CN103387668B - With the preparation method of the aliphatic polyester amide of urea key - Google Patents

Abstract

The preparation method of the aliphatic polyester amide with urea bond belongs to the technical field of polyester amide. The present invention adopts urea monomer with terminal amino group and terminal hydroxyl group to carry out melt polycondensation with aliphatic dibasic acid and dibasic alcohol. To adjust the amide content, a series of prepolymers of polyesteramides with urea bonds with both carboxyl-terminated and hydroxyl-terminated structures were prepared, and then extended with diacyl bis-lactam and bisoxazoline chain extenders. Chain, to prepare biodegradable polyester amide containing urea bond, its intrinsic viscosity is between 0.38~0.72dL/g at 30℃.

Description

Process for the preparation of aliphatic polyester amides with urea bonds

technical field

The invention belongs to the technical field of polyester amides, and relates to a method for preparing an aliphatic polyester amide with a urea bond, in particular to an aliphatic dibasic acid, a diol, and an amino-terminated hydroxyl monomer with a urea bond. Raw Materials Synthesis of aliphatic polyester amides with urea linkages.

technical background

Polyurea has good thermal stability and has excellent properties in terms of tensile strength, modulus, elongation, flexibility, wear resistance, aging resistance, and corrosion resistance. Polyurea is mainly synthesized by two methods: 1) polymerization of isocyanate and diamine; 2) reaction polymerization of diisocyanate and water. Yeh et al. used polytetrahydrofuran as the soft segment, and reacted MDI with ethylenediamine to obtain the polyurea hard segment, forming a polyurea elastomer with good toughness. Unal et al. used diisocyanate and trifunctional amine to prepare polyurea. As the amount of isocyanate increases, gelation will occur, making it difficult to determine the molecular weight. The diisocyanate used in the traditional synthetic polyurea is highly toxic, has accumulation and latent properties in the human body, and has a strong irritating effect on the skin, eyes and respiratory tract.

Aliphatic polyester amide (PEA) is a new type of biodegradable polymer material. Compared with aliphatic polyester, due to the introduction of amide groups, the formation of hydrogen bonds between amide groups makes the polymer have better mechanical properties and strength, while the presence of ester bonds endows the material with good biodegradability, making it It has broad application prospects. U.S. Patent US 0,065,314 (2005) reported the synthesis of a tri-block biodegradable polyester amide using adipic acid, 1,4-butanediol, caprolactam, and hexamethylenediamine as raw materials under the action of the branching agent pentaerythritol , the material has good tensile properties, elongation at break and biodegradability, but the preparation method used is a direct melt polycondensation method, which requires a high degree of vacuum, which must be below 0.5mmHg. 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. Diols and dibasic acids undergo melt co-condensation reactions, 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 CN 1,310,194A (2001), CN 1,124,304C (2003), CN 101,020,746A (2007) reported the preparation of high molecular weight polyesteramides with diisocyanate or bisoxazoline extended chain aliphatic polyester prepolymers, but The polyester amides prepared by this method have a low amide bond content, and the thermal and mechanical properties are not significantly improved compared with the corresponding aliphatic polyesters.

Compared with the traditionally synthesized polyurea, the polyester amide with urea bonds synthesized by the invention has environmentally friendly raw materials and a green and pollution-free synthesis route.

Invention content:

The object of the present invention is to provide a pollution-free and easy-to-operate synthetic method for preparing polyesteramides with urea bonds through chain extension. The raw materials of the method are cheap and easy to obtain, and the preparation of the prepolymer is simple.

