Functional bio-based polyesters by enzymatic polymerization

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Abstract

During recent years enzymatic polymerization has become increasingly popular as an alternative to classical polyesterification processes. The high regioselectivity observed for lipases permits preparation of novel polyesters with a high number of functional groups.1 This is particularly interesting when considering monomers from bio-based feedstock that generally contain a high number of functional groups such as a both secondary and primary alcohols. Enzymatic polymerization can be conducted at relatively low temperature and thereby is well suited for sensitive monomers.
Recently enzymatic polymerization was applied to prepare functional water soluble polyesters based on dimethyl itaconate and poly(ethyleneglycol).2 The monomer permits postfunctionalization using thiol-ene chemistry or aza-michael additions, which was used to illustrate the possibilites of preparing functional hydrogels. Hydrogels based on the polyesters were shown to be degradable and could be prepared either from the pure polyester or from prefunctionalized polyesters, though the thiol-ene reactions were found to be less effective. Since then a new monomer, trans-2,5-dihydroxy-3-pentenoic acid methyl ester (DPM) has been prepared directly from pentoses using using tin containing zeolites.3 The monomer was prepared in yields of up to 32% and contains both a vinyl as well as a secondary alcohol in addition to the primary alcohol and ester functionality, and as such is an interesting building block for polymers. DPM was copolymerized together with ethyl-6-hydroxyhexanoate yielding copolymers with molecular weights of up to 12,000 g/mol. The polymers were postfunctionalized using trifluoroacetic anhydride, which resulted in 100% conversion of the secondary alcohols, illustrating the possibility to use the secondary alcohol for grafting. In addition to this, thiol-ene reactions using hexanethiol, mercaptoethanol, mercaptoacetic acid, 2-ethylhexanethiol and thiophenol were conducted on the internal double bond resulting in conversions of 32-100%. Given the lower reactivity of the internal double bond the extent of functionalization was found acceptable for use as a general method for dual functionality polyesters.
Original languageEnglish
Publication date2016
Number of pages1
Publication statusPublished - 2016
EventNordic Polymer Days 2016 Nordic Rheology Conference - University of Helsinki, Helsinki, Finland
Duration: 30 May 20161 Jun 2016

Conference

ConferenceNordic Polymer Days 2016 Nordic Rheology Conference
LocationUniversity of Helsinki
CountryFinland
CityHelsinki
Period30/05/201601/06/2016

Cite this

Daugaard, A. E., Hoffmann, C., & Andersen, C. (2016). Functional bio-based polyesters by enzymatic polymerization. Abstract from Nordic Polymer Days 2016 Nordic Rheology Conference, Helsinki, Finland.
Daugaard, Anders Egede ; Hoffmann, Christian ; Andersen, Christian. / Functional bio-based polyesters by enzymatic polymerization. Abstract from Nordic Polymer Days 2016 Nordic Rheology Conference, Helsinki, Finland.1 p.
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abstract = "During recent years enzymatic polymerization has become increasingly popular as an alternative to classical polyesterification processes. The high regioselectivity observed for lipases permits preparation of novel polyesters with a high number of functional groups.1 This is particularly interesting when considering monomers from bio-based feedstock that generally contain a high number of functional groups such as a both secondary and primary alcohols. Enzymatic polymerization can be conducted at relatively low temperature and thereby is well suited for sensitive monomers.Recently enzymatic polymerization was applied to prepare functional water soluble polyesters based on dimethyl itaconate and poly(ethyleneglycol).2 The monomer permits postfunctionalization using thiol-ene chemistry or aza-michael additions, which was used to illustrate the possibilites of preparing functional hydrogels. Hydrogels based on the polyesters were shown to be degradable and could be prepared either from the pure polyester or from prefunctionalized polyesters, though the thiol-ene reactions were found to be less effective. Since then a new monomer, trans-2,5-dihydroxy-3-pentenoic acid methyl ester (DPM) has been prepared directly from pentoses using using tin containing zeolites.3 The monomer was prepared in yields of up to 32{\%} and contains both a vinyl as well as a secondary alcohol in addition to the primary alcohol and ester functionality, and as such is an interesting building block for polymers. DPM was copolymerized together with ethyl-6-hydroxyhexanoate yielding copolymers with molecular weights of up to 12,000 g/mol. The polymers were postfunctionalized using trifluoroacetic anhydride, which resulted in 100{\%} conversion of the secondary alcohols, illustrating the possibility to use the secondary alcohol for grafting. In addition to this, thiol-ene reactions using hexanethiol, mercaptoethanol, mercaptoacetic acid, 2-ethylhexanethiol and thiophenol were conducted on the internal double bond resulting in conversions of 32-100{\%}. Given the lower reactivity of the internal double bond the extent of functionalization was found acceptable for use as a general method for dual functionality polyesters.",
author = "Daugaard, {Anders Egede} and Christian Hoffmann and Christian Andersen",
year = "2016",
language = "English",
note = "Nordic Polymer Days 2016 Nordic Rheology Conference ; Conference date: 30-05-2016 Through 01-06-2016",

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Daugaard, AE, Hoffmann, C & Andersen, C 2016, 'Functional bio-based polyesters by enzymatic polymerization' Nordic Polymer Days 2016 Nordic Rheology Conference, Helsinki, Finland, 30/05/2016 - 01/06/2016, .

