CN103881086A - Biodegradable alternate polyesteramide preparation method - Google Patents

Abstract

The invention relates to a biodegradable alternate polyesteramide preparation method, and belongs to the technical field of polyesteramides. The preparation method adopts a condensation polymerization-chain extension method to prepare the aliphatic alternate polyesteramide, and comprises that: an aliphatic nylon salt and a dicarboxylic acid are subjected to condensation polymerization to prepare diamide diacid, the diamide diacid and a diol are subjected to condensation polymerization to prepare an aliphatic alternate polyesteramide prepolymer, and chain extenders such as bisoxazoline and diacyl di-lactam are adopted to carry out chain extension on the prepolymer to prepare the biodegradable alternate type polyesteramide with the intrinsic viscosity of 0.49-0.75 dL/g. The biodegradable alternate polyesteramide has characteristics of regular structure, good thermal property and good mechanical property.

Description

Preparation method of biodegradable alternating polyester amide

technical field

The invention relates to a method for preparing an aliphatic alternating polyester amide, in particular to preparing a diamide diacid by polycondensation of an aliphatic nylon salt and a dibasic acid, and then polycondensing with a dibasic alcohol to prepare an aliphatic alternating polyester amide prepolymer. A biodegradable alternating polyester amide with an intrinsic viscosity at 30°C of 0.49-0.75 dL/g is prepared through chain extension of a binary oxazoline and a diacyl bislactam chain extender, and belongs to the technical field of polyester amides.

technical background

Aliphatic polyester amide (PEA) is a new type of biodegradable polymer material. Compared with aliphatic polyester, due to the introduction of amide groups and the formation of hydrogen bonds between amide groups, the polymer has better mechanical properties. Performance and strength, while the presence of ester bonds endows the material with good biodegradability, making it have a wide range of application prospects.

U.S. Patent US0,065,314 (2005) reported the synthesis of a tri-block biodegradable polyester with adipic acid, 1,4-butanediol, caprolactam, and hexamethylenediamine as raw materials and under the action of the branching agent pentaerythritol Amide, this material has good tensile properties, elongation at break and biodegradability, but the preparation method used is the direct melt polycondensation method, which requires a high degree of vacuum, which must be below 0.5mmHg.

Bayer company patents DE4327024 (1995), WO9928371 (1999), WO9935179 (1999) have reported the synthesis of biodegradable polyester amide by the reaction of adipic acid, 1,4-butanediol, caprolactam or hexamethylenediamine. The product has Good mechanical properties and biodegradability, and a series of such polyester amides are produced under the trademark of BAK. However, in this type of polyester amides, the ester bonds and amide bonds are randomly distributed, the crystallinity of the polymer is poor or the melting point is low, and the heat resistance is poor; and the preparation method used is a direct melt polycondensation method. The vacuum degree is very high, and the vacuum degree must be below 0.5mmHg.

Domestic Liu Xiaobo et al. (Synthetic Chemistry, 1999, 7(4), 354) reacted glycolic acid with 1,12-dodecanediamine or hexamethylenediamine and caprolactone to obtain two diamide diols. Amide diols and dibasic acids undergo melt co-condensation reaction, and by adjusting the ratio of the two diamide diols, a series of polyester amide copolymers with different properties and degradation rates are obtained. However, the polycondensation of dibasic acid and diamide diol is not easy to control the feed ratio, and it is easy to cause volatilization loss of monomers under high temperature and high vacuum, which affects the ratio of raw materials, so it is difficult to obtain high molecular weight polymers.

Chinese patents CN1,310,194A (2001), CN1,124,304C (2003), CN101,020,746A (2007) reported the preparation of high molecular weight polyesters by diisocyanate or dioxazoline extended chain aliphatic polyester prepolymers However, the polyester amide prepared by this method has a low amide bond content, and compared with the corresponding aliphatic polyester, the thermal and mechanical properties are not significantly improved.