The present invention adopts chain extension method to prepare aliphatic polyester amide containing urea bond, adopts urea monomer with terminal amino group and terminal hydroxyl group to carry out melt polycondensation with aliphatic dibasic acid and dibasic alcohol, by changing The proportion of hydroxyl-terminated urea monomer to dibasic acid and dibasic alcohol was used to adjust the amide content, and a series of prepolymers of polyesteramides with urea bonds with both carboxyl-terminated and hydroxyl-terminated structures were prepared. Diacylbislactam and bisoxazoline chain extender are used for chain extension to prepare biodegradable polyester amide containing urea bonds with an intrinsic viscosity of 0.38~0.72dL/g at 30°C. The specific steps are as follows:

1) Add 2-oxazolidinone-dissolved dimethylformamide (DMF) solution dropwise to the DMF solution of diamine at 160°C, react for 5 hours after the dropwise addition, and cool to obtain an amino group with an amino group at one end. A monomer containing a urea bond with a hydroxyl group at one end;

2) The monomer containing urea bonds prepared in step 1) is melt-condensed with aliphatic diols and dibasic acids, and the urea bonds are counted as two amide bonds, according to the final formation of amide bonds and ester bonds in the polymer The molar ratio is (0.1～0.5):(0.9～0.5), the sum of amide bonds and ester bonds is 1, and the molar ratio of the total (monomers containing urea bonds + diols) to dibasic acids is 1: (1.0~1.4), carry out polymerization, and add phosphorous acid of 0.2% of the total weight of the monomer as a stabilizer, in the presence of a catalyst, in a nitrogen atmosphere, and react under normal pressure at 160~210°C, collect the generated water to the theoretical amount 60-80%, and then change to decompression reaction, first use the water pump to gradually depressurize the reaction for 2.5h, continue to use the oil pump to depressurize to make the vacuum degree below 5mmHg, and react for 3h until the acid value does not change, and the urea bond is obtained. A prepolymer of polyester amide, wherein the amount of catalyst used is 0.05-0.3wt% of the total weight of monomers;

3) The prepolymer of polyester amide with urea bond prepared in step 2), with chain extender bisoxazoline and diacyl bislactam, catalyst stannous chloride and p-toluenesulfonic acid, in N ₂ Under protection, react at 200°C under normal pressure for 1.5 hours, and then react at 1-5 mm Hg for 2.5-9 hours to obtain a biodegradable polyester amide with urea bonds; wherein, 100 parts by weight of In terms of the polyester amide prepolymer, the consumption of chain extender diacylbislactam is 1.6～15.8 parts by weight, the consumption of bisoxazoline chain extender is 4.8～10.9 parts by weight; the percentage of catalyst stannous chloride is 0.05~0.3%, the percentage of p-toluenesulfonic acid is 0.05~0.2%.

Among them, the urea bond-containing monomer with an amino group at one end and a hydroxyl group at one end described in step 1) has the structure shown in general formula (I):

In the above formula, n=2～12;

The general formula of the aliphatic diamine described in step 1) is NH ₂ (CH ₂ ) _n NH ₂ , n=2~12, commonly used are ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine , octanediamine, etc., or one or both of them.

The general formula of the aliphatic dibasic acid described in step 2) is HOOC(CH ₂ ) _m COOH, m=2~10, and the commonly used one is adipic acid, suberic acid, sebacic acid, etc. or two kinds.

The aliphatic dihydric alcohol described in step 2) is selected from the general formula HO(CH ₂ ) _x OH, x=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 more mixtures of dibutyltin oxide, tin oxide, stannous chloride, 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 is -(CH ₂ ) _p -, where p=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, q=3~12; R is -(CH ₂ ) _y -, y=0~20 or a benzene ring, connected to the dicarbonyl through the ortho, meta, or para position;

Commonly used aliphatic diacylbislactams include: N,N'-oxalylbispyrrolidone, N,N'-oxalylbiscaprolactam, N,N'-oxalylbislaurolactam, N,N'-butyrolactam Diacylbispyrrolidone, N,N'-succinoylbiscaprolactam, N,N'-succinoylbislaurolactam, N,N'-glutarylbispyrrolidone, N,N'-glutarylbiscaprolactam Caprolactam, N,N'-Glutaryl Dilaurolactam, N,N'-Adipyl Bispyrrolidone, N,N'-Adipyl Biscaprolactam, N,N'-Adipyl Dilaurolactam Amide, N,N'-Azelayl bispyrrolidone, N,N'-Azelayl biscaprolactam, N,N'-Azelayl bislaurolactam, N,N'-Sebacoyl bispyrrolidone, N , N'-sebacylbiscaprolactam or N,N'-sebacylbisundecalactam; preferably N,N'-succinoylbiscaprolactam and N,N'-adipylbiscaprolactam.

