WO2021167559A1

WO2021167559A1 - Novel triazine-based plasticizers

Info

Publication number: WO2021167559A1
Application number: PCT/TR2020/051095
Authority: WO
Inventors: Lokman TORUN; Mohamed Hadi Ali AL-JUMAILI; Ammar Abdulkareem Saadi AL-OBAIDI; Nihat AKKURT
Original assignee: Yildiz Teknik Universitesi
Priority date: 2020-02-20
Filing date: 2020-11-12
Publication date: 2021-08-26
Also published as: TR202002641A2

Abstract

The invention is related to triazine-based plasticizers comprising an ether functional group instead of an ester functional group that is used in the plasticizer substances.

Description

NOVEL TRIAZINE-BASED PLASTICIZERS

Technical Field

The invention is related to novel triazine-based plasticizers. The invention is particularly related to plasticizers that are triazine-based and that contain an ether functional group instead of an ester functional group

Prior Art

During the production by injection moulding or other similar methods, of plastic bottles having different volumes, carboys and other various plastic-based kitchen tools, various amounts of plasticizers are added to the plastic raw material. A considerable part of these plasticizers is phthalate-based and widely used in the industry. The plasticizers used in the production of plastic containers that contain various foods and drinks, get mixed into the food and drinks in the course of time and they enter the body through nutrition.

Phthalate-based plasticizers contain an ester functional group and they can penetrate into the skin through contact as well, since they are straight chain molecules. Besides this, they hydrolyze within the body and decompose to smaller- size components. The components which have aromatic structure carry health risks.

Since phthalate-based plasticizers pose health risks, restrictions are expected regarding their use. Therefore, intensive studies have been carried out on the development of non-phthalate-based plasticizers.

In the Chinese patent document numbered CN102741235 of the prior art; a triazine derivative which has high-temperature resistance and high cross-linking speed is described. In the Chinese patent document number CN105440282 of the prior art; 1,3,5- triazine derivative compounds with high or low polymerization degrees and the preparation method thereof is described.

The International patent document numbered WO2013041592 of the prior art is related to special amino-triazine based Mannich compounds for increasing the resistance against the deterioration caused by the oxidation of organic materials.

However, the plasticizers of the prior art include phthalate-based plasticizers that are used in the production of plastics and they carry health risks. Developing novel triazine-based plasticizers which can be used instead of phthalate-based plasticizers is required in order to solve this problem.

The Aim of the Invention

The aim of the invention is to provide triazine-based plasticizers which do not carry health risks.

Another aim of the invention is to provide triazine-based plasticizers which contain an ether functional group.

Another purpose of the invention is to provide triazine-based plasticizers which do not carry a hydrolyzation risk.

Another aim of the invention is to provide plasticizers that prevent the plasticizers used in the production of plastic containers produced with the purpose of storing foods and drinks, from carrying health risks.

