EP3710215A2 - A method for inhibiting harmful chemicals formed in manufactured and semi-manufactured materials produced from pet - Google Patents
A method for inhibiting harmful chemicals formed in manufactured and semi-manufactured materials produced from petInfo
- Publication number
- EP3710215A2 EP3710215A2 EP18879477.0A EP18879477A EP3710215A2 EP 3710215 A2 EP3710215 A2 EP 3710215A2 EP 18879477 A EP18879477 A EP 18879477A EP 3710215 A2 EP3710215 A2 EP 3710215A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- pet
- polyethylene terephthalate
- production
- harmful chemicals
- cooh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Definitions
- the present invention relates to a method for inhibiting acetaldehyde, carboxyl end groups, and diethylene glycol chemicals in case Mg 2 B 2 0s compound in ratio of 0.2% is added into PET during injection.
- Polyethylene terephthalate is polyester which has various fields of use such as beverage, food and drink containers, synthetic fiber, and which can change its form with heat treatment.
- PET polyethylene terephthalate
- the most important advantage of polyethylene terephthalate (PET) is that it is a recyclable plastic.
- two different production techniques of polyethylene terephthalate are known.
- dimethyl terephthalate and ethylene glycol are used in the first method.
- production is performed in two different ways, namely continuous and discontinuous.
- PET polyethylene terephthalate
- PET resins are comprised of small particles sold as pellet. First, these pellets are melted at a specific temperature, and then transferred to the injection machine in order to produce preform. Preforms generally have test tube appearance and are in different colors depending on the characteristics of the product to be manufactured. The weight of the preforms is generally 14-103 grams. PET production starts with preform.
- the injection machine is comprised of two main parts; its first part is the part which comprises the components that melt the plastic materials and can inject into the mold. Its other part comprises the mechanisms which carry the mold and which can cover and uncover the mold, provide the molding pressure after it is covered, actuate the drivers, provide water supply and discharge for the cooling channels of the mold thereon.
- the preform is heated with lamps called as "heating boxes”.
- the assembly of the said lamps is called as profile.
- the preform is sent into the mold.
- the hot preform is stretched in the system.
- the stretching rod enters into the preform and stretches the preform longitudinally.
- the bottle takes its final form and the air therein is discharged.
- Carboxyl end groups are one of the parameters affecting the reaction speed. In general, thermal and thermal oxidative degradation and the increase of carboxyl end groups cause degradation of PET and losses in molecular weight. The thermal degradation of PET chains generally originates from the carboxyl end groups and the presence of acetaldehyde. Yellowing in the PET material is observed with the increase of carboxyl end groups and acetaldehyde.
- acetaldehyde is among the compounds which are likely to show carcinogenic effects on human health.
- FIG 1 is the flowchart of the Polyethylene Terephthalate production.
- Figure 4 is a graphical representation of the change of the diethylene glycol (DEG) in the mixture by weight (%) depending on the use of the pure g 2 B 2 0s compound (%) in PET mixture within the scope of the invention.
- DEG diethylene glycol
- PET Polyethylene Terephthalate
- An inventive method for inhibiting harmful chemicals in production of PET materials enables the harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), diethylene glycol (DEG) which are created upon the chemical degradation of Polyethylene Terephthalate (PET) material during the period passing from the raw material until the final product in Polyethylene Terephthalate (PET) production process and which are by-products threatening human health, and comprises the steps of
- step of mixing magnesium nitrate, boric acid and urea solutions 2 moles of Mg(N0 3 ) 2 , 2 moles of H 3 BO 3 and 4 moles of CH 4 N 2 O solutions are used.
- the mixture in step of sintering the mixture in powder form in ash furnace, the mixture is sintered in the ash furnace at 900 °C.
- Polyethylene terephthalate (PET) material chemically degrades in the period passing from the raw material until the final product and causes by-products threatening human health to be formed.
- PET Polyethylene terephthalate
- the formation of harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), diethylene glycol (DEG) is prevented in certain amounts by means of adding Mg 2 B 2 0s mineral in ratio of 0.2% into polyethylene terephthalate (PET) material in preform stage with injection.
