Polybutylene succinate

Last updated
Polybutylene succinate
Polybutylene succinate.svg
PBS 3D.gif
Names
Other names
Poly(tetramethylene succinate)
Identifiers
AbbreviationsPBS
Properties
(C8H12O4)n
Density 1.26 g/cm3
Melting point 115 °C (239 °F; 388 K)
Insoluble
Solubility in chloroform Soluble
Related compounds
Related Monomers
Succinic acid
Butanediol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Polybutylene succinate (PBS) (sometimes written polytetramethylene succinate) is a thermoplastic polymer resin of the polyester family. PBS is a biodegradable aliphatic polyester with properties that are comparable to polypropylene.

Contents

It may also be referred to by the brand names GsPLA or BioPBS (Mitsubishi Chemical). [1] PBS consists of polymerized units of butylene succinate, with repeating C8H12O4 units.

History

A. V. Lourenco Lourenco.jpg
A. V. Lourenço
W. H. Carothers Wallace H. Carothers (head).png
W. H. Carothers

The synthesis of succinic acid based polyesters was first performed in 1863. In that time the Portuguese professor Agostinho Vicente Lourenço described in his "Recherche sur les composés polyatomiques" (Research on polyatomic compounds), the reaction between succinic acid and ethylene glycol to form what he named "succino-ethylenic acid". He noticed that this acid was losing water when it was heated at high temperatures (300 °C) and that a crystalline mass when obtained after cooling. [2] Unfortunately, Lourenço did not study much the structure of the material he obtained.

Later Davidoff (1886), [3] and then Voländer (1894) prepared this same material by using different methods. This early work was pursued in the 1930s by Wallace Carothers (E.I. du Pont de Nemours and Co.), with a more systematic study of succinic acid based polyesters. In that time the purpose of such study was to find a synthetic alternative to natural silk fiber.

Carothers, by eliminating water in a continuous distillation process, obtained polymers with molar masses significantly higher than what was previously synthesized. [4] Nevertheless, the properties of the final products did not show the expected qualities. Thus Carothers put more attention on polyamides and invented with his colleague Julian Hill Nylon 6,6.

Later Flory (1946) proposed an improved synthesis of aliphatic polyesters with diacid chloride. [5]

In the beginning of the 1990s, after being forgotten for more than 40 years, these polymers received a renewed interest due to the increasing demand on biodegradable and bio-based polymers.

Synthesis

Like other polyesters such as polyethylene terephthalate, two main routes exist for the synthesis of PBS: the trans-esterification process (from succinate diesters) and the direct esterification process starting from the diacid. The direct esterification of succinic acid with 1,4-butanediol is the most common way to produce PBS. It consists of a two step process. First, an excess of the diol is esterified with the diacid to form PBS oligomers with elimination of water. PBS esterification.png

Then, these oligomers are trans-esterified under vacuum to form a high molar mass polymer. This step requires an appropriate catalyst such as titanium, zirconium, tin or germanium derivatives. [6] PBS polycondensation.png

Biodegradability

Amycolatopsis sp. HT-6 and Penicillium sp. strain 14-3 can degrade PBS. Microbispora rosea , Excellospora japonica and E. viridilutea can consume samples of emulsified PBS. [7]

Applications

As PBS decomposes into water and CO2 through naturally occurring degrading enzymes and microorganisms, [8] it may be a biodegradable alternative to some common plastics. The scope of PBS application fields is still growing and several areas can be identified but it remains difficult to know precisely in which specific object PBS is actually used. First in the packaging field, PBS could be processed into films, bags, or boxes, for both food and cosmetic packagings. Other applications of PBS could be found as disposable products such as tableware or medical articles. In agriculture, PBS finds interest in the fabrication of mulching films or delayed release materials for pesticide and fertilizer. PBS is also promise to find market shares in fishery (for fishing nets), forestry, civil engineering or other fields in which recovery and recycling of materials after use is problematic. [9] In the medical field, PBS could be used as biodegradable drug encapsulation systems, [10] and is also investigated for implants.