Contents of the invention

The object of the present invention is to provide a method for preparing aliphatic alternating polyester amide by polycondensation-chain extension with low requirements on vacuum degree and equipment, no pollution, and easy operation. The raw materials of the method are cheap and easy to obtain, the preparation of the prepolymer is simple, the chain extension reaction time is short, and the prepared alternating polyester amide has a regular structure and good thermal and mechanical properties.

The present invention adopts polycondensation-chain extension method to prepare aliphatic alternating polyester amide, first prepares diamide diacid by condensation polymerization of aliphatic nylon salt and dibasic acid, and then prepares aliphatic alternating polyester amide prepolymer by polycondensation with dibasic alcohol, The prepolymer chain is extended by binary oxazoline and diacylbislactam chain extender to prepare biodegradable alternating polyester amide with intrinsic viscosity between 0.49 and 0.75dL/g. The specific steps are as follows:

1) Feed the aliphatic nylon salt and the aliphatic dibasic acid according to the molar ratio of 1: (1~1.1), add 0.2% of the total monomer weight of phosphorous acid as a stabilizer, and in nitrogen atmosphere, at 200 ℃ React at normal pressure for 1-2 hours, then raise the temperature to 210°C, and react at normal pressure for 3 hours until no more water evaporates to obtain diamide diacid;

2) The diamide diacid prepared in step 1) and the aliphatic dihydric alcohol are polycondensed according to the molar ratio of (1-1.1): 1, and phosphorous acid of 0.1% of the total monomer weight is added as a stabilizer, and in the presence of a catalyst , nitrogen atmosphere, 200-230°C under normal pressure reaction, collect the generated water to 80% of the theoretical amount, then gradually decompress the reaction with a water pump for 4 hours, continue to decompress with an oil pump to keep the vacuum degree below 5mmHg, and react for 4 hours until Until the acid value is basically unchanged, an aliphatic alternating polyester amide prepolymer containing terminal hydroxyl groups and terminal carboxyl groups is obtained, wherein the amount of the catalyst is 0.01 to 0.3% of the total weight of the monomers;

3) The aliphatic alternating polyester amide prepolymer containing terminal hydroxyl group and carboxyl terminal group prepared in step 2) and chain extender diacylbislactam and bisoxazoline are mixed at 210-230°C under nitrogen protection After reacting with normal pressure for 1.5h, and then reacting at 1-5mmHg for 0.5-4.6h, a biodegradable alternating polyester amide with an intrinsic viscosity of 0.49-0.75dL/g is obtained; wherein, 100 parts by weight of polyester Based on the amide prepolymer, the amount of the chain extender diacylbislactam is 0.2-2.1 parts by weight, and the amount of the bisoxazoline chain extender is 6.1-9.9 parts by weight.

Wherein, the diamide diacid described in step 1) has the structure shown in general formula (I):

In the above formula: m=0~10, p=2~12.

The general structural formula of the nylon salt in step 1) is: ⁺ H ₃ N(CH ₂ ) _p NH ₃ ^+- OOC(CH ₂ ) _m COO ^- , where m=0-10, p=2-12. Commonly used is one or more of nylon 26 salt, nylon 210 salt, nylon 36 salt, nylon 310 salt, nylon 46 salt, nylon 410 salt, nylon 66 salt, nylon 610 salt, nylon 1010 salt, etc.; The general formula of aliphatic dibasic acid is HOOC(CH ₂ ) _m COOH, m=0~10, and the commonly used one is oxalic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, etc. or several.

The aliphatic dihydric alcohol described in step 2) is selected from the general formula HO(CH ₂ ) _n OH, n=2~6, commonly used are ethylene glycol, 1,3-propanediol, 1,4-butanediol One or more of alcohol, 1,6-hexanediol or diethylene glycol, etc.

The catalyst described in step 2) is one or a mixture of dibutyltin oxide, tin oxide, stannous chloride, zinc oxide, zinc acetate, tetrabutyl titanate or tetraisopropyl titanate.

The phosphorous acid stabilizer added in steps 1) and 2) can prevent the oxidation reaction in the polycondensation process.