- Mg 2 B 2 0 5 particles used within the scope of the invention are produced with sol- gel method.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to a method for inhibiting acetaldehyde, carboxyl end groups, and diethylene glycol chemicals in case Mg2B2O5 compound in ratio of 0.2% is added into PET during injection. The objective of the present invention is to prevent the formation of harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), diethylene glycol (DEG) which increase with chemical degradation of PET material in the period passing from raw material to final product.
Description
A METHOD FOR INHIBITING HARMFUL CHEMICALS FORMED IN MANUFACTURED AND SEMI-MANUFACTURED MATERIALS
PRODUCED FROM PET
Field of the Invention
The present invention relates to a method for inhibiting acetaldehyde, carboxyl end groups, and diethylene glycol chemicals in case Mg2B20s compound in ratio of 0.2% is added into PET during injection.
Background of the Invention
Polyethylene terephthalate is polyester which has various fields of use such as beverage, food and drink containers, synthetic fiber, and which can change its form with heat treatment. The most important advantage of polyethylene terephthalate (PET) is that it is a recyclable plastic. In state of the art, two different production techniques of polyethylene terephthalate are known.
a) In the first method, dimethyl terephthalate and ethylene glycol are used. In this method, production is performed in two different ways, namely continuous and discontinuous.
b) In the second method, pure terephthalic acid is reacted with ethylene glycol.
Here, again production is performed as continuous or discontinuous.
Formula 1. PET polymerization-condensation reaction
n C6H4(C02H)2 + n HOCH2CH2OH [(C0)C6H4(C02CH2CH20)]„ + 2n H20
In Figure 1, flowchart of polyethylene terephthalate (PET) production is shown. PET is produced by using ethylene glycol, dimethyl terephthalate and pure terephthalic acid with polymerization and condensation (stepwise reaction).
Polyethylene Terephthalate Bottle Production Stages
In production of PET bottle, PET preform material specifically prepared, compatible with food laws and suitable for where it is to be used. Production process of PET bottle is quite complex. The process starts with PET wastes or raw materials.
Preparation of Preform
PET resins are comprised of small particles sold as pellet. First, these pellets are melted at a specific temperature, and then transferred to the injection machine in order to produce preform. Preforms generally have test tube appearance and are in different colors depending on the characteristics of the product to be manufactured. The weight of the preforms is generally 14-103 grams. PET production starts with preform.
1. Stage: Unused and reformed pellets are mixed in the dryer. The said resin is dried such that the humidity content will be below 50 ppm.
2. Stage: A couple of hours later, the mixed resin is injected into a preform mold in order to mold and fastening.
Injection is the process of melting molding the raw plastic material. Here, the plastic cools down and takes the form of the mold. The machines which heat the plastic material up to a specific temperature and inject into the mold, and support the mechanism enabling the cooling of the material after it is filled, and enable it to be removed from the mold after it hardens are known as injection machines.
The covering force applied in the injection machine and the amount of plastic which is pressed are two important parameters enabling the classification of the machine. While the covering force varies between 10 tons and 5000 tons, the
amount of plastic which can be pressed varies between a couple of grams and 40 kilograms.
The injection machine is comprised of two main parts; its first part is the part which comprises the components that melt the plastic materials and can inject into the mold. Its other part comprises the mechanisms which carry the mold and which can cover and uncover the mold, provide the molding pressure after it is covered, actuate the drivers, provide water supply and discharge for the cooling channels of the mold thereon.
Blowing of the bottle (Inflating the bottle)
The stage after forming the preform is the last stage.
1. Stage:
The preform is heated with lamps called as "heating boxes”. The assembly of the said lamps is called as profile.
2. Stage:
The preform is sent into the mold. The hot preform is stretched in the system.
3. Stage:
The stretching rod enters into the preform and stretches the preform longitudinally.
4. Stage:
Low pressurized air is blown into the preform so that the bottle takes its actual form.
5. Stage:
The high pressurized air is blown into the bottle in order to create the specific features of the bottle such as logo.
6. Stage:
The bottle takes its final form and the air therein is discharged.