Industrial production

In industry, the improvement of the PBS synthesis allowed the large scale production of this polymer. The Japanese company Showa High Polymer, built in 1993 a semi-commercial plant able to produce 3,000 tons of polymer per year. [11] Sold under the tradename Bionolle, these polyesters are synthesized via melt condensation polymerization followed by a chain-extension with a diisocyanate. [12] Much later, in April 2003, Mitsubishi Chemicals built a 3,000 tons/year capacity and launched to the market a PBS named GS Pla (Green and Sustainable Plastic). This polymer has high molar masses without the use of a chain extender. Since then, several PBS producers such as Hexing Chemical (Anhui, China), Xinfu Pharmaceutical (Hangzhou, China) or IRe Chemical (South Korea) appeared on the market. In 2010 Hexing Chemical became China's first large-scale PBS enterprise, with the annual capacity of 10,000 tons. The same year Xinfu Pharmaceutical announced the building up of the world's largest continuous PBS production line with an annual capacity of 20,000 tons. At the moment most of these polyalkylene succinates are synthesized from petrochemical precursors. Nevertheless most of the producers are evaluating or developing bio-based succinic acid for the synthesis of these polyesters. In 2016, Showa Denko announced termination of the production and sale of Bionolle, citing delay in permeation of environmental regulations on plastic shopping bags and a fall in market prices of biodegradable plastics. [13]

Related Research Articles

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<span class="mw-page-title-main">Succinic acid</span> Dicarboxylic acid

Succinic acid is a dicarboxylic acid with the chemical formula (CH2)2(CO2H)2. In living organisms, succinic acid takes the form of an anion, succinate, which has multiple biological roles as a metabolic intermediate being converted into fumarate by the enzyme succinate dehydrogenase in complex 2 of the electron transport chain which is involved in making ATP, and as a signaling molecule reflecting the cellular metabolic state.

A polyamide is a polymer with repeating units linked by amide bonds.

<span class="mw-page-title-main">Malonic acid</span> Carboxylic acid with chemical formula CH2(COOH)2

Malonic acid (IUPAC systematic name: propanedioic acid) is a dicarboxylic acid with structure CH2(COOH)2. The ionized form of malonic acid, as well as its esters and salts, are known as malonates. For example, diethyl malonate is malonic acid's diethyl ester. The name originates from the Greek word μᾶλον (malon) meaning 'apple'.

Polymer chemistry is a sub-discipline of chemistry that focuses on the structures of chemicals, chemical synthesis, and chemical and physical properties of polymers and macromolecules. The principles and methods used within polymer chemistry are also applicable through a wide range of other chemistry sub-disciplines like organic chemistry, analytical chemistry, and physical chemistry. Many materials have polymeric structures, from fully inorganic metals and ceramics to DNA and other biological molecules. However, polymer chemistry is typically related to synthetic and organic compositions. Synthetic polymers are ubiquitous in commercial materials and products in everyday use, such as plastics, and rubbers, and are major components of composite materials. Polymer chemistry can also be included in the broader fields of polymer science or even nanotechnology, both of which can be described as encompassing polymer physics and polymer engineering.

<span class="mw-page-title-main">Step-growth polymerization</span>

Step-growth polymerization refers to a type of polymerization mechanism in which bi-functional or multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually long chain polymers. Many naturally occurring and some synthetic polymers are produced by step-growth polymerization, e.g. polyesters, polyamides, polyurethanes, etc. Due to the nature of the polymerization mechanism, a high extent of reaction is required to achieve high molecular weight. The easiest way to visualize the mechanism of a step-growth polymerization is a group of people reaching out to hold their hands to form a human chain—each person has two hands. There also is the possibility to have more than two reactive sites on a monomer: In this case branched polymers production take place.

<span class="mw-page-title-main">Polyhydroxyalkanoates</span> Polyester family

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3H
4O
2)
n or [–C(CH
3)HC(=O)O–]
n, formally obtained by condensation of lactic acid C(CH
3)(OH)HCOOH with loss of water. It can also be prepared by ring-opening polymerization of lactide [–C(CH
3)HC(=O)O–]
2, the cyclic dimer of the basic repeating unit.

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<span class="mw-page-title-main">Biodegradable plastic</span> Plastics that can be decomposed by the action of living organisms

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<span class="mw-page-title-main">2-Ethylhexanoic acid</span> Chemical compound

2-Ethylhexanoic acid is the organic compound with the formula CH3(CH2)3CH(C2H5)CO2H. It is a carboxylic acid that is widely used to prepare lipophilic metal derivatives that are soluble in nonpolar organic solvents. 2-Ethylhexanoic acid is a colorless viscous oil. It is supplied as a racemic mixture.

