Reaction yield of the present invention is 90.0%～98.1%, the degradable polyester-amide copolymer thermoplastic elastomer of preparation, and different according to raw materials used and formula rate can obtain 54-170 ℃ of product fusing point (Tm); Anti-open test what 15 ℃ of room temperatures, humidity 50%, speed 200mm/min carried out, the tensile strength of 1.00mm thickness, 6.00mm width hot pressing matrix is at 13-60MPa, elongation at break 21%-1200%; In the buffered soln of 37 ℃ of PH=7.2,100 days degradable 0.10wt%-12.50wt% of 1.0mm thickness matrix; When the content of ester bond in the polyester-amide copolymer during greater than 50% molar content, multipolymer can be dissolved in the chloroform solvent.

The present invention has the following advantages:

1. reaction was finished by one step of melt polymerization, basically identical in the ratio of key-amido linkage and the reaction monomers in the polyesteramide ester of reaction yield height, generation, and method is simply effective.

2. polyester-amide copolymer well combines the degradation property of aliphatic polyester and the thermal characteristics and the mechanical property of fatty polyamide.

3. use 6-caprolactone to be reaction monomers,, can in very large range control the structure and the performance of product by regulating its kind and proportioning with different chain length omega-amino acid.

Below be embodiments of the invention.

Embodiment 1. starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 6-aminocaprolc acid (AC) 10.06 (0.077mol) and about 0.4wt% butyl (tetra) titanate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AC) obtained_70/30Polyesteramide, reaction yield are 95.5%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.The matrix that obtains is cold-pressed into the anti-used batten of test of opening with Standard Module, and batten thickness is about 1.00mm, and width is 6.00mm.

The product index

Reaction yield is 95.5%

Ester/acid amides mol ratio: 1/0.42 viscosity (30 ℃, 0.5g dl^-1M-cresol solution in): 0.88 (dlg^-1)

Fusing point (Tm): 57.7 ℃ of degree of crystallinity: 17.7%

Tensile strength: 25.7MPa Young's modulus: 160.0MPa

Yield point strength: 6.7MPa extension at break: 1015.1%

Degradation speed: 15.6wt%/100D (the thick matrix of 1.00mm is in the buffered soln of 37 ℃ of PH=7.2)

Be dissolvable in water in the chloroform solvent

Embodiment 2: the starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 6-aminocaprolc acid (AC) 35.52g (0.269mol) and about 0.5wt% stannous octoate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AC) obtained_40/60Polyesteramide, reaction yield are 92.3%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.The matrix that obtains is cold-pressed into the anti-used batten of test of opening with Standard Module, and batten thickness is about 1.00mm, and width is 6.00mm.

The product index

Ester/acid amides mol ratio: 1/1.34 viscosity (30 ℃, 0.5g dl^-1M-cresol solution in): 0.83 (dl/g)

Fusing point (Tm): 102.9 ℃ of degree of crystallinity: 16.2%

Tensile strength: 43.1MPa Young's modulus: 309.0MPa

Yield point strength: 15.6MPa extension at break: 566.0%

Degradation speed: 8.9wt%/100D (in the buffered soln of 37 ℃ of PH=7.2)

Be not dissolved in the chloroform solvent

Embodiment 3: the starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 11-aminoundecanoic acid (AU) 24.00g (0.119mol), 0.5wt% butyl (tetra) titanate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AU) obtained_60/40Polyesteramide, reaction yield are 94.7%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.Matrix thickness is about 1.00mm.

The product index

Ester/acid amides mol ratio: 1/0.68 viscosity (30 ℃, 0.5g dl^-1M-cresol solution in); 0.70 (dl/g)

Fusing point (Tm): 72.9 ℃ of degree of crystallinity: 21.3%

Tensile strength: 38.1MPa Young's modulus: 233.0MPa

Yield point strength: 11.6MPa extension at break: 180.0%

Degradation speed: 1.8wt%/100D

Be dissolvable in water in the chloroform solvent

Embodiment 4. starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 11-hexosamine (AU) 83.91g (0.417mol) and about 0.5wt% butyl (tetra) titanate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AU) obtained_30/70Polyesteramide, reaction yield are 91.0%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.The matrix that obtains is cold-pressed into the anti-used batten of test of opening with Standard Module, and batten thickness is about 1.00mm, and width is 6.00mm.