Several chemicals are added inside the PET granules produced in the present production method. Some of these are UV stabilizer, others are antioxidants, and the remaining are antistatic materials. However none of these materials provide chemical stability. Therefore, chemicals having harmful effects on human health, specifically reproductive cells, such as carboxylic acid, acetaldehyde, diethylene glycol and isopthalic acid are formed during production of resin and passing to the final product from the resin. The reason for these is that the molecules forming the PET polymer are often exposed to severe process conditions such as high temperature, high shear forces at the point of chemical stability. Under these conditions, molecules having a reversible bond structure begin to decompose and therefore transform into the first chemicals forming themselves. These chemicals have harmful effects on human health. The chemical material which is the subject of the present patent reverses the said processes, and eliminates the harmful chemicals that are formed.
-CQQH End Groups
Carboxyl end groups are one of the parameters affecting the reaction speed. In general, thermal and thermal oxidative degradation and the increase of carboxyl end groups cause degradation of PET and losses in molecular weight. The thermal degradation of PET chains generally originates from the carboxyl end groups and the presence of acetaldehyde. Yellowing in the PET material is observed with the increase of carboxyl end groups and acetaldehyde.
Sami Al-AbdulRazzak and Saleh A. Jabarin (2002) showed in their study that the increase in carboxyl end groups in PET increases the moisture holding capacity of the resin. The reason for this is the hydrogen bonds formed between the carboxyl end groups and the water, the said bonds hold onto the resin and then cause water to be there more. This case enables the resin to hold more moisture, and thus enabling a medium more suitable for the realization of hydrolysis reaction to be
prepared. Accordingly, the increase in number of the carboxyl end groups in PET reduces the resistance of PET against the hydrolysis. The content of the carboxyl end groups also affects the thermal stability of the PET.
DEG (Diethylene Glycol)
Diethylene glycol causes the melting point of PET to drop. DEG, which is a byproduct of polymerization reaction, is a comonomer which decreases the melting temperature. However, it is not effective in crystallization rates.
DEG comonomer is added in ratio of 5% by mole into PET in order to prevent crystallization during preform injection molding and inflation. Diethylene glycol is toxic for human beings and animals. It is a material which damages kidney and liver among its other effects.
Acetaldehyde
There is normally less than 2.5 ppm of residual acetaldehyde (A) in bottle resins. AA values are typically seen either in blown-molded jars or in small bottles with small bottle-cap distance. Excessive AA levels affect the taste of the beverages.
Acetaldehyde has a characteristic smell and taste, and its perception threshold is really small. For this reason, acetaldehyde migration may cause taste and smell changes in foods put in PET bottles. They can cause smell and taste changes even in trace amounts.
It has been found that acetaldehyde is among the compounds which are likely to show carcinogenic effects on human health.
Many researchers and institutions have stated that the acetaldehyde in PET can negatively affect the organoleptic characteristics of the product inside the bottle.
Summary of the Invention
The objective of the present invention is to prevent the formation of harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), diethylene glycol (DEG) which increase with chemical degradation of PET material in the period passing from raw material to final product.
Detailed Description of the Invention
“A method for inhibiting harmful chemicals in production of PET materials” developed to fulfill the objective of the present invention is illustrated in the accompanying figure, in which;
Figure 1 is the flowchart of the Polyethylene Terephthalate production.
Figure 2 is a graphical representation of the change of the COOH end group content (COOH) in the mixture by weight (%) depending on the use of the pure Mg2B205 compound (%) in PET mixture within the scope of the invention.
Figure 3 is a graphical representation of the change of the acetaldehyde (AA) in the mixture by weight (%) depending on the use of the pure Mg2B20s compound (%) in PET mixture within the scope of the invention.
Figure 4 is a graphical representation of the change of the diethylene glycol (DEG) in the mixture by weight (%) depending on the use of the pure g2B20s compound (%) in PET mixture within the scope of the invention.
The components shown in the figures are each given reference numbers as follows:
100. Polyethylene Terephthalate production flowchart
1. Ethylene production
2. Methanol production
3. p-xylene production
4. Acetic acid production
5. Dimethylterephthalate production
6. Terephthalic acid production and purification
7. Ester exchange process
8. Melting polymerization
9. Direct esterification process
10. Solid state polymerization
EG. Ethylene glycol (EG)
DMT. Dimethylterephthalate
PTA. Purified terephthalic acid
BHET . Bihydroxylethylterephthalate
Et. Ethylene
DG. Natural gas
KK. Mixed xylene
PET. Polyethylene Terephthalate An inventive method for inhibiting harmful chemicals in production of PET materials enables the harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), diethylene glycol (DEG) which are created upon the chemical degradation of Polyethylene Terephthalate (PET) material during the period passing from the raw material until the final product in Polyethylene Terephthalate (PET) production process and which are by-products threatening human health, and comprises the steps of
- mixing magnesium nitrate, boric acid and urea solutions,
- drying the mixture,
- milling and grinding the obtained white solid agate in a mortar,
- sintering the mixture in powder form in an ash furnace,
- adding the obtained sample in ratio of 0.2% into the molten Polyethylene Terephthalate (PET) used in production of Polyethylene Terephthalate (PET) and then mixing,
- pelletizing the mixture in double screw extruder,
- obtaining polyethylene terephthalate (PET) material the acetaldehyde (AA), COOH end group (COOH), diethylene glycol (DEG) content of which is reduced.
In one embodiment of the invention, in step of mixing magnesium nitrate, boric acid and urea solutions, 2 moles of Mg(N03)2, 2 moles of H3BO3 and 4 moles of CH4N2O solutions are used.
In one embodiment of the invention, in step of drying the mixture, the mixture is dried at 165 °C.
In one embodiment of the invention, in step of sintering the mixture in powder form in ash furnace, the mixture is sintered in the ash furnace at 900 °C.
Within the scope of the invention, the compound Mg2B20s is used in order to be added into molten polyethylene terephthalate (PET) in ratio of 0.02% during injection stage in polyethylene terephthalate (PET) material production for the purpose of inhibiting harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), and diethylene glycol (DEG) which created by the chemical degradation of polyethylene terephthalate (PET) material in the period passing from raw material until the final product in polyethylene terephthalate (PET) production process and which are by-products threatening human health.
Polyethylene terephthalate (PET) material chemically degrades in the period passing from the raw material until the final product and causes by-products threatening human health to be formed. Within the scope of the invention, the formation of harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), diethylene glycol (DEG) is prevented in certain amounts by means of adding Mg2B20s mineral in ratio of 0.2% into polyethylene terephthalate (PET) material in preform stage with injection.
Mg2B205 particles used within the scope of the invention are produced with sol- gel method. In the studies carried out within the scope of the invention, different samples prepared in such a way were mixed into the polyethylene terephthalate (PET) material in double screw extruder, and Mg2B2Os/Polyethylene Terephthalate (PET) samples were prepared in injection machine. X-ray analysis was performed in order to observe magnesium borate formation, and scanned electron microscope (SEM) analysis was performed in order to display the material distribution. Thermogravimetric analysis (TGA) was applied in order to measure thermal strengths. Viscosity measurements were made, and their chemical contents (acetaldehyde (AA), COOH end group content (COOH), diethylene glycol (DEG)) were determined.
Magnesium Borate Synthesis with Sol-Gel Method and Preparation of Polyethylene Terephthalate (PET) Samples
Sol-gel method was used in production of Mg2B20s compound. (Formula 2) Formula 2. Synthesis reaction of Mg2B20s compound.
2Mg(N03)2 + 2H3B03 + 4CO(NH2)2 Mg2B205 + 16/3 N2 + 4C02 + 4/3 NH3 + 9H20
2 moles of Mg(N03)2, 2 moles of H3BO3 and 4 moles of CH4N20 were prepared and dried at 165 °C by stirring in calculated amounts in crucibles. The obtained white solid agate is milled in a mortar and sintered in ash furnace at 900 °C The different samples obtained were added into the polyethylene terephthalate (PET) material according to their percentages and pelletized in a double screw extruder. The prepared samples were analyzed for viscosity, diethylene glycol content, acetaldehyde content, COOH end group content, ash content, Tm, Tg temperatures.
