CN103387668B - With the preparation method of the aliphatic polyester amide of urea key - Google Patents
With the preparation method of the aliphatic polyester amide of urea key Download PDFInfo
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Abstract
With the preparation method of the aliphatic polyester amide of urea key, belong to polyesteramide technical field.The present invention adopts and carries out melt phase polycondensation with the urea monomer of Amino End Group and terminal hydroxy group and aliphatic dibasic acid, dibasic alcohol; amide content is regulated by the ratio changed with the urea monomer of Amino End Group and terminal hydroxy group and diprotic acid, dibasic alcohol; with the performed polymer of the polyesteramide with urea key of end carboxyl and terminal hydroxy group structure while of preparing a series of; again with the two lactan of diacyl with bisoxazoline chainextender carries out chain extension; preparation is containing the Biodegradable polyester amides of urea key, and its limiting viscosity 30 DEG C is between 0.38 ~ 0.72dL/g.
Description
Technical field
The invention belongs to polyesteramide technical field, relate to a kind of preparation method of the aliphatic polyester amide with urea key, be specifically related to aliphatic dibasic acid, dibasic alcohol and with the Amino End Group terminal hydroxy group monomer of urea key for Material synthesis is with the aliphatic polyester amide of urea key.
Technical background
The Heat stability is good of polyureas, all has excellent performance in tensile strength, modulus, elongation, snappiness, wear-resisting ageing-resistant, protection against corrosion.Polyureas synthesizes mainly through two kinds of methods: 1) isocyanic ester and diamines polymerization; 2) vulcabond and water reactive polymeric.Yeh etc. are soft section with polytetrahydrofuran, obtain the hard section of polyureas, define the polyurea elastomer with better toughness with MDI and reacting ethylenediamine.Unal etc. prepare polyureas with the amine effect of vulcabond and trifunctional, along with the increase of isocyanic ester consumption there will be gelatin phenomenon, make molecular weight be difficult to measure.Conventional synthesis polyureas vulcabond toxicity used is very large, has characteristic of concentration and latent, have intense stimulus effect to skin, eyes and respiratory tract in human body.
Aliphatic polyester amide (PEA) is a kind of novel biodegradable polymer.Compared with aliphatic polyester, owing to introducing amide group, form hydrogen bond, make polymkeric substance have better mechanical property and intensity between amide group, the existence of ester bond simultaneously gives again material good biodegradability, makes it have application prospect widely.US Patent No. 0,065,314(2005) report with hexanodioic acid, 1,4-butyleneglycol, hexanolactam, hexanediamine are raw material, under the effect of branching agent tetramethylolmethane, synthesize a kind of three block biodegradable polyesteramides, this material has good tensile property, elongation at break and biodegradable, but preparation method used is direct melt polycondensation method, very high to vacuum level requirements, vacuum tightness need at below 0.5mmHg.(the synthetic chemistry such as Liu Xiaobo, 1999,7 (4), 354) with oxyacetic acid and 1,12-12 diamines or hexanediamine and caprolactone are obtained by reacting two kinds of diamide glycol, these two kinds of diamide glycol and diprotic acid being carried out Melt polycondensation, by regulating the ratio of two kinds of diamide glycol, obtaining the polyester-amide copolymer that a series of performance is different, degradation speed is different.But with diprotic acid and the polycondensation of diamide glycol, feed ratio is wayward, and easily causes monomer volatilization loss under high temperature high vacuum, have impact on proportioning raw materials, is therefore difficult to obtain the polymkeric substance of high molecular.Chinese patent CN 1,310,194A(2001), CN 1,124,304C(2003), CN 101,020,746A(2007) report the polyesteramide preparing high molecular with vulcabond Huo bisoxazoline chain extension aliphatic polyester performed polymer, but the amido linkage content of polyesteramide prepared by this method is lower, and compare with corresponding aliphatic polyester, thermal characteristics and mechanical property do not significantly improve.
The polyesteramide with urea key synthesized by the present invention, compared with conventional synthesis polyureas, raw material environmental protection, synthetic route green non-pollution.
Summary of the invention:
The object of the invention is for the deficiencies in the prior art, provide the synthetic method of a kind of chain extension pollution-free, easy and simple to handle preparation with the polyesteramide of urea key.The method raw material is cheaply easy to get, and performed polymer preparation is simple.