Detailed Description of the Invention

Triazine-based plasticizers were developed with the present invention. The methods of obtaining the plasticizers developed, and their chemical formulas are described in detail in the below. 2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), methanol (1,73 g, 54,2 mmol), potassium carbonate (23,9 g, 173,5 mmol) and 50 ml dioxane was placed in a round-bottom flask and the mixture was stirred for 3 hours at room temperature. 2-ethylhexane- 1 -ol (Formula XI, 14,1 g, 108,4 mmol) was added to the obtained mixture. The obtained mixture was stirred for 5 hours at 85 °C. The solution was poured into ethylacetate:water mixture (50 mL:50 mL). After the aqueous phase was resolved, the remaining organic phase was washed twice with 50 mL water and dried over sodium sulfate. After the solvent was removed under vacuum, 17 g substance was obtained with 85% yield. (Formula (I))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), methanol (1,73 g, 54,2 mmol), potassium carbonate (23,9 g, 173,5 mmol) and 50 ml dioxane was placed in a round-bottom flask and the mixture was stirred for 3 hours at room temperature. To the obtained mixture, dodecan-l-ol (Formula XII, 20.18 g, 108,4 mmol) was added. The obtained mixture was stirred for 5 hours at 85 °C. The solution was poured into ethylacetate:water mixture (50 mL:50 mL). The aqueous phase was resolved and the remaining organic phase was washed twice with 50 mL water and dried over sodium sulfate. After the solvent was removed under vacuum 23 g substance was obtained with 88% yield. (Formula (Π))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), 2-ethylhexane-l-ol (Formula XI, 21.13 g, 162.6 mmol), potassium carbonate (23.94 g, 173.5 mmol) and 50 ml dioxane was placed in a round-bottom flask and the mixture was stirred for 6 hours at 85 °C. The solution was poured into ethyl acetate:water mixture (50 mL:50 mL). The aqueous phase was resolved and the remaining organic phase was washed twice with 50 mL waterand dried over sodium sulfate. After the solvent was removed under vacuum 20 g substance was obtained with 79% yield. (Formula (ΙΠ))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), dodecan-l-ol (Formula XII, 30,29 g, 162,6 mmol), potassium carbonate (23.94 g, 173.5 mmol) and 50 ml dioxane was placed in a round-bottom flask and the mixture was stirred for 6 hours at 85 °C. The solution was poured into the ethyl acetate:water mixture (50 mL:50 mL). The aqueous phase was resolved and the remaining organic phase was washed twice with 50 mL water and dried over sodium sulfate. After the solvent was removed under vacuum 28 g substance was obtained with 81,4% yield.(Formula (TV))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), 2-ethylhexane-1-ol (Formula XI, 14.09 g, 108.45 mmol), potassium carbonate (23.93 g, 173.44 mmol) and 50 ml dioxane was placed in a round-bottom flask and the mixture was stirred for 3 hours first at 60 °C, afterwards, 2,2- dimethylpropane-1,3-diol (2.8 g, 27.1 mmol) was added and the obtained mixture was stirred for 5 hours at 90 °C. After the mixture was cooled down to room temperature, it was poured into the ethylacetate:water mixture (50 mL:50 mL). The aqueous phase was resolved and the remaining organic phase was washed twice with 50 mL water and dried over sodium sulfate. After the solvent was removed under vacuum 18,5 g substance was obtained with 88% yield. (Formula (V))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), 2-ethylhexane-l-ol (Formula XI, 14.09 g, 108.45 mmol), potassium carbonate (23.93 g, 173.44 mmol) and 50 ml dioxane was put in a round-bottom flask and the mixture was stirred for 3 hours first at 60 °C, after, ethane- 1,2-diol (1.68 g, 27.07 mmol) was added and the obtained mixture was stirred for 5 hours at 90 °C. After the mixture was cooled down to room temperature, it was poured into the ethylacetate:water mixture (50 mL:50 mL). Aqueous phase was resolved and the remaining organic phase was washed twice with 50 mL water and dried over sodium sulfate. After the solvent was removed under vacuum 18 g substance was obtained with 90% yield. (Formula (VI))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), 2-ethylhexane- 1 -ol (Formula XI, 14.09 g, 108.45 mmol), potassium carbonate (23.93 g, 173.44 mmol) and 50 ml dioxane was put in a round-bottom flask and the mixture was stirred for 3 hours first at 60 °C, after, 2,2'-oxydiethanol (2.87 g, 27.1 mmol) was added and the obtained mixture was stirred for 5 hours at 90 °C. After the mixture was cooled down to room temperature, it was poured into the ethylacetate: water mixture (50 mL:50 mL). The aqueous phase was resolved and the remaining organic phase was washed twice with 50 mL waterand dried over sodium sulfate. After the solvent was removed under vacuum 18 g substance was obtained with 85% yield. (Formula (VII))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), 2-ethylhexane- l-ol (Formula XI, 14.09 g, 108.45 mmol), potassium carbonate (23.93 g, 173.44 mmol) and 50 ml dioxane was placed in a round-bottom flask and the mixture was stirred for 3 hours first at 60 °C, afterwards, butane- 1,4-diol (2.44 g, 27.11 mmol) was added and the obtained mixture was stirred for 5 hours at 90 °C. After the mixture was cooled down to room, it was poured into the ethylacetate:water mixture (50 mL:50 mL). The aqueous phase was resolved and the remainingorganic phasewas washed twice with 50 mL waterand dried over sodium sulfate. After the solvent was removed trader vacuum 18 g substance was obtained with 87% yield. (Formula (VIII))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), 2-ethy lhexane- 1 -ol (Formula XI, 14.09 g, 108.45 mmol), potassium carbonate (23.93 g, 173.44 mmol) and 50 ml dioxane was placed in a round-bottom flask and the mixture was stirred for 3 hours first at 60 °C, after, butane- 1,4-diol (2.44 g, 27.11 mmol) was added and the obtained mixture was stirred for 5 hours at 90 °C. After the mixture was cooled down to room temperature, it was poured into the ethylacetate:water mixture (50 mL:50 mL). The aqueous phase was resolved and the remaining organic phase was washed twice with 50 mL water and dried over sodium sulfate. After the solvent was removed trader vacuum 18 g substancewas obtained with 87% yield. (Formula (IX))