The chain extender bisoxazoline described in step 3) includes aliphatic binary oxazoline or aromatic binary oxazoline, and its general structural formula is shown in (II):

In the formula, R ₁ is -(CH ₂ ) _h -, where h=0~20 or is phenyl or pyridyl, connected to the oxazoline ring through the ortho, meta, or para position; commonly used aliphatic binary Oxazolines include bis(2-oxazoline), 1,1-bis(2-oxazoline)methane, 1,2-bis(2-oxazoline)ethane, 1,3-bis(2- oxazoline)propane, 1,4-bis(2-oxazoline)butane, 1,5-bis(2-oxazoline)pentane, 1,6-bis(2-oxazoline)hexane , 1,7-bis(2-oxazoline) heptane, 1,8-bis(2-oxazoline) octane, 1,9-bis(2-oxazoline) nonane, 1,10- Bis(2-oxazoline)decane, 1,11-bis(2-oxazoline)undecane, etc.; commonly used aromatic binary oxazolines include 1,2-phenyl-bis(2-oxazoline) oxazoline), 1,3-phenyl-bis(2-oxazoline), 1,4-phenyl-bis(2-oxazoline), and 2,3-pyridyl-bis(2-oxazole line), 2,4-pyridyl-bis(2-oxazoline), 2,5-pyridyl-bis(2-oxazoline), 2,6-pyridyl-bis(2-oxazoline) or 3,4-pyridyl-bis(2-oxazoline); among them, 1,4-phenyl-bis(2-oxazoline), 1,3-phenyl-bis(2-oxazoline) are preferred ), 1,4-bis(2-oxazoline)butane, 1,2-bis(2-oxazoline)ethane or bis(2-oxazoline).

The chain extender diacyl bis-lactam described in step 3) includes aliphatic diacyl bis-lactam or aromatic diacyl bis-lactam, and the general structural formula is shown in (III):

(III)

In the formula, i=3~12; R ₂ is -(CH ₂ ) _q -, q=0~20 or a benzene ring, connected to the dicarbonyl through the ortho, meta, or para position.

Commonly used aliphatic diacyl bis-lactams include: N,N'-oxalyl bis-caprolactam, N,N'-oxalyl bis-undecalactam, N,N'-oxalyl bis-laurolactam, N,N '-Succinoyl biscaprolactam, N,N'-Succinoyl bis-undecalactam, N,N'-Succinoyl bis-laurolactam, N,N'-Glutaryl bis-caprolactam, N,N '-glutaryl bis-undecalactam, N,N'-glutaryl bis-undecalactam, N,N'-adipyl bis-undecalactam, N,N'-adipyl bis-undecalactam, N,N'-Adipyl Dilaurolactam, N,N'-Azelayl Biscaprolactam, N,N'-Azelayl Diundecalactam, N,N'-Azelayl Didodecanoyl Lactam, N,N'-sebacyl biscaprolactam or N,N'-sebacyl bisundecalactam; preferably N,N'-succinoyl biscaprolactam or N,N'-adipyl biscaprolactam .

Commonly used N,N'-aromatic diacylbislactams include: N,N'-phthalyl biscaprolactam, N,N'-phthaloyl bis-undecalactam, N,N'- Phthalyl dilaurolactam, N,N'-isophthaloyl biscaprolactam, N,N'-isophthaloyl diundecalactam, N,N'-isophthaloyl bis-undecalactam Dilaurolactam, N,N'-terephthaloylbiscaprolactam, N,N'-terephthaloyldiundecalactam or N,N'-terephthaloylbislaurolactam ; preferably N,N'-isophthaloyl biscaprolactam or N,N'-terephthaloyl biscaprolactam.

Based on 100 parts by weight of the alternating polyester amide prepolymer, the optimal dosage of the chain extender bisoxazoline in the chain extension reaction in step 3) is between 6.1 and 9.9 parts by weight, and the chain extender The amount of diacylbislactam used is between 0.2 and 2.1 parts. When the amount is too low, the chain extension reaction is incomplete and the effect of chain extension is poor; when the amount is too high, the cost is too high and the effect of chain extension becomes poor.