The present invention adopts the standby aliphatic polyester amide containing urea key of chain extension legal system, adopt the urea monomer with Amino End Group and terminal hydroxy group and aliphatic dibasic acid, dibasic alcohol carries out melt phase polycondensation, by changing urea monomer with Amino End Group and terminal hydroxy group and diprotic acid, the ratio of dibasic alcohol regulates amide content, with the performed polymer of the polyesteramide with urea key of end carboxyl and terminal hydroxy group structure while of preparing a series of, again with the two lactan of diacyl with bisoxazoline chainextender carries out chain extension, the Biodegradable polyester amides containing urea key of preparation limiting viscosity 30 DEG C between 0.38 ~ 0.72dL/g, concrete steps comprise as follows:
1) at 160 DEG C, dimethyl formamide (DMF) solution being dissolved with 2-oxazolidone is added drop-wise in the DMF solution of diamines, drips rear reaction 5 hours, cooling, obtain one end with amino, one end monomer containing urea key with hydroxyl;
2) monomer containing urea key will prepared in step 1), with aliphatic dihydroxy alcohol and diprotic 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 (monomer+dibasic alcohol containing urea key) is 1:(1.0 ~ 1.4 with the mol ratio of diprotic 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, the one end described in step 1) 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;
The general formula of the aliphatic diamine described in step 1) is NH
2(CH
2)
nnH
2, n=2 ~ 12, conventional is in quadrol, propylene diamine, butanediamine, hexanediamine, octamethylenediamine etc. one or both.
Step 2) described in the general formula of aliphatic dibasic acid be HOOC (CH
2)
mcOOH, m=2 ~ 10, conventional is in hexanodioic acid, suberic acid, sebacic acid etc. one or both.
Step 2) described in aliphatic dihydroxy alcohol to be selected from general formula be HO (CH
2)
xoH, x=2 ~ 6, conventional have in ethylene glycol, 1,3-PD, BDO, 1,6-hexylene glycol or glycol ether etc. one or more.
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;
Chainextender bisoxazoline described in step 3) comprises Zhi fat race Er Yuan oxazoline or the fragrant race Er Yuan oxazoline of Fang, and 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;
The two lactan of chainextender diacyl described in step 3) comprises the two lactan of aliphatics diacyl or the two lactan of aromatic series diacyl, and 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;
The two lactan of conventional aliphatics diacyl comprises: N, the two pyrrolidone of N '-oxalyl, N, the two hexanolactam of N '-oxalyl, N, the two laurolactam of N '-oxalyl, N, the two pyrrolidone of N '-succinyl, N, the two hexanolactam of N '-succinyl, N, the two laurolactam of N '-succinyl, N, the two pyrrolidone of N '-glutaryl, N, the two hexanolactam of N '-glutaryl, N, the two laurolactam of N '-glutaryl, N, the two pyrrolidone of N '-hexanedioyl, N, N '-adipoyl biscaprolactamate, N, the two laurolactam of N '-hexanedioyl, N, the two pyrrolidone of N '-azelaoyl, N, the two hexanolactam of N '-azelaoyl, N, the two laurolactam of N '-azelaoyl, N, the two pyrrolidone of N '-sebacoyl, N, the two hexanolactam of N '-sebacoyl or N, two 11 lactan of N '-sebacoyl, preferred N, N '-succinyl two hexanolactam and N, N '-adipoyl biscaprolactamate.
Conventional N, the two lactan of N '-aromatic series diacyl comprises: N, the two pyrrolidone of N '-phthalyl, N, N ' the two hexanolactam of-phthalyl, N, N '-phthalyl two laurolactam, N, N '-isophthaloyl two pyrrolidone, N, N '-isophthaloybiscaprolactam, N, N '-isophthaloyl two laurolactam, N, N '-paraphenylene terephthalamide two pyrrolidone, N, N '-terephthaloylbiscapro-lactamate or N, N ' the two laurolactam of-paraphenylene terephthalamide; Preferred N, N '-isophthaloybiscaprolactam and N, N '-terephthaloylbiscapro-lactamate.
In the polyesteramide performed polymer of parts by weight 100 parts with urea key, in the chain extending reaction of step 3), the optimum amount of chainextender bisoxazoline is between 4.8 ~ 10.9 parts (parts by weight), the consumption of the two lactan of chainextender diacyl is between 1.6 ~ 15.8 parts, when consumption is too low, chain extending reaction is incomplete, chain extension weak effect; Time too high, cost is too high, and chain extension effect is also deteriorated.
