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Stability study of 1-methylidene ethane-1,2-dicarboxylic acid against isomerization during the synthesis of polyesters

Tu, Cam-Bich LU (2013) KEMP37 20131
Department of Chemistry
Abstract (Swedish)
Populärvetenskaplig sammanfattning
Monomerer är mindre kemiska byggstenar som bygger upp en större molekylstruktur kallad
polymer och kan jämföras med tegelstenar i ett hus. Monomererna i vår produkt binds samman
genom så kallade esterbindningar och polymeren som bildas kallas därför en polyester.
Polyestrar har många användningsområden såsom plast i PET flaskor, färg, och konstfiber i
textilmaterial som till exempel fleecetröjor, duschdraperier med mera.
I detta projekt var vi ute efter att minska belastningen på miljön genom att ersätta de
traditionella produkterna som framställts från oljebaserade råvaror med förnyelsebara och icke
oljebaserade råvaror. Genom detta minskas även koldioxidutsläppet vid
produktframställningen. Ett... (More)
Populärvetenskaplig sammanfattning
Monomerer är mindre kemiska byggstenar som bygger upp en större molekylstruktur kallad
polymer och kan jämföras med tegelstenar i ett hus. Monomererna i vår produkt binds samman
genom så kallade esterbindningar och polymeren som bildas kallas därför en polyester.
Polyestrar har många användningsområden såsom plast i PET flaskor, färg, och konstfiber i
textilmaterial som till exempel fleecetröjor, duschdraperier med mera.
I detta projekt var vi ute efter att minska belastningen på miljön genom att ersätta de
traditionella produkterna som framställts från oljebaserade råvaror med förnyelsebara och icke
oljebaserade råvaror. Genom detta minskas även koldioxidutsläppet vid
produktframställningen. Ett mått på utsläppen av växthusgaser såsom koldioxid, som uppstår
till följd av en aktivitet, en grupp aktiviteter eller en produkt, kallas för ”carbon footprint”.
Denna faktor beräknas för att kunna mäta samt minska ett företags påverkan på klimatet. Det
är viktigt att hålla koldioxidutsläppet så lågt som möjligt för ett mer hållbart samhälle vilket är
anledningen till att vi vill använda oss av förnyelsebara alternativ.
Hållbarhet i samhället är viktigt för att vi ska fortsätta ha vatten, material och tillgångar för att
kunna skydda det ekologiska kretsloppet och miljön. En produkt som ständigt behöver bytas ut
kan tära mycket på miljön. Det finns många sätt att värna om miljön och människan, och alla
kan göra skillnad. Bland annat kan man släcka lampor som inte används, duscha istället för att
bada, använda vattenkokare istället för att koka på kokplatta, återvinna för att spara på
resurser samt energi, panta burkar och flaskor, cykla eller gå för små sträckor. Återvinning är
nödvändigt då de oljebaserade råvarorna är begränsade resurser. I detta projekt siktar vi på att
utveckla nya produkter som både håller länge och är skonsammare mot miljön genom att byta
ut de oljebaserade råvarorna mot förnyelsebara alternativ. (Less)
Abstract
The main purpose of the study was to investigate the effect of reaction conditions such as
reaction temperature and time on the isomerization of 1‐methylidene ethane‐1,2‐dicarboxylic
acid (MIA) during the synthesis of MIA to 1‐methyl‐trans‐ethene‐1,2‐dicarboxylic acid (MTA)
and 1‐methyl‐cis‐ethene‐1,2‐dicarboxylic acid (MCA) based polyesters. Twelve batches of
poly(neopentyl itaconate) and one batch of poly(PEG 200 itaconate) were synthesized through
the condensation reaction with neopentyl glycol (NPG) or poly(ethylene glycol) (PEG) and MIA.
Different reaction temperatures (160, 180, 200, 225 and 250°C) and reaction times (between 5
min to 11 h) were tested. The kinetics of the isomerization of MIA to MTA was measured and
the... (More)
The main purpose of the study was to investigate the effect of reaction conditions such as
reaction temperature and time on the isomerization of 1‐methylidene ethane‐1,2‐dicarboxylic
acid (MIA) during the synthesis of MIA to 1‐methyl‐trans‐ethene‐1,2‐dicarboxylic acid (MTA)
and 1‐methyl‐cis‐ethene‐1,2‐dicarboxylic acid (MCA) based polyesters. Twelve batches of
poly(neopentyl itaconate) and one batch of poly(PEG 200 itaconate) were synthesized through
the condensation reaction with neopentyl glycol (NPG) or poly(ethylene glycol) (PEG) and MIA.
Different reaction temperatures (160, 180, 200, 225 and 250°C) and reaction times (between 5
min to 11 h) were tested. The kinetics of the isomerization of MIA to MTA was measured and
the activation energy was calculated.