Step 3) The suitable temperature for the chain extension reaction is 200-230°C. If the temperature of the chain extension reaction is too low, the activity of the chain extender is low, and the chain extension reaction is slow and the effect is poor; if the temperature is too high, the polymer is prone to thermal decomposition, Side reactions such as thermal oxidation, chain extension effect is poor, and the product color is darker.

Effect of the invention

The present invention first prepares diamide diacid by polycondensation of aliphatic nylon salt and dibasic acid, and then polycondenses with dibasic alcohol to synthesize an aliphatic alternating polyester amide prepolymer with both carboxyl-terminated and hydroxyl-terminated structures, and then uses its The terminal hydroxyl group reacts with the diacyl bis-lactam, and the terminal carboxyl group reacts with the binary oxazoline to realize the chain extension of the prepolymer and obtain a biodegradable alternating polyester amide with high molecular weight. The reaction of the terminal hydroxyl group of the prepolymer with the diacyl bis-lactam is expressed as follows:

The caprolactam formed is removed by sublimation in a vacuum system.

The reaction of terminal carboxyl group and bisoxazoline can be expressed as follows:

The resulting polyesteramide has the following alternating structure:

Among them, m=0~10, n=2~6, p=2~12, because the proportion of chain extender in the structure is very low, its influence can be ignored.

The alternating polyester amide prepolymer prepared by the present invention does not need to require both ends to be completely hydroxyl-terminated or carboxyl-terminated, and a high-molecular-weight polymer is obtained through the common chain extension of binary oxazoline and diacyl bis-lactam. The method has the advantages of mild conditions, cheap and easy-to-obtain raw materials, and environmental protection.

The present invention will be further described below in combination with specific embodiments.

Detailed ways

The present invention uses nylon salt and dibasic acid to react to prepare diamide diacid, and then polycondenses with dibasic alcohol to prepare alternate polyester amide prepolymer with terminal hydroxyl group and carboxyl group, through binary oxazoline and diacyl Combined chain extension of bis-lactam chain extenders to prepare biodegradable alternating polyester amides with intrinsic viscosity at 30°C of 0.49-0.75dL/g.

The molecular weight of the polymer is characterized by measuring the intrinsic viscosity, measured with m-cresol as solvent. According to the above-mentioned implementation modes, preferred examples are listed below to describe the present invention in detail, but the realization of the present invention is not limited to the following examples. The intrinsic viscosity of the following examples is measured at 30°C.

Example 1:

1) Preparation of diamide diacid: Weigh 61.15 parts of nylon 610 salt, 38.85 parts of sebacic acid, and 0.20 parts of phosphorous acid in parts by weight, and react at 200°C under normal pressure for 1 hour under the protection of nitrogen, and then heat up to Reaction at 210° C. for 3 hours under normal pressure to obtain a diamide diacid with an acid value of 218.96 mgKOH/g and a hydroxyl value of 1.01 mgKOH/g.

2) Preparation of alternating polyester amide prepolymer (alt-PEA): Weigh 84.98 parts of diamide diacid prepared in step 1), 15.02 parts of 1,4-butanediol, and 0.10 parts of phosphorous acid in parts by weight. 0.20 parts of tin protochloride, heated up to 200°C under the protection of nitrogen for 4 hours under normal pressure, then switched to a decompression device, raised the temperature to 210°C, first gradually decompressed with a water pump for 4 hours, and then decompressed to After reacting at 3mmHg for 4 hours, an alt-PEA prepolymer with an intrinsic viscosity of 0.26dL/g, an acid value of 37.25mgKOH/g and a hydroxyl value of 1.44mgKOH/g was obtained.

3) Weigh 60.0 parts of alt-PEA prepolymer prepared in step 2), 4.30 parts of 1,4-phenyl-bis(2-oxazoline) and 0.26 parts of adipyl biscaprolactam in nitrogen gas Under the protection of 210 ° C under normal pressure for 1.5 hours, and then 1.3 hours in a 2 mmHg reduced pressure system, the resulting alternating polyester amide has an intrinsic viscosity of 0.62 dL/g and a melting point T _m of 182.5 ° C. Its tensile strength is 28.8MPa, its elongation at break is 14.3%, and its thermal decomposition temperature is 371.4°C.