In step 3), the optimal temperature of chain extending reaction is 180 ~ 220 DEG C, and chain extending reaction temperature is too low, and the activity of chainextender is lower, and chain extending reaction carries out slowly and weak effect; Temperature is too high, and the side reaction such as thermolysis, thermooxidizing easily occurs polymkeric substance, and chain extension effect is poor, and coloured product is darker.
Advantage of the present invention and effect thereof:
The present invention is reacted by 2-oxazolidone and aliphatie diamine; prepare the urea monomer with Amino End Group and terminal hydroxy group; then urea monomer and aliphatic diacid, glycol react; generate the performed polymer with the polyesteramide of urea key; this performed polymer is simultaneously containing end carboxyl and terminal hydroxy group; its terminal hydroxy group and the two lactan of diacyl is utilized to react afterwards; its end carboxyl and Er Yuan oxazoline is utilized to react; realize the chain extension of prepolymer; obtain the polyesteramide with urea key of the biodegradable of high molecular, the limiting viscosity of about 30 DEG C is 0.38 ~ 0.72dL/g.The reaction of the terminal hydroxy group of prepolymer and the two lactan of diacyl is expressed as follows:
The hexanolactam formed distils removing in vacuum system.
End carboxyl is Yu the reaction of bisoxazoline can be expressed as follows:
The polymer molecule formula of the polyesteramide with urea key of final formation is as follows:
Wherein n=2 ~ 12, m=2 ~ 10, x=2 ~ 6, the ratio shared in the structure because of chainextender is very low, can not consider that it affects.
1) performed polymer prepared by the present invention, is entirely terminal hydroxy group or end carboxyl without requiring two ends, by the common chain extension of the two lactan of Er Yuan oxazoline and diacyl; obtain the polymkeric substance of high molecular; the advantages such as this method has mild condition, and raw material is cheaply easy to get, environmental protection.
2) by regulating the ratio of urea monomer and diprotic acid, dibasic alcohol, the ratio of ester bond and amido linkage in polymkeric substance can be controlled, with the polyester amide polymer with urea key of obtained different amido linkage and bond content.Particularly adopt polycondensation, the preparation of chain extension two-step approach with the method for the biodegradable polyamidoester of urea key, the limiting viscosity of the prepared aliphatic polyester amide with urea key is 0.38 ~ 0.72dL/g's at 30 DEG C.
Below in conjunction with embodiment, the invention will be further described.
Embodiment:
The present invention utilizes 2-oxazolidone and aliphatie diamine to prepare the urea monomer with Amino End Group and terminal hydroxy group by the mol ratio ring-opening reaction of 1:1; performed polymer is prepared through melt phase polycondensation again with aliphatic dibasic acid, dibasic alcohol; by the associating chain extension of the two lactan chainextender of Er Yuan oxazoline and diacyl, preparation limiting viscosity is the biodegradable polyesteramide containing urea key between 0.38 ~ 0.72dL/g at about 30 DEG C.
The molecular weight of polymkeric substance characterizes by measuring limiting viscosity, is that solvent measures with m-cresol.According to above-described embodiment, the present invention is described in detail below to enumerate good embodiment, but realization of the present invention is not limited to following instance.The intrinsic viscosity of following examples is for record at 30 DEG C.
Embodiment 1:
1) preparation of Amino End Group terminal hydroxy group urea monomer (HAU): 39.6 parts of octamethylenediamines are dissolved in 50ml DMF (DMF), are warmed up to 160 DEG C; Take 60.4 parts of 2-oxazolidones to be by weight dissolved in 50ml DMF, and be added drop-wise in above-mentioned octamethylenediamine solution; Drip rear continuation reaction 5 hours, cool to room temperature, adularescent solid is separated out, and decompress filter, obtains white solid, is 487.05mgKOH/g through surveying hydroxyl value, and its molecular weight 230.36 is consistent with theoretical molecular 231.