Isomerization experiments under basic conditions were also studied and divided into two parts
using two different batches. One batch of MIA‐NPG polyester was exposed to different amines;
primary‐, secondary‐ and tertiary amines at 60 °C to study the effect of basic conditions on the
isomerization of MIA polyesters. In the second batch, isomerization studies were done on a
water soluble system using MIA‐PEG polyester by exposing it to acidic (pH 2.7, reference
sample), neutral and basic pH (7, 8, 9, and 10) both at R.T and at 40 °C.
The synthesized polyesters were characterized using potentiometric titration (acid value and
hydroxyl value), size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR)
spectroscopy.
The results showed that isomerization and etherification occurred during the synthesis of MIA
based polyesters. Isomerization of MIA to both MCA and MTA was observed, but higher
conversion to MTA than to MCA was found. The conversion of MIA to MTA was almost the
same at 160 °C and 180 °C (6 %) but was significantly higher at 200 °C (19 %), 225 °C (34 %) and
250 °C (41 %). The conversion of MIA to MCA was rapid in the beginning but remained almost
constant (about 11 %) during the rest of the experiments. The MIA isomerization fitted well to a
first order reaction.
When testing the amines under non aqueous conditions, the tertiary amine affected the
isomerization the most. The isomerization was not affected by the primary amine while some
isomerization had occurred during the end of test period using the secondary amine.
Tests with different pH were also performed on a water soluble MIA‐PEG polyester where no
difference could be seen for acidic (pH 2.7, reference sample), neutral and basic pH (7, 8, 9, and
10) both at R.T and at 40 °C during the test period. (Less)
Please use this url to cite or link to this publication:
author
Tu, Cam-Bich LU
supervisor
organization
course
KEMP37 20131
year
type
H2 - Master's Degree (Two Years)
subject
keywords
fysikalisk kemi, Physical Chemistry
language
English
id
4295332
date added to LUP
2014-02-14 13:43:16
date last changed
2014-02-14 13:43:16
@misc{4295332,
  abstract     = {The main purpose of the study was to investigate the effect of reaction conditions such as
reaction temperature and time on the isomerization of 1‐methylidene ethane‐1,2‐dicarboxylic
acid (MIA) during the synthesis of MIA to 1‐methyl‐trans‐ethene‐1,2‐dicarboxylic acid (MTA)
and 1‐methyl‐cis‐ethene‐1,2‐dicarboxylic acid (MCA) based polyesters. Twelve batches of
poly(neopentyl itaconate) and one batch of poly(PEG 200 itaconate) were synthesized through
the condensation reaction with neopentyl glycol (NPG) or poly(ethylene glycol) (PEG) and MIA.
Different reaction temperatures (160, 180, 200, 225 and 250°C) and reaction times (between 5
min to 11 h) were tested. The kinetics of the isomerization of MIA to MTA was measured and
the activation energy was calculated.
Isomerization experiments under basic conditions were also studied and divided into two parts
using two different batches. One batch of MIA‐NPG polyester was exposed to different amines;
primary‐, secondary‐ and tertiary amines at 60 °C to study the effect of basic conditions on the
isomerization of MIA polyesters. In the second batch, isomerization studies were done on a
water soluble system using MIA‐PEG polyester by exposing it to acidic (pH 2.7, reference
sample), neutral and basic pH (7, 8, 9, and 10) both at R.T and at 40 °C.
The synthesized polyesters were characterized using potentiometric titration (acid value and
hydroxyl value), size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR)
spectroscopy.
The results showed that isomerization and etherification occurred during the synthesis of MIA
based polyesters. Isomerization of MIA to both MCA and MTA was observed, but higher
conversion to MTA than to MCA was found. The conversion of MIA to MTA was almost the
same at 160 °C and 180 °C (6 %) but was significantly higher at 200 °C (19 %), 225 °C (34 %) and
250 °C (41 %). The conversion of MIA to MCA was rapid in the beginning but remained almost
constant (about 11 %) during the rest of the experiments. The MIA isomerization fitted well to a
first order reaction.
When testing the amines under non aqueous conditions, the tertiary amine affected the
isomerization the most. The isomerization was not affected by the primary amine while some
isomerization had occurred during the end of test period using the secondary amine.
Tests with different pH were also performed on a water soluble MIA‐PEG polyester where no
difference could be seen for acidic (pH 2.7, reference sample), neutral and basic pH (7, 8, 9, and
10) both at R.T and at 40 °C during the test period.},
  author       = {Tu, Cam-Bich},
  keyword      = {fysikalisk kemi,Physical Chemistry},
  language     = {eng},
  note         = {Student Paper},
  title        = {Stability study of 1-methylidene ethane-1,2-dicarboxylic acid against isomerization during the synthesis of polyesters},
  year         = {2013},
}