grafted chains may be homopolymers or copolymers. Graft polymers have been synthesized for many decades and are especially used as impact resistant materials, thermoplastic elastomers, compatibilizers, or emulsifiers for the preparation of stable blends or alloys. One of the better-known examples of a graft polymer is a component used in high impact polystyrene, consisting of a polystyrene backbone with polybutadiene grafted chains.

Dimethylaminoethyl acrylate or DMAEA is an unsaturated carboxylic acid ester having a tertiary amino group. It is a colorless to yellowish, water-miscible liquid with a pungent, amine-like odor. DMAEA is an important acrylic monomer that gives basic properties to copolymers.

References

  1. ↑ "~/media/Main/Files/Material_Spec_Sheets/MSS_FDM_ASA". stratasys.com. Archived from the original on 2016-11-14. Retrieved 2017-01-11.
  2. ↑ "Acrylonitrile Styrene Acrylate (ASA) Plastic | UL Prospector". plastics.ides.com. Retrieved 2017-01-11.
  3. ↑ "PETG vs ABS vs ASA". filament2print. Retrieved 31 January 2020.
  4. 1 2 3 4 5 6 7 Staff, PDL (1997). Handbook of Plastics Joining: A Practical Guide. Elsevier Science. p. 515. ISBN   9780815517665 . Retrieved 2017-01-11.
  5. ↑ "Shrinkage value of Plastics Material & Injection Molding - Chart". Omnexus. Retrieved 31 January 2020.
  6. 1 2 3 Fink, J.K. (2010). Handbook of Engineering and Specialty Thermoplastics, Polyolefins and Styrenics. Wiley. ISBN   9781118029282 . Retrieved 2017-01-11.
  7. ↑ Jin, Dongzhao; Meyer, Theresa K.; Chen, Siyu; Ampadu Boateng, Kwadwo; Pearce, Joshua M.; You, Zhanping (2022-07-04). "Evaluation of lab performance of stamp sand and acrylonitrile styrene acrylate waste composites without asphalt as road surface materials". Construction and Building Materials. 338: 127569. doi:10.1016/j.conbuildmat.2022.127569. ISSN   0950-0618. S2CID   248437937.
  8. ↑ Meyer, Theresa K.; Tanikella, Nagendra G.; Reich, Matthew J.; Pearce, Joshua M. (2020-09-01). "Potential of distributed recycling from hybrid manufacturing of 3-D printing and injection molding of stamp sand and acrylonitrile styrene acrylate waste composite". Sustainable Materials and Technologies. 25: e00169. doi:10.1016/j.susmat.2020.e00169. ISSN   2214-9937. S2CID   218967394.
  9. 1 2 Scheirs, J.; Priddy, D. (2003). Modern Styrenic Polymers: Polystyrenes and Styrenic Copolymers. Wiley. p. 341. ISBN   9780471497523 . Retrieved 2017-01-11.
  10. ↑ Scheirs, J.; Priddy, D. (2003). Modern Styrenic Polymers: Polystyrenes and Styrenic Copolymers. Wiley. ISBN   9780471497523.
  11. ↑ McKeen, Laurence W. (2009). "Chapter 2 - Styrenic Plastics". The Effect of Creep and Other Time Related Factors on Plastics and Elastomers (Second ed.). William Andrew Publishing. pp. 33–81. ISBN   978-0-8155-1585-2.
  12. ↑ "SABIC - GELOY Resin". www.sabic.com.
  13. ↑ Ramteke, Amol A.; Maiti, S. N. (5 April 2010). "Mechanical properties of polycarbonate/modified acrylonitrile-styrene-acrylate terpolymer blend". Journal of Applied Polymer Science. 116 (1): 486–492. doi:10.1002/app.31560.
  14. ↑ "3D-Druck: Aktuelle Anwendungsbeispiele". 15 February 2016.
  15. ↑ El Magri, Anouar; Ouassil, Salah-Eddine; Vaudreuil, Sébastien (2022). "Effects of printing parameters on the tensile behavior of 3D -printed acrylonitrile styrene acrylate ( ASA ) material in Z direction". Polymer Engineering & Science. 62 (3): 848–860. doi:10.1002/pen.25891. ISSN   0032-3888. S2CID   245825632.
  16. ↑ Hameed, Abdul Zubar; Aravind Raj, Sakthivel; Kandasamy, Jayakrishna; Shahzad, Muhammad Atif; Baghdadi, Majed Abubakr (January 2022). "3D Printing Parameter Optimization Using Taguchi Approach to Examine Acrylonitrile Styrene Acrylate (ASA) Mechanical Properties". Polymers. 14 (16): 3256. doi: 10.3390/polym14163256 . ISSN   2073-4360. PMC   9416275 . PMID   36015513.
  17. ↑ Khalil, Abdullah; Ahmed, Farah Ejaz; Hilal, Nidal (2021-10-10). "The emerging role of 3D printing in water desalination". Science of the Total Environment. 790: 148238. Bibcode:2021ScTEn.790n8238K. doi:10.1016/j.scitotenv.2021.148238. ISSN   0048-9697. PMID   34107408.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.