Commonly used N,N'-aromatic diacyl bis-lactams include: N,N'-phthaloyl bis-pyrrolidone, N,N'-phthaloyl bis-caprolactam, N,N'-phthaloyl bis- Formyl bislaurolactam, N,N'-isophthaloyl bispyrrolidone, N,N'-isophthaloyl biscaprolactam, N,N'-isophthaloyl bislaurolactam, N,N'-terephthaloylbispyrrolidone, N,N'-terephthaloylbiscaprolactam or N,N'-terephthaloylbislaurolactam; preferably N,N'-m-phenylene Diformyl biscaprolactam and N,N'-terephthaloyl biscaprolactam.

Based on 100 parts by weight of the polyester amide prepolymer with urea bonds, the optimal amount of the chain extender bisoxazoline in the chain extension reaction of step 3) is between 4.8 and 10.9 parts by weight , The dosage of the chain extender diacylbislactam is between 1.6 and 15.8 parts. When the dosage is too low, the chain extension reaction is incomplete and the chain extension effect is poor; when it is too high, the cost is too high and the chain extension effect becomes poor.

The suitable temperature for the chain extension reaction in step 3) is 180-220°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 , thermal oxidation and other side reactions, the chain extension effect is poor, and the product color is darker.

Advantage of the present invention and effect thereof:

The present invention reacts 2-oxazolidinone with aliphatic diamine to prepare urea monomers with terminal amino groups and terminal hydroxyl groups, and then reacts urea monomers with aliphatic diacids and diols to generate polyurea compounds with urea bonds. The prepolymer of ester amide, the prepolymer contains both carboxyl and hydroxyl groups, and then uses its terminal hydroxyl to react with diacylbislactam, and uses its terminal carboxyl to react with binary oxazoline to realize the expansion of the prepolymer. Chain, obtain high molecular weight biodegradable polyester amide with urea bond, intrinsic viscosity around 30°C is 0.38~0.72dL/g. 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 polymer molecular formula of the polyester amide with urea bond finally formed is as follows:

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

1) The prepolymer prepared by the present invention does not require both ends to be completely hydroxyl-terminated or carboxyl-terminated, and a high-molecular-weight polymer can be obtained through the joint chain extension of binary oxazoline and diacyl bis-lactam. This method has Mild conditions, cheap and easy-to-get raw materials, green and environmental protection and other advantages.

2) By adjusting the ratio of urea monomer to dibasic acid and diol, the ratio of ester bond and amide bond in the polymer can be controlled to obtain polyester amides with urea bonds with different amide bond and ester bond contents polymer. Especially the two-step method of polycondensation and chain extension to prepare biodegradable polyamide ester with urea bond, the intrinsic viscosity of the prepared aliphatic polyester amide with urea bond is 0.38-0.72dL/g at 30°C of.

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

Detailed ways:

The present invention utilizes 2-oxazolidinone and aliphatic diamine to prepare the urea monomer with terminal amino group and terminal hydroxyl group by ring-opening reaction at a molar ratio of 1:1, and then melts it with aliphatic dibasic acid and dibasic alcohol The prepolymer is prepared by polycondensation. Through the joint chain extension of binary oxazoline and diacyl bislactam chain extender, the biodegradable urea bond-containing biodegradable polystyrene with intrinsic viscosity between 0.38 and 0.72dL/g at about 30°C is prepared. permanent polyester amide.