Functional bio-based polyesters by enzymatic polymerization. / Daugaard, Anders Egede; Hoffmann, Christian; Andersen, Christian.

2016. Abstract from Nordic Polymer Days 2016 Nordic Rheology Conference, Helsinki, Finland.

Research output: Contribution to conferenceConference abstract for conferenceResearchpeer-review

TY - ABST

T1 - Functional bio-based polyesters by enzymatic polymerization

AU - Daugaard, Anders Egede

AU - Hoffmann, Christian

AU - Andersen, Christian

PY - 2016

Y1 - 2016

N2 - During recent years enzymatic polymerization has become increasingly popular as an alternative to classical polyesterification processes. The high regioselectivity observed for lipases permits preparation of novel polyesters with a high number of functional groups.1 This is particularly interesting when considering monomers from bio-based feedstock that generally contain a high number of functional groups such as a both secondary and primary alcohols. Enzymatic polymerization can be conducted at relatively low temperature and thereby is well suited for sensitive monomers.Recently enzymatic polymerization was applied to prepare functional water soluble polyesters based on dimethyl itaconate and poly(ethyleneglycol).2 The monomer permits postfunctionalization using thiol-ene chemistry or aza-michael additions, which was used to illustrate the possibilites of preparing functional hydrogels. Hydrogels based on the polyesters were shown to be degradable and could be prepared either from the pure polyester or from prefunctionalized polyesters, though the thiol-ene reactions were found to be less effective. Since then a new monomer, trans-2,5-dihydroxy-3-pentenoic acid methyl ester (DPM) has been prepared directly from pentoses using using tin containing zeolites.3 The monomer was prepared in yields of up to 32% and contains both a vinyl as well as a secondary alcohol in addition to the primary alcohol and ester functionality, and as such is an interesting building block for polymers. DPM was copolymerized together with ethyl-6-hydroxyhexanoate yielding copolymers with molecular weights of up to 12,000 g/mol. The polymers were postfunctionalized using trifluoroacetic anhydride, which resulted in 100% conversion of the secondary alcohols, illustrating the possibility to use the secondary alcohol for grafting. In addition to this, thiol-ene reactions using hexanethiol, mercaptoethanol, mercaptoacetic acid, 2-ethylhexanethiol and thiophenol were conducted on the internal double bond resulting in conversions of 32-100%. Given the lower reactivity of the internal double bond the extent of functionalization was found acceptable for use as a general method for dual functionality polyesters.

AB - During recent years enzymatic polymerization has become increasingly popular as an alternative to classical polyesterification processes. The high regioselectivity observed for lipases permits preparation of novel polyesters with a high number of functional groups.1 This is particularly interesting when considering monomers from bio-based feedstock that generally contain a high number of functional groups such as a both secondary and primary alcohols. Enzymatic polymerization can be conducted at relatively low temperature and thereby is well suited for sensitive monomers.Recently enzymatic polymerization was applied to prepare functional water soluble polyesters based on dimethyl itaconate and poly(ethyleneglycol).2 The monomer permits postfunctionalization using thiol-ene chemistry or aza-michael additions, which was used to illustrate the possibilites of preparing functional hydrogels. Hydrogels based on the polyesters were shown to be degradable and could be prepared either from the pure polyester or from prefunctionalized polyesters, though the thiol-ene reactions were found to be less effective. Since then a new monomer, trans-2,5-dihydroxy-3-pentenoic acid methyl ester (DPM) has been prepared directly from pentoses using using tin containing zeolites.3 The monomer was prepared in yields of up to 32% and contains both a vinyl as well as a secondary alcohol in addition to the primary alcohol and ester functionality, and as such is an interesting building block for polymers. DPM was copolymerized together with ethyl-6-hydroxyhexanoate yielding copolymers with molecular weights of up to 12,000 g/mol. The polymers were postfunctionalized using trifluoroacetic anhydride, which resulted in 100% conversion of the secondary alcohols, illustrating the possibility to use the secondary alcohol for grafting. In addition to this, thiol-ene reactions using hexanethiol, mercaptoethanol, mercaptoacetic acid, 2-ethylhexanethiol and thiophenol were conducted on the internal double bond resulting in conversions of 32-100%. Given the lower reactivity of the internal double bond the extent of functionalization was found acceptable for use as a general method for dual functionality polyesters.

M3 - Conference abstract for conference

ER -

Daugaard AE, Hoffmann C, Andersen C. Functional bio-based polyesters by enzymatic polymerization. 2016. Abstract from Nordic Polymer Days 2016 Nordic Rheology Conference, Helsinki, Finland.