A kind of multi-block copolyester and its preparation method and the preparation method of its compound

Abstract

The invention relates to a multi-block copolyester, a preparation method of the multi-block copolyester and a preparation method of a compound of the multi-block copolyester, especially relates to a multi-block copolyester which contains a furan ring in a molecular main chain undergoing a Diels-Alder reaction, and belongs to the technical field of polyester material preparation. The furan ring in the molecular main chain of the multi-block copolyester can undergo a Diels-Alder reaction and a reverse Diels-Alder reaction. The multi-block copolyester has excellent thermosetting resin performances and wide performance adjustability at a room temperature and has good processing molding performances of thermoplastic resin at a high temperature. The thermoplastic crosslinked polyester has a property of self-repairing micro-cracks in a wide temperature zone and can be used in fields of mulching films and packaging materials.

Description

technical field

[0001] The present invention relates to a kind of multi-block copolyester and its preparation method and the preparation method of its compound, especially relate to a kind of multi-block copolyester whose main chain contains furan ring and its preparation method and its compound preparation method , particularly relates to a multi-block copolyester which contains a furan ring in the molecular main chain and can undergo Diels-Alder reaction, and belongs to the technical field of polyester material preparation. Background technique

[0002] Due to its good comprehensive properties, polyester is widely used in electrical, electronic, chemical, packaging and other fields. Compared with thermoplastic resins, thermosetting resins are cross-linked between molecules to form a network structure, so they have the characteristics of high temperature resistance, high hardness, high rigidity, and good dimensional stability of products. However, due to the irreversibilit...

Examples

preparation example Construction

[0045] The preparation method of the multi-block copolyester that the present invention proposes comprises the following steps:

[0046] (1) Solution polymerization:

[0047] (1-1) Evenly mix dibasic alcohol and dibasic acid, wherein, the molar weight of dibasic alcohol is 1.05-1.3 times of dibasic acid molar weight, pass into inert gas protection, add catalyst, the addition amount of catalyst is two 5%-15% of the molar weight of the basic acid, the catalyst is 4-methylaminopyridine, and the stirring is started until the reactants are completely dissolved to obtain the first solution;

[0048] (1-2) In the first solution of the above-mentioned step (1-1), add dehydrating agent in 3-5 times, the addition of dehydrating agent is 100%-200% of dibasic acid molar weight, described dehydrating agent N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N-hydroxysuccinimide, N-hydroxysulfosuccinimide or 1-(3 -One or more of dimethylaminopropyl)-3-ethylcarbodiimide hydrochlor...

Embodiment 1

[0065] Add 0.4 mol of succinic acid and 0.44 mol of 2,5-furandimethanol into 500 ml of dichloromethane and mix evenly, pass through nitrogen protection, add 0.02 mol of 4-methylaminopyridine as a catalyst, and start stirring until the reactants are completely dissolved. 0.8 mol of dehydrating agent N,N-dicyclohexylcarbodiimide was added to the solution in the above step in four times, and the addition time was 0 hour, 3 hours, 6 hours and 9 hours after the reaction started, and 0.2 mol was added each time. Reaction at normal temperature, the reaction time is 12 hours. Purify to obtain hydroxyl-terminated polysuccinate 2,5-furandimethanol oligomer;

[0066] Add 0.6 mol of succinic acid and 0.66 mol of 1,4-butanediol into 500 ml of dichloromethane and mix evenly, pass through nitrogen protection, add 0.02 mol of 4-methylaminopyridine as a catalyst, and start stirring until the reactants are completely dissolved. 1.2 moles of dehydrating agent N,N-dicyclohexylcarbodiimide was ad...

Embodiment 2

[0069] Add 0.4 moles of terephthalic acid and 0.42 moles of 2,5-furandimethanol into 500 ml of dichloromethane and mix evenly, pass through nitrogen protection, add 0.06 moles of 4-methylaminopyridine as a catalyst, start stirring until the reactants are completely dissolved . Add 0.8 moles of dehydrating agent N,N'-diisopropylcarbodiimide to the solution in the above steps in four times, the addition time is 0 hour, 3 hours, 6 hours and 9 hours after the reaction starts, and add 0.2 moles each time . Reaction at normal temperature, the reaction time is 24 hours. Purify to obtain hydroxyl-terminated poly(2,5-furandimethylene terephthalate) oligomer;