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 amino-terminated hydroxyurea monomer (HAU): Dissolve 39.6 parts of octanediamine in 50ml of N,N-dimethylformamide (DMF), raise the temperature to 160°C; weigh 60.4 parts by weight A part of 2-oxazolidinone was dissolved in 50ml of DMF, and added dropwise to the above-mentioned octanediamine solution; after the dropwise addition, the reaction was continued for 5 hours, cooled to room temperature, a white solid was precipitated, filtered under reduced pressure to obtain a white solid , the measured hydroxyl value is 487.05mgKOH/g, and its molecular weight is 230.36, which is consistent with the theoretical molecular weight of 231.

2) Preparation of polyester amide prepolymer with urea bonds: 69.3 parts of HAU monomer prepared in step 1), 145.6 parts of sebacic acid, 27.1 parts of 1,4-butanediol were weighed in parts by weight, 0.48 parts of phosphorous acid, 0.24 parts of stannous chloride, under the protection of nitrogen, heat up to 160 ° C, slowly heat up to 200 ° C within 2 hours, then use a decompression device, first use a water pump to gradually reduce the pressure for 2.5 hours, Then use an oil pump to reduce the pressure to 3 mmHg and react for 3 hours to obtain a PrePEAU prepolymer with an intrinsic viscosity of 0.19 dL/g, an acid value of 56.95 mgKOH/g, and a hydroxyl value of 33.65 mgKOH/g.

3) Weigh 71.1 parts of PrePEAU prepolymer prepared in step 2), 7.8 parts of 1,4-phenyl-bis(2-oxazoline), 7.2 parts of adipyl biscaprolactam, and chlorinate the catalyst 0.17 parts of stannous and 0.043 parts of p-toluenesulfonic acid were reacted at 200°C under normal pressure for 1.5 hours under the protection of nitrogen, and then reacted in a 2 mmHg reduced pressure system for 8.3 hours. The intrinsic viscosity of the obtained polymer was 0.72 dL/g.

Example 2:

1) Preparation of polyester amide prepolymer with urea bonds: Weigh 11.6 parts of HAU monomer prepared in step 1) in Example 1, 141.6 parts of sebacic acid, 1,4-butanediol in parts by weight 58.6 parts, 0.42 parts of phosphorous acid, 0.21 parts of stannous chloride, under the protection of nitrogen, heat up to 160 ° C, slowly heat up to 200 ° C within 2 hours, and then switch to a decompression device, first use a water pump to gradually decompress the reaction After 2.5 hours, the oil pump was used to reduce the pressure to 3mmHg and react for 3 hours to obtain a PrePEAU prepolymer with an intrinsic viscosity of 0.26dL/g, an acid value of 39.19mgKOH/g, and a hydroxyl value of 32.01mgKOH/g.

3) Weigh 51.5 parts of PrePEAU prepolymer prepared in step 2), 3.9 parts of 1,4-phenyl-bis(2-oxazoline), 4.9 parts of adipyl biscaprolactam, catalyst chlorinated chlorinated 0.12 parts of tin and 0.003 parts of p-toluenesulfonic acid were reacted at 200°C under normal pressure for 1.5 hours under the protection of nitrogen, and then reacted in a 2 mmHg reduced pressure system for 4.3 hours. The intrinsic viscosity of the obtained polymer was 0.38 dL/g.

Example 3:

1) Preparation of polyester amide prepolymer with urea bonds: Weigh 23.1 parts of HAU monomer prepared in step 1) in Example 1, 131.5 parts of sebacic acid, 1,4-butanediol in parts by weight 49.5 parts, 0.41 parts of phosphorous acid, 0.20 parts of stannous chloride, under the protection of nitrogen, raise the temperature to 160°C, slowly raise the temperature to 200°C within 2 hours, then switch to a decompression device, and first use a water pump to gradually depressurize the reaction After 2.5 hours, the oil pump was used to reduce the pressure to 3 mmHg and react for 3 hours to obtain a PrePEAU prepolymer with an intrinsic viscosity of 0.29 dL/g, an acid value of 31.13 mgKOH/g, and a hydroxyl value of 45.76 mgKOH/g.