The product index

Ester/acid amides mol ratio: 1/2.35 viscosity (30 ℃, 0.5g dl^-1M-cresol solution in): 0.88 (dlg^-1)

Fusing point (Tm): 65.7 ℃, 155.3 ℃ degree of crystallinity: 24.3%

Tensile strength: 55.7MPa Young's modulus: 369.0MPa

Yield point strength: 21.7MPa extension at break: 46.1%

Degradation speed; 0.13wt%/100D (the thick matrix of 1.00mm is in the buffered soln of 37 ℃ of PH=7.2)

Be not dissolved in the chloroform solvent

Embodiment 5. starting raw material 6-caprolactone that above-mentioned biologically degradable polyester-polyamide copolymer is the used (20.60g (0.179mol) of ε-CL), 6-aminocaprolc acid (AC) 11.81g (0.0895mol), 11-hexosamine (AU) 18.03g (0.0895mol) and about 0.5wt% butyl (tetra) titanate are added in the four-necked bottle, the feeding nitrogen replacement goes out air wherein, elevated temperature, earlier 140 ℃ of reactions 1 hour, then be warming up to 180 ℃ and insulation reaction 1 hour, in 10 minutes, be decompressed to 2.5kPa then, and be warmed up to 240～260 ℃, discharging when the pole-climbing phenomenon appears in system, thus P (CL/AC/AU) obtained_50/25/25Polyesteramide, reaction yield are 94.5%.The PEAs multipolymer that obtains is put into heat pressing forming machines, and temperature is made as higher 30 ℃ than melting point polymer temperature, and peak pressure 20MP is hot-forming.The matrix that obtains is cold-pressed into the anti-used batten of test of opening with Standard Module, and batten thickness is about 1.00mm, and width is 6.00mm.

The product index

Ester/acid amides mol ratio: 1/0.48 viscosity (30 ℃, 0.5gdl^-1M-cresol solution in): 0.85 (dlg^-1)

Fusing point (Tm): 77.7 ℃ of degree of crystallinity: 18.7%

Tensile strength: 43.7MPa Young's modulus: 281.0MPa

Yield point strength: 16.7MPa extension at break: 246.1%

Degradation speed: 3.56wt%/100D (the thick matrix of 1.00mm is in the buffered soln of 37 ℃ of PH=7.2)

Be dissolvable in water in the chloroform solvent

Used starting material all are marketable material among the above embodiment.

Claims

1. the preparation method of a degradable polyester-amide copolymer, it is characterized in that: with 6-caprolactone, omega-amino acid and catalyzer are added in the four-necked bottle, feed nitrogen protection, elevated temperature, earlier 120～140 ℃ of reactions one hour, then be warming up to 160～180 ℃ and also keep reaction 1 hour, remove nitrogen then, in 10 minutes, be decompressed to 2.5kPa and be warmed up to 230～270 ℃ of reactions, discharging when rod climbing phenomenon appears in system, thus polyester-amide copolymer obtained; Wherein, in the composition of raw materials, 6-caprolactone and omega-amino acid component count by molar, 6-caprolactone is 25-75 part, omega-amino acid is 75-25 part, catalyst levels accounts for 0.1～0.5% of above-mentioned 6-caprolactone and omega-amino acid total mass, and omega-amino acid is a kind of or 6-aminocaprolc acid in 6-aminocaprolc acid, the 11-aminoundecanoic acid and the mixture of 11-aminoundecanoic acid, and catalyzer is butyl (tetra) titanate or stannous octoate.