Claims
1. A method for inhibiting harmful chemicals in production of PET materials enabling the harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), diethylene glycol (DEG) which are created upon the chemical degradation of Polyethylene Terephthalate (PET) material during the period passing from the raw material until the final product in Polyethylene Terephthalate (PET) production process and which are by products threatening human health, characterized by the steps of
- mixing magnesium nitrate, boric acid and urea solutions,
- drying the mixture,
- milling and grinding the obtained white solid agate in a mortar,
- sintering the mixture in powder form in an ash furnace,
- adding the obtained sample in ratio of 0.2% into the molten Polyethylene Terephthalate (PET) used in production of Polyethylene Terephthalate (PET) and then mixing,
- pelletizing the mixture in double screw extruder,
- obtaining polyethylene terephthalate (PET) material the acetaldehyde (AA), COOH end group (COOH), diethylene glycol (DEG) content of which is reduced.
2. A method for inhibiting harmful chemicals in production of PET materials according to claim 1, characterized in that 2 moles of magnesium nitrate (Mg(N03)2), 2 moles of boric acid (H3BO3) and 4 moles of urea
(CH4N2O) solution are mixed.
3. A method for inhibiting harmful chemicals in production of PET materials according to claim 1, characterized in that the mixture is dried at 165 °C.
4. A method for inhibiting harmful chemicals in production of PET materials according to claim 1, characterized in that the mixture in powder form is sintered in ash furnace at 900 °C.
5. A compound Mg2B20s used in order to be added into molten polyethylene terephthalate (PET) in ratio of 0.02% during injection stage in polyethylene terephthalate (PET) material production for the purpose of inhibiting harmful chemicals such as acetaldehyde (AA), COOH end group content (COOH), and diethylene glycol (DEG) which created by the chemical degradation of polyethylene terephthalate (PET) material in the period passing from raw material until the final product in polyethylene terephthalate (PET) production process and which are by-products threatening human health.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR201718204 | 2017-11-17 | ||
| PCT/TR2018/050648 WO2019098979A2 (en) | 2017-11-17 | 2018-11-01 | A method for inhibiting harmful chemicals formed in manufactured and semi-manufactured materials produced from pet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3710215A2 true EP3710215A2 (en) | 2020-09-23 |
| EP3710215A4 EP3710215A4 (en) | 2021-08-18 |
Family
ID=66539124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP18879477.0A Withdrawn EP3710215A4 (en) | 2017-11-17 | 2018-11-01 | A method for inhibiting harmful chemicals formed in manufactured and semi-manufactured materials produced from pet |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP3710215A4 (en) |
| WO (1) | WO2019098979A2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1196490A1 (en) * | 1999-06-30 | 2002-04-17 | The Dow Chemical Company | Extruded products from polyethylene terephthalate with reduced acetaldehyde content and process of their production |
| DE10045719B4 (en) * | 2000-09-15 | 2018-01-11 | Inventa-Fischer Gmbh & Co. Kg | Process for the preparation of polyesters with reduced content of acetaldehyde |
| US7915374B2 (en) * | 2009-04-27 | 2011-03-29 | Eastman Chemical Company | Copolyesters having improved thermal stability and methods for making them |
| US9828461B2 (en) * | 2012-03-01 | 2017-11-28 | Sabic Global Technologies B.V. | Poly(alkylene co-adipate terephthalate) prepared from recycled polyethylene terephthalate having low impurity levels |
| CN104151577A (en) * | 2014-08-19 | 2014-11-19 | 南通瑞隆新材料有限公司 | Preparation method of enhanced PET modified engineering plastic |
-
2018
- 2018-11-01 WO PCT/TR2018/050648 patent/WO2019098979A2/en unknown
- 2018-11-01 EP EP18879477.0A patent/EP3710215A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019098979A3 (en) | 2019-06-13 |
| WO2019098979A2 (en) | 2019-05-23 |
| EP3710215A4 (en) | 2021-08-18 |
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