2) Weigh 50.9 parts of PrePEAU prepolymer prepared in step 1), 3.1 parts of 1,4-phenyl-bis(2-oxazoline), 6.9 parts of adipyl biscaprolactam, and chlorinate the catalyst 0.12 parts of stannous and 0.003 parts of p-toluenesulfonic acid were reacted at 200°C under normal pressure for 1.5 hours under the protection of nitrogen, and then reacted in a 2 mmHg reduced pressure system for 2.5 hours. The intrinsic viscosity of the obtained polymer was 0.57 dL/g.

Example 4:

1) Preparation of polyester amide prepolymer with urea bonds: Weigh 11.6 parts of HAU monomer prepared in step 1) in Example 1, 40.5 parts of sebacic acid, 1,4-butanediol in parts by weight 13.5 parts, 0.13 parts of phosphorous acid, 0.066 parts of stannous chloride, under the protection of nitrogen, raise the temperature to 160°C, slowly raise the temperature to 200°C within 2 hours, then switch to a decompression device, and first use a water pump to gradually decompress the reaction After 2.5 hours, the oil pump was used to reduce the pressure to 3 mmHg and react for 3 hours to obtain a PrePEAU prepolymer with an intrinsic viscosity of 0.31 dL/g, an acid value of 31.38 mgKOH/g, and a hydroxyl value of 24.1 mgKOH/g.

2) Weigh 59.3 parts of PrePEAU prepolymer prepared in step 1), 3.6 parts of 1,4-phenyl-bis(2-oxazoline), 4.2 parts of adipyl biscaprolactam, and chlorinate the catalyst 0.13 parts of stannous and 0.034 parts of p-toluenesulfonic acid were reacted at 200°C under normal pressure for 1.5 hours under the protection of nitrogen, and then reacted in a 2 mmHg reduced pressure system for 2.8 hours. The intrinsic viscosity of the obtained polymer was 0.62 dL/g.

Example 5:

1) Preparation of polyester amide prepolymer with urea bonds: Weigh 46.2 parts of HAU monomer prepared in step 1) in Example 1, 111.2 parts of sebacic acid, 1,4-butanediol in parts by weight 31.5 parts, 0.38 parts of phosphorous acid, 0.19 parts of stannous chloride, under the protection of nitrogen, heat up to 160 ° C, slowly heat up to 200 ° C within 2 hours, and then switch to a decompression device, first use a water pump to gradually decompress the reaction After 2.5 hours, use an oil pump to reduce the pressure to 3 mmHg and react for 3 hours to obtain a PrePEAU prepolymer with an intrinsic viscosity of 0.23 dL/g, an acid value of 25.6 mgKOH/g, and a hydroxyl value of 5.4 mgKOH/g.

2) Weigh 50.1 parts of PrePEAU prepolymer prepared in step 1), 2.4 parts of 1,4-phenyl-bis(2-oxazoline), 0.8 parts of adipyl biscaprolactam, and chlorinate the catalyst 0.11 parts of stannous and 0.027 parts of p-toluenesulfonic acid were reacted at 200°C under normal pressure for 1.5 hours under the protection of nitrogen, and then reacted in a 2 mmHg reduced pressure system for 9 hours. The intrinsic viscosity of the obtained polymer was 0.50 dL/g.

Claims (6)

1. with a preparation method for the aliphatic polyester amide of urea key, it is characterized in that, comprise the following steps:

1) at 160 DEG C, dimethyl formamide (DMF) solution being dissolved with 2-oxazolidone is added drop-wise in the DMF solution of aliphatic diamine, drip rear reaction 5 hours, cooling, obtains one end with amino, one end monomer containing urea key with hydroxyl;

2) by step 1) the middle monomer containing urea key prepared, with aliphatic dihydroxy alcohol and aliphatic dibasic acid melt phase polycondensation, be two amido linkages in urea key, be (0.1 ~ 0.5) according to the final mol ratio forming amido linkage and ester bond in polymkeric substance: (0.9 ~ 0.5), amido linkage and ester bond sum are 1, total is 1:(1.0 ~ 1.4 containing the monomer+aliphatic dihydroxy alcohol of urea key and the mol ratio of aliphatic dibasic acid), be polymerized, and the phosphorous acid adding total monomer weight 0.2% is as stablizer, in the presence of a catalyst, in nitrogen atmosphere, synthesis under normal pressure at 160 ~ 210 DEG C, collect the water of generation to 60 ~ 80% of theoretical amount, change Depressor response into again, first with water pump decompression step by step reaction 2.5h, the decompression of continuation oil pump makes vacuum tightness be below 5mmHg, reaction 3h, till acid number is constant, obtain the performed polymer of the polyesteramide with urea key, wherein catalyst levels is 0.05 ~ 0.3wt% of total monomer weight,

3) by step 2) in the performed polymer of the polyesteramide with urea key of preparation, with chainextender bisoxazoline and diacyl two lactan, catalyzer tin protochloride and tosic acid, at N ₂in 200 DEG C of synthesis under normal pressure 1.5 hours under protection, then react 2.5 ~ 9 hours under 1-5mm mercury column, obtain the Biodegradable polyester amides with urea key; Wherein, in the polyesteramide performed polymer with urea key of 100 weight parts, the consumption of the two lactan of chainextender diacyl is the consumption of 1.6 ~ 15.8 weight part ， bisoxazoline chainextenders is 4.8 ~ 10.9 weight parts; The percentage ratio of catalyzer tin protochloride is 0.05 ~ 0.3%, and the percentage ratio of tosic acid is 0.05 ~ 0.2%;

Wherein, step 1) described in one end with amino, one end monomer containing urea key with hydroxyl, for having the structure shown in logical formula I:

N=2 ~ 12 in above formula;

Step 1) described in the general formula of aliphatic diamine be NH ₂(CH ₂) _nnH ₂, n=2 ~ 12,

Step 2) described in the general formula of aliphatic dibasic acid be HOOC (CH ₂) _mcOOH, m=2 ~ 10,

Step 2) described in aliphatic dihydroxy alcohol to be selected from general formula be HO (CH ₂) _xoH, x=2 ~ 6,

Step 2) described in catalyzer be in Dibutyltin oxide, stannic oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate or titanium isopropylate one or more mixing;

Step 3) described in chainextender bisoxazoline comprise the fragrant race Er Yuan oxazoline of Zhi fat race Er Yuan oxazoline or Fang, its general structure is as shown in (II):

In formula, R is-(CH ₂) _p-, wherein p=0 ~ 20 or be phenyl or pyridyl, are connected Yu oxazoline ring by ortho position, a position or contraposition;

Step 3) described in the two lactan of chainextender diacyl comprise the two lactan of aliphatics diacyl or the two lactan of aromatic series diacyl, general structure is as shown in (III):

In formula, q=3 ~ 12; R is-(CH ₂) _y-, y=0 ~ 20 or phenyl ring, be connected with dicarbapentaborane by ortho position, a position or contraposition.

2. according to the method for claim 1, it is characterized in that, aliphatic diamine is one or both in quadrol, propylene diamine, butanediamine, hexanediamine, octamethylenediamine.

3., according to the method for claim 1, it is characterized in that, step 2) aliphatic dibasic acid is one or both in hexanodioic acid, suberic acid, sebacic acid.

4. according to the method for claim 1, it is characterized in that, aliphatic dihydroxy alcohol is one or more in ethylene glycol, 1,3-PD, BDO, 1,6-hexylene glycol or glycol ether.

5. according to the method for claim 1, it is characterized in that, step 3) described in bisoxazoline chainextender conventional have 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 two (2-oxazoline).

6. according to the method for claim 1, it is characterized in that, the two lactan of aliphatics diacyl is N, N ' the two hexanolactam of-succinyl or N, N '-adipoyl biscaprolactamate; N, N '-aromatic series diacyl two lactan be N, N '-isophthaloybiscaprolactam or N, N '-terephthaloylbiscapro-lactamate.