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Poly(ethylene adipate) Chemical compound

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<span class="mw-page-title-main">Poly(ethylene succinate)</span> Chemical compound

Poly(ethylene succinate) (PES) is an aliphatic synthetic polyester with a melting point from 103–106 °C. It is synthesized from dicarboxylic acids; either by ring-opening polymerization of succinic anhydride with ethylene oxide or by polycondensation of succinic acid and ethylene glycol. Thermophilic Bacillus sp. TT96 is found in soil and can degrade PES. Mesophilic PES degrading microorganisms were found in the Bacillus and Paenibacillus species; strain KT102; a relative of Bacillus pumilus was the most capable of degrading PES film. The fungal species NKCM1003 a type of Aspergillus clavatus also degrades PES film. The solubility of lithium salts (e.g. lithium perchlorate, LiClO4) in PES made it a good alternative to poly(ethylene oxide) (PEO) during early development of solid polymer electrolytes for lithium ion batteries.

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Polysuccinimide (PSI), also known as polyanhydroaspartic acid or polyaspartimide, is formed during the thermal polycondensation of aspartic acid and is the simplest polyimide. Polysuccinimide is insoluble in water, but soluble in some aprotic dipolar solvents. Its reactive nature makes polysuccinimide a versatile starting material for functional polymers made from renewable resources.

References

  1. ↑ "Biodegradable Polymer "BioPBS" | Products".
  2. ↑ Lourenço, A.V. (1863). "Recherches sur les composés polyatomiques". Ann. Chim. Phys. 67 (3).
  3. ↑ Davidoff,O. (1886). "Ein Fall der Bildung von Bernsteinsäureäthylester". Ber. Dtsch. Chem. Ges. 19: 2. doi:10.1002/cber.18860190196.
  4. ↑ Carothers, W.H. (1929). "Studies on polymerization and ring formation II. Poly-esters". J. Am. Chem. Soc. 51 (8): 10. doi:10.1021/ja01383a042.
  5. ↑ U.S. Patent 2,589,687
  6. ↑ Jacquel, N.; et al. (2011). "Synthesis and properties of poly (butylene succinate): Efficiency of different transesterification catalysts". J. Polym. Sci., Part A: Polym. Chem. 49 (24): 5301–5312. Bibcode:2011JPoSA..49.5301J. doi:10.1002/pola.25009.
  7. ↑ Yutaka Tokiwa; Buenaventurada P. Calabia; Charles U. Ugwu; Seiichi Aiba (September 2009). "Biodegradability of Plastics". International Journal of Molecular Sciences. 10 (9): 3722–3742. doi: 10.3390/ijms10093722 . PMC   2769161 . PMID   19865515.
  8. ↑ Xu, J. (2010). "Microbial Succinic Acid, Its Polymer Poly(butylene succinate), and Applications". Plastics from Bacteria. Microbiology Monographs. Vol. 14. pp. 347–388. doi:10.1007/978-3-642-03287-5_14. ISBN   978-3-642-03286-8.
  9. ↑ Xu, J. (2010). "Microbial Succinic Acid, Its Polymer Poly(butylene succinate), and Applications". Plastics from Bacteria. Microbiology Monographs. Vol. 14. pp. 347–388. doi:10.1007/978-3-642-03287-5_14. ISBN   978-3-642-03286-8.
  10. ↑ Brunner, C.T. (2011). "Performance of biodegradable microcapsules of poly(butylene succinate), poly(butylene succinate-co-adipate)and poly(butylene terephthalate-co-adipate) as drug encapsulation systems". Colloids and Surfaces B:Biointerfaces. 84 (2): 498–507. doi:10.1016/j.colsurfb.2011.02.005. hdl: 1822/14234 . PMID   21376545.
  11. ↑ Xu, J. (2010). "Microbial Succinic Acid, Its Polymer Poly(butylene succinate), and Applications". Plastics from Bacteria. Microbiology Monographs. Vol. 14. pp. 347–388. doi:10.1007/978-3-642-03287-5_14. ISBN   978-3-642-03286-8.
  12. ↑ Fujimaki, T. (1998). "Processability and properties of aliphatic polyesters, 'BIONOLLE', synthesized by polycondensation reaction". Polymer Degradation and Stability. 29 (1–3): 209–214. doi:10.1016/s0141-3910(97)00220-6.
  13. ↑ "SDK to Terminate Production and Sale of Biodegradable Plastic | News Releases | SHOWA DENKO K.K." www.sdk.co.jp. Retrieved 2017-04-26.
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