Example 2:

1) Preparation of polyester amide prepolymer (alt-PEA): Weigh 82.78 parts of diamide diacid prepared in step 1) in Example 1, 17.22 parts of diethylene glycol, and 0.10 parts of phosphorous acid in parts by weight Parts, 0.20 part of stannous chloride, under the protection of nitrogen, the temperature was raised to 210 °C for 4 hours under normal pressure, and then a decompression device was used instead, and the water pump was used to gradually reduce the pressure for 4 hours, and then the oil pump was used to reduce the pressure to 3mmHg for 4 hours. hours, an alt-PEA prepolymer with an intrinsic viscosity of 0.28 dL/g, an acid value of 42.81 mgKOH/g, and a hydroxyl value of 4.78 mgKOH/g was obtained.

2) Weigh 60.0 parts of alt-PEA prepolymer prepared in step 1) in Example 2, 4.95 parts of 1,4-phenyl-bis(2-oxazoline), 0.86 parts of adipyl biscaprolactam in parts by weight Under the protection of nitrogen, react at 210°C under normal pressure for 1.5 hours, and then react in a 2mmHg reduced pressure system for 1.2 hours. The intrinsic viscosity of the obtained alternating polyester amide is 0.66dL/g, and the melting point T _m is 179.5°C. Its tensile strength is 22.0MPa, its elongation at break is 180.8%, and its thermal decomposition temperature is 364.2°C.

Example 3:

1) Preparation of diamide diacid: Weigh 63.10 parts of nylon 66 salt, 36.90 parts of adipic acid, and 0.20 parts of phosphorous acid in parts by weight, and react at 200°C under normal pressure for 2 hours under nitrogen protection, and then heat up to Reaction at 210°C for 3 hours under normal pressure to obtain a diamide diacid with an acid value of 278.42 mgKOH/g and a hydroxyl value of 1.27 mgKOH/g.

2) Preparation of polyester amide prepolymer (alt-PEA): Weigh 82.38 parts of diamide diacid prepared in step 1) in Example 3, 17.62 parts of 1,4-butanediol, and phosphorous acid in parts by weight 0.10 parts, 0.20 parts of stannous chloride, under the protection of nitrogen, heat up to 220°C for 4 hours at normal pressure, then use a decompression device, heat up to 230°C, first use a water pump to gradually reduce the pressure for 4 hours, and then use an oil pump Reduce the pressure to 3mmHg and react for 4 hours to obtain an alt-PEA prepolymer with an intrinsic viscosity of 0.37dL/g, an acid value of 32.57mgKOH/g, and a hydroxyl value of 0.54mgKOH/g.

3) Weigh 60.0 parts of alt-PEA prepolymer prepared in step 2) of Example 3, 3.76 parts of 1,4-phenyl-bis(2-oxazoline), 0.10 parts of adipyl biscaprolactam in parts by weight Under the protection of nitrogen, react at 230°C under normal pressure for 1.5 hours, and then react in a 2mmHg reduced pressure system for 4.6 hours. The intrinsic viscosity of the obtained alternating polyester amide is 0.75dL/g, and the melting point T _m is 190.1°C. Its tensile strength is 34.1MPa, its elongation at break is 364.5%, and its thermal decomposition temperature is 342.1°C.

Example 4:

1) Preparation of polyester amide prepolymer (alt-PEA): Weigh 79.88 parts of diamide diacid prepared in step 1) in Example 3, 20.12 parts of diethylene glycol, and 0.10 parts of phosphorous acid in parts by weight Parts, 0.20 part of stannous chloride, under the protection of nitrogen, the temperature was raised to 210 °C for 4 hours under normal pressure, and then a decompression device was used instead, and the water pump was used to gradually reduce the pressure for 4 hours, and then the oil pump was used to reduce the pressure to 3mmHg for 4 hours. hours, an alt-PEA prepolymer with an intrinsic viscosity of 0.27 dL/g, an acid value of 51.68 mgKOH/g and a hydroxyl value of 7.03 mgKOH/g was obtained.