2,4,6-trichloro-l,3,5-triazine (10 g, 54.2 mmol), 2-ethy lhexane- 1 -ol dodecan-l-ol (Formula ΧII, 20.20 g, 108,4 mmol), potassium carbonate (15,96115,67 mmol) and 50 ml dioxane was placed in a round-bottom flask and the mixture was stirred for 6 hours at 85 °C. The solution was poured into ethyl acetate:water mixture (50 mL:50 mL). The aqueous phase was resolved and the remaining organic phase was washed twice with 50 mL water and dried over sodium sulfate. After the solvent was removed under vacuum 18,5 g substance was obtained with 81,1% yield. (Formula (X))

The plasticizers having the Formula (I) - (TV) developed with the invention are monotriazine-based and they contain 8-carbon and/or 12-carbon alkoxy sub-groups bonded to a triazine center.

The plasticizers having the Formula (V) - (X) developed with the invention, contain triazine structures that are two of each, comprising 8-carbon and/or 12- carbon alkoxy groups, and they are bonded together with flexible and short chains.

Among these, the compounds having the Formula (V) and Formula (VI) contain the bonding elements of the -O-CH₂-C(CH₃)₂-CH₂-0- group, compounds having the Formula (VII) and Formula (VIII) comprise the bonding elements of the O-CH₂-CH₂-O- chain, and compounds having the Formula (IX) and Formula (X) comprise the bonding elements of the-O-CH₂-CH₂-CH₂-CH₂-0- chain.

Claims

1. The invention is related to novel plasticizers, wherein the plasticizer is characterized in that it comprises;

- alkoxy sub-groups with 8-carbons and/or 12-carbons that are bonded to a monotriazine based triazine center.

2. The invention is related to plasticizers according to Claim 1, characterized in that the plasticizer has any one of the following

Formula (I),

Formula (II),

Formula (ΙII),

Formula (IV).

3. The invention is related to novel plasticizers, characterized in that the plasticizer comprises; alkoxy groups having 8-carbons and/or 12-carbons, where two triazine structures are bonded together with flexible and short chains.

4. Plasticizers according to Claim 3, characterized in that the plasticizer has any one of the following;

10

Formula (V),

Formula (VI)

Formula (VII),

Formula (VIII),

Formula (IX),

Formula (X).

5. A plasticizer according to Claim 4, characterized in that the plasticizers that have Formula (V) and Formula (VI) comprise the -O-CH₂-C(CH3)₂-CH₂-0- group.

6. Plasticizer according to Claim 4, characterized in that the plasticizers that have Formula (VII) and Formula (VIII) comprise the O-CH₂-CH₂-O- chain.

7. Plasticizer according to Claim 4, characterized in that the plasticizers that have Formula (IX) and Formula (X) comprise the -O-CH₂-CH₂-CH₂-CH₂-O- chain.