[0070] Add 0.6 mol of terephthalic acid and 0.66 mol of ethylene glycol into 500 ml of dichloromethane and mix evenly, pass through nitrogen protection, add 0.09 mol of 4-methylaminopyridine as a catalyst, and start stirring until the reactants are completely dissolved. Add 1.2 moles of dehydrating agent N,N'-diisopropylcarbod...

technical field

[0001] The present invention relates to a kind of multi-block copolyester and its preparation method and the preparation method of its compound, especially relate to a kind of multi-block copolyester whose main chain contains furan ring and its preparation method and its compound preparation method , particularly relates to a multi-block copolyester which contains a furan ring in the molecular main chain and can undergo Diels-Alder reaction, and belongs to the technical field of polyester material preparation. Background technique

[0002] Due to its good comprehensive properties, polyester is widely used in electrical, electronic, chemical, packaging and other fields. Compared with thermoplastic resins, thermosetting resins are cross-linked between molecules to form a network structure, so they have the characteristics of high temperature resistance, high hardness, high rigidity, and good dimensional stability of products. However, due to the irreversibilit...

Examples

preparation example Construction

[0045] The preparation method of the multi-block copolyester that the present invention proposes comprises the following steps:

[0046] (1) Solution polymerization:

[0047] (1-1) Evenly mix dibasic alcohol and dibasic acid, wherein, the molar weight of dibasic alcohol is 1.05-1.3 times of dibasic acid molar weight, pass into inert gas protection, add catalyst, the addition amount of catalyst is two 5%-15% of the molar weight of the basic acid, the catalyst is 4-methylaminopyridine, and the stirring is started until the reactants are completely dissolved to obtain the first solution;

[0048] (1-2) In the first solution of the above-mentioned step (1-1), add dehydrating agent in 3-5 times, the addition of dehydrating agent is 100%-200% of dibasic acid molar weight, described dehydrating agent N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N-hydroxysuccinimide, N-hydroxysulfosuccinimide or 1-(3 -One or more of dimethylaminopropyl)-3-ethylcarbodiimide hydrochlor...

Embodiment 1

[0065] Add 0.4 mol of succinic acid and 0.44 mol of 2,5-furandimethanol into 500 ml of dichloromethane and mix evenly, pass through nitrogen protection, add 0.02 mol of 4-methylaminopyridine as a catalyst, and start stirring until the reactants are completely dissolved. 0.8 mol of dehydrating agent N,N-dicyclohexylcarbodiimide was added to the solution in the above step in four times, and the addition time was 0 hour, 3 hours, 6 hours and 9 hours after the reaction started, and 0.2 mol was added each time. Reaction at normal temperature, the reaction time is 12 hours. Purify to obtain hydroxyl-terminated polysuccinate 2,5-furandimethanol oligomer;

[0066] Add 0.6 mol of succinic acid and 0.66 mol of 1,4-butanediol into 500 ml of dichloromethane and mix evenly, pass through nitrogen protection, add 0.02 mol of 4-methylaminopyridine as a catalyst, and start stirring until the reactants are completely dissolved. 1.2 moles of dehydrating agent N,N-dicyclohexylcarbodiimide was ad...

Embodiment 2

[0069] Add 0.4 moles of terephthalic acid and 0.42 moles of 2,5-furandimethanol into 500 ml of dichloromethane and mix evenly, pass through nitrogen protection, add 0.06 moles of 4-methylaminopyridine as a catalyst, start stirring until the reactants are completely dissolved . Add 0.8 moles of dehydrating agent N,N'-diisopropylcarbodiimide to the solution in the above steps in four times, the addition time is 0 hour, 3 hours, 6 hours and 9 hours after the reaction starts, and add 0.2 moles each time . Reaction at normal temperature, the reaction time is 24 hours. Purify to obtain hydroxyl-terminated poly(2,5-furandimethylene terephthalate) oligomer;

[0070] Add 0.6 mol of terephthalic acid and 0.66 mol of ethylene glycol into 500 ml of dichloromethane and mix evenly, pass through nitrogen protection, add 0.09 mol of 4-methylaminopyridine as a catalyst, and start stirring until the reactants are completely dissolved. Add 1.2 moles of dehydrating agent N,N'-diisopropylcarbod...

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