2) Weigh 60.0 parts of alt-PEA prepolymer prepared in step 1) in Example 4, 5.97 parts of 1,4-phenyl-bis(2-oxazoline), 1.26 parts of adipyl biscaprolactam in parts by weight Under the protection of nitrogen, react at 230°C under normal pressure for 1.5 hours, and then react in a 2mmHg reduced pressure system for 0.5 hours. The intrinsic viscosity of the obtained alternating polyester amide is 0.49dL/g, and the melting point T _m is 189.6°C. Its tensile strength is 26.4MPa, its elongation at break is 433.8%, and its thermal decomposition temperature is 341.2°C.

Claims (8)

1. the preparation method of biodegradable alternating polyester amide is characterized in that, comprises the following steps: 1) Feed the aliphatic nylon salt and the aliphatic dibasic acid according to the molar ratio of 1: (1~1.1), add 0.2% of the total monomer weight of phosphorous acid as a stabilizer, and in nitrogen atmosphere, at 200 ℃ React at normal pressure for 1-2 hours, then raise the temperature to 210°C, and react at normal pressure for 3 hours until no more water evaporates to obtain diamide diacid; 2) The diamide diacid prepared in step 1) and the aliphatic dihydric alcohol are polycondensed according to the molar ratio of (1-1.1): 1, and phosphorous acid of 0.1% of the total monomer weight is added as a stabilizer, and in the presence of a catalyst , nitrogen atmosphere, 200-230°C under normal pressure reaction, collect the generated water to 80% of the theoretical amount, then gradually decompress the reaction with a water pump for 4 hours, continue to decompress with an oil pump to keep the vacuum degree below 5mmHg, and react for 4 hours until Until the acid value is basically unchanged, an aliphatic alternating polyester amide prepolymer containing terminal hydroxyl groups and terminal carboxyl groups is obtained, wherein the amount of the catalyst is 0.01 to 0.3% of the total weight of the monomers; 3) The aliphatic alternating polyester amide prepolymer containing terminal hydroxyl group and carboxyl terminal group prepared in step 2) and chain extender diacylbislactam and bisoxazoline are mixed at 210-230°C under nitrogen protection After reacting with normal pressure for 1.5h, and then reacting at 1-5mmHg for 0.5-4.6h, a biodegradable alternating polyester amide with an intrinsic viscosity of 0.49-0.75dL/g is obtained; wherein, 100 parts by weight of polyester Based on the amide prepolymer, the amount of the chain extender diacylbislactam is 0.2-2.1 parts by weight, and the amount of the bisoxazoline chain extender is 6.1-9.9 parts by weight. 2. According to the method of claim 1, it is characterized in that, the diamide diacid described in step 1) has a structure shown in general formula (I):

In the above formula: m=0~10, p=2~12; The general structural formula of the nylon salt in step 1) is: ⁺ H ₃ N(CH ₂ ) _p NH ₃ ^+- OOC(CH ₂ ) _m COO ^- , where m=0~10, p=2~12; The general formula of the aliphatic dibasic acid is HOOC(CH ₂ ) _m COOH, m=0～10; The aliphatic dihydric alcohol described in step 2) is selected from the general formula HO(CH ₂ ) _n OH, n=2~6; the catalyst described in step 2) is dibutyltin oxide, tin oxide, chlorine One or more of stannous oxide, zinc oxide, zinc acetate, tetrabutyl titanate or tetraisopropyl titanate; The chain extender bisoxazoline described in step 3) includes aliphatic binary oxazoline or aromatic binary oxazoline, and its general structural formula is shown in (II):

In the formula, R ₁ is -(CH ₂ ) _h -, where h=0~20 or is phenyl or pyridyl, connected to the oxazoline ring through the ortho, meta, or para position; The chain extender diacyl bis-lactam described in step 3) includes aliphatic diacyl bis-lactam or aromatic diacyl bis-lactam, and the general structural formula is shown in (III):