2) with the preparation of the polyesteramide performed polymer of urea key: take the HAU monomer 69.3 parts prepared in step 1) with parts by weight, sebacic acid 145.6 parts, 1, 4-butyleneglycol 27.1 parts, 0.48 part, phosphorous acid, tin protochloride 0.24 part, under the protection of nitrogen, be warming up to 160 DEG C, 200 DEG C are slowly warmed up in 2 hours, then reliever is used instead, first react 2.5 hours with water pump decompression step by step, be decompressed to 3mmHg with oil pump again and react 3 hours, obtaining limiting viscosity is 0.19dL/g, acid number is 56.95mgKOH/g, hydroxyl value is the PrePEAU performed polymer of 33.65mgKOH/g.
3) step 2 is taken with parts by weight) the middle PrePEAU prepolymer 71.1 parts prepared; 1; 4-phenyl-bis-(2-oxazoline) 7.8 parts, adipoyl biscaprolactamate 7.2 parts; catalyzer tin protochloride 0.17 part and tosic acid 0.043 part; in 200 DEG C of synthesis under normal pressure 1.5 hours under the protection of nitrogen; then react 8.3 hours in 2mmHg depressurized system, the limiting viscosity of resulting polymers is 0.72dL/g.
Embodiment 2:
1) with the preparation of the polyesteramide performed polymer of urea key: take HAU monomer 11.6 parts prepared by step 1) in embodiment 1 with parts by weight, sebacic acid 141.6 parts, 1, 4-butyleneglycol 58.6 parts, 0.42 part, phosphorous acid, tin protochloride 0.21 part, under the protection of nitrogen, be warming up to 160 DEG C, 200 DEG C are slowly warmed up in 2 hours, then reliever is used instead, first react 2.5 hours with water pump decompression step by step, be decompressed to 3mmHg with oil pump again and react 3 hours, obtaining limiting viscosity is 0.26dL/g, acid number is 39.19mgKOH/g, hydroxyl value is the PrePEAU performed polymer of 32.01mgKOH/g.
3) step 2 is taken with parts by weight) the PrePEAU prepolymer 51.5 parts prepared; 1; 4-phenyl-bis-(2-oxazoline) 3.9 parts, adipoyl biscaprolactamate 4.9 parts; catalyzer tin protochloride 0.12 part and tosic acid 0.003 part under the protection of nitrogen in 200 DEG C of synthesis under normal pressure 1.5 hours; then react 4.3 hours in 2mmHg depressurized system, the limiting viscosity of resulting polymers is 0.38dL/g.
Embodiment 3:
1) with the preparation of the polyesteramide performed polymer of urea key: take HAU monomer 23.1 parts prepared by step 1) in embodiment 1 with parts by weight, sebacic acid 131.5 parts, 1, 4-butyleneglycol 49.5 parts, 0.41 part, phosphorous acid, tin protochloride 0.20 part, under the protection of nitrogen, be warming up to 160 DEG C, 200 DEG C are slowly warmed up in 2 hours, then reliever is used instead, first react 2.5 hours with water pump decompression step by step, be decompressed to 3mmHg with oil pump again and react 3 hours, obtaining limiting viscosity is 0.29dL/g, acid number is 31.13mgKOH/g, hydroxyl value is the PrePEAU performed polymer of 45.76mgKOH/g.
2) the PrePEAU prepolymer 50.9 parts prepared in step 1) is taken with parts by weight; 1; 4-phenyl-bis-(2-oxazoline) 3.1 parts, adipoyl biscaprolactamate 6.9 parts; catalyzer tin protochloride 0.12 part and tosic acid 0.003 part; in 200 DEG C of synthesis under normal pressure 1.5 hours under the protection of nitrogen; then react 2.5 hours in 2mmHg depressurized system, the limiting viscosity of resulting polymers is 0.57dL/g.
Embodiment 4:
1) with the preparation of the polyesteramide performed polymer of urea key: take HAU monomer 11.6 parts prepared by step 1) in embodiment 1 with parts by weight, sebacic acid 40.5 parts, 1, 4-butyleneglycol 13.5 parts, 0.13 part, phosphorous acid, tin protochloride 0.066 part, under the protection of nitrogen, be warming up to 160 DEG C, 200 DEG C are slowly warmed up in 2 hours, then reliever is used instead, first react 2.5 hours with water pump decompression step by step, be decompressed to 3mmHg with oil pump again and react 3 hours, obtaining limiting viscosity is 0.31dL/g, acid number is 31.38mgKOH/g, hydroxyl value is the PrePEAU performed polymer of 24.1mgKOH/g.
2) the PrePEAU prepolymer 59.3 parts prepