Poly-2,5-butanediol furadicarboxylic acid copolyester and preparation method thereof

Abstract

The invention provides copolyester of the structure as shown in the formula (I), wherein a is more than or equal to 1; b is more than or equal to 1; n is more than or equal to 1; x is more than or equal to 0; y is more than or equal to 0; x and y are not 0 at the same time. According to the preparation method, the crystallization behavior of 2,5-furadicarboxylic acid or a derivative thereof is changed by polymerization reaction of 2,5-furadicarboxylic acid or the derivative thereof with ethanediol, 1,4-butanediol, long-chain dihydric alcohol of a structure as shown in the formula (II) and a catalyst, so as to finally obtain the structure as shown in the formula (I), which is high in co-polyester toughness and high in elongation at break and impact strength.

Description

technical field

[0001] The invention relates to the technical field of materials and macromolecules, in particular to a poly(2,5-butylene furandicarboxylate) copolyester and a preparation method thereof. Background technique

[0002] Polybutylene 2,5-furandicarboxylate (PBF), which is similar in structure to polybutylene terephthalate (PBT), is considered to be a substitute for PBT. It is composed of 2,5-furandicarboxylic acid and It is obtained by polymerization of 1,4-butanediol. It is 100% bio-based polyester with good thermal stability and mechanical properties. It is a new type of environmentally friendly green polyester material.

[0003] Although PBF has good mechanical properties, it is easy to crystallize, brittle, and has poor impact strength. Therefore, it is very necessary to develop a polyester with good impact strength and good toughness. Contents of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to pro...

Examples

preparation example Construction

[0030] The present invention provides a kind of preparation method of the copolyester of formula (I) structure, comprising:

[0031] A) 2,5-furandicarboxylic acid or its derivatives are mixed with 1,4-butanediol and a long-chain diol of formula (II) and a catalyst to obtain a prepolymer; the 2,5-furandicarboxylic acid or its derivatives are 2,5-furandicarboxylic acid or dimethyl 2,5-furandicarboxylate;

[0032] B) the prepolymer is carried out polycondensation reaction, obtains the poly-2,5-furandiol copolyester of formula (I) structure;

[0033]

[0034] Where a≧1, b≧1, n≧1, x≧0, y≧0, and x and y are both 0.

[0035] In the present invention, first, 2,5-furandicarboxylic acid or its derivatives, 1,4-butanediol, long-chain dihydric alcohols with the structure of formula (II), and a catalyst are added into a reaction flask, and stirred and reacted under the protection of an inert gas to obtain prepolymer.

[0036] According to the present invention, the molar ratio of the...

Embodiment 1

[0054] Add 1.00mol 2,5-furandicarboxylic acid, 1.52mol 1,4-butanediol and 0.08mol 1,2-decanediol into the reaction flask, stannous oxalate is used as catalyst, accounting for 0.3 mole fraction of 2,5-furandicarboxylic acid %, under the protection of nitrogen, stirred and reacted at 230°C for 2h to form a prepolymer;

[0055] Vacuumize the above prepolymer to 0.070MPa, and stir at 240°C for 6h to obtain poly-2,5-furandicarboxylic acid-butylene glycol-1,2-decanediol copolyester (PBSF). Polybutylene 2,5-furandicarboxylate (PBF) synthesized under the same conditions was used as a comparison.

[0056] The performance of the poly-2,5-furandicarboxylic acid-butylene glycol-1,2-decanediol copolyester prepared in Example 1 of the present invention was measured, and at the same time, the poly-2,5-furandiol synthesized under the same conditions Butylene glycol formate (PBF) was used for comparative determination. The result is as figure 1 and shown in Table 1. in figure 1 The NMR fi...

Embodiment 2

[0060] Add 1.00mol of 2,5-furandicarboxylic acid, 1.52mol of 1,4-butanediol and 0.08mol of 1,2-dodecanediol into the reaction flask, tetrabutyl titanate is used as a catalyst, accounting for 2,5-furandicarboxylic acid moles 0.1% of the fraction, under the protection of nitrogen, stirred and reacted at 230°C for 1.5h to form a prepolymer;

[0061] The above prepolymer was evacuated to 0.070MPa, stirred and reacted at 240° C. for 6 hours to obtain poly-2,5-furandicarboxylic acid-butylene glycol-1,2-dodecanediol copolyester (PBTF).

[0062] The poly-2,5-furandicarboxylic acid-butylene glycol-1,2-dodecanediol copolyester prepared in Example 2 of the present invention was tested for performance, and at the same time, the poly-2,5-furan synthesized under the same conditions Butylene glycol diformate (PBF) was used for comparative determination. The results are shown in Table 2.

[0063] Table 2

[0064]

technical field

[0001] The invention relates to the technical field of materials and macromolecules, in particular to a poly(2,5-butylene furandicarboxylate) copolyester and a preparation method thereof. Background technique

[0002] Polybutylene 2,5-furandicarboxylate (PBF), which is similar in structure to polybutylene terephthalate (PBT), is considered to be a substitute for PBT. It is composed of 2,5-furandicarboxylic acid and It is obtained by polymerization of 1,4-butanediol. It is 100% bio-based polyester with good thermal stability and mechanical properties. It is a new type of environmentally friendly green polyester material.

[0003] Although PBF has good mechanical properties, it is easy to crystallize, brittle, and has poor impact strength. Therefore, it is very necessary to develop a polyester with good impact strength and good toughness. Contents of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to pro...

Examples

preparation example Construction

[0030] The present invention provides a kind of preparation method of the copolyester of formula (I) structure, comprising:

[0031] A) 2,5-furandicarboxylic acid or its derivatives are mixed with 1,4-butanediol and a long-chain diol of formula (II) and a catalyst to obtain a prepolymer; the 2,5-furandicarboxylic acid or its derivatives are 2,5-furandicarboxylic acid or dimethyl 2,5-furandicarboxylate;

[0032] B) the prepolymer is carried out polycondensation reaction, obtains the poly-2,5-furandiol copolyester of formula (I) structure;

[0033]

[0034] Where a≧1, b≧1, n≧1, x≧0, y≧0, and x and y are both 0.

[0035] In the present invention, first, 2,5-furandicarboxylic acid or its derivatives, 1,4-butanediol, long-chain dihydric alcohols with the structure of formula (II), and a catalyst are added into a reaction flask, and stirred and reacted under the protection of an inert gas to obtain prepolymer.

[0036] According to the present invention, the molar ratio of the...

Embodiment 1

[0054] Add 1.00mol 2,5-furandicarboxylic acid, 1.52mol 1,4-butanediol and 0.08mol 1,2-decanediol into the reaction flask, stannous oxalate is used as catalyst, accounting for 0.3 mole fraction of 2,5-furandicarboxylic acid %, under the protection of nitrogen, stirred and reacted at 230°C for 2h to form a prepolymer;

[0055] Vacuumize the above prepolymer to 0.070MPa, and stir at 240°C for 6h to obtain poly-2,5-furandicarboxylic acid-butylene glycol-1,2-decanediol copolyester (PBSF). Polybutylene 2,5-furandicarboxylate (PBF) synthesized under the same conditions was used as a comparison.

[0056] The performance of the poly-2,5-furandicarboxylic acid-butylene glycol-1,2-decanediol copolyester prepared in Example 1 of the present invention was measured, and at the same time, the poly-2,5-furandiol synthesized under the same conditions Butylene glycol formate (PBF) was used for comparative determination. The result is as figure 1 and shown in Table 1. in figure 1 The NMR fi...

Embodiment 2

[0060] Add 1.00mol of 2,5-furandicarboxylic acid, 1.52mol of 1,4-butanediol and 0.08mol of 1,2-dodecanediol into the reaction flask, tetrabutyl titanate is used as a catalyst, accounting for 2,5-furandicarboxylic acid moles 0.1% of the fraction, under the protection of nitrogen, stirred and reacted at 230°C for 1.5h to form a prepolymer;

[0061] The above prepolymer was evacuated to 0.070MPa, stirred and reacted at 240° C. for 6 hours to obtain poly-2,5-furandicarboxylic acid-butylene glycol-1,2-dodecanediol copolyester (PBTF).

[0062] The poly-2,5-furandicarboxylic acid-butylene glycol-1,2-dodecanediol copolyester prepared in Example 2 of the present invention was tested for performance, and at the same time, the poly-2,5-furan synthesized under the same conditions Butylene glycol diformate (PBF) was used for comparative determination. The results are shown in Table 2.

[0063] Table 2

[0064]

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