In the formula, i=3~12; R ₂ is -(CH ₂ ) _q -, q=0~20 or a benzene ring, connected to the dicarbonyl through the ortho, meta, or para position. 3. according to the method for claim 1, it is characterized in that, step 1) described nylon salt is nylon 26 salt, nylon 210 salt, nylon 36 salt, nylon 310 salt, nylon 46 salt, nylon 410 salt, nylon 66 salt, One or more of nylon 610 salt and nylon 1010 salt. 4. The method according to claim 1, wherein the aliphatic dibasic acid is one or more of oxalic acid, adipic acid, suberic acid, azelaic acid, sebacic acid and the like. 5. according to the method for claim 1, it is characterized in that, aliphatic glycol is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol or diethylene glycol One or more of alcohols. 6. according to the method for claim 1, it is characterized in that, the chain extender bisoxazoline described in step 3) comprises aliphatic binary oxazoline or aromatic binary oxazoline; Aliphatic binary oxazole The morphine is bis(2-oxazoline), 1,1-bis(2-oxazoline)methane, 1,2-bis(2-oxazoline)ethane, 1,3-bis(2-oxazole phenoline) propane, 1,4-bis(2-oxazoline)butane, 1,5-bis(2-oxazoline)pentane, 1,6-bis(2-oxazoline)hexane, 1 ,7-bis(2-oxazoline)heptane, 1,8-bis(2-oxazoline)octane, 1,9-bis(2-oxazoline)nonane, 1,10-bis( 2-oxazoline)decane or 1,11-bis(2-oxazoline)undecane; aromatic binary oxazolines include 1,2-phenyl-bis(2-oxazoline), 1 ,3-phenyl-bis(2-oxazoline), 1,4-phenyl-bis(2-oxazoline), and 2,3-pyridyl-bis(2-oxazoline), 2, 4-pyridyl-bis(2-oxazoline), 2,5-pyridyl-bis(2-oxazoline), 2,6-pyridyl-bis(2-oxazoline) or 3,4- Pyridyl-bis(2-oxazoline); among them, 1,4-phenyl-bis(2-oxazoline), 1,3-phenyl-bis(2-oxazoline), 1,4 - Bis(2-oxazoline)butane, 1,2-bis(2-oxazoline)ethane or bis(2-oxazoline). 7. according to the method for claim 1, it is characterized in that, chain extender diacyl bis-lactam comprises aliphatic diacyl bis-lactam or aromatic diacyl bis-lactam; Aliphatic diacyl bis-lactam comprises: N, N '-oxalylbiscaprolactam, N,N'-oxalylbisundecalactam, N,N'-oxalylbislaurolactam, N,N'-succinylbiscaprolactam, N,N'-butyrolactam Diacyl diundecalactam, N,N'-succinoyl dilaurolactam, N,N'-glutaryl biscaprolactam, N,N'-glutaryl diundecalactam, N,N '-glutaryl dilaurolactam, N,N'-adipyl biscaprolactam, N,N'-adipyl bis-undecalactam, N,N'-adipyl bis-laurolactam, N,N'-Azelayl biscaprolactam, N,N'-Azelayl bisundecalactam, N,N'-Azelayl bislaurolactam, N,N'-Sebacoyl biscaprolactam or N,N'-sebacyl bis-undecalactam; Aromatic diacyl bis-lactams include: N,N'-phthaloyl bis-caprolactam, N,N'-phthaloyl bis-undecalactam Amide, N,N'-phthaloyl dilaurolactam, N,N'-isophthaloyl biscaprolactam, N,N'-isophthaloyl diundecalactam, N,N '-isophthaloyl dilaurolactam, N,N'-terephthaloyl biscaprolactam, N,N'-terephthaloyl bis-undecalactam or N,N'-terephthaloyl bis-undecalactam Formyldilaurolactam. 8. The method according to claim 7, characterized in that the aliphatic diacyl bis-lactam is N,N'-succinoyl bis-caprolactam or N,N'-adipyl bis-lactam; the aromatic diacyl bis-lactam It is N,N'-isophthaloyl biscaprolactam or N,N'-terephthaloyl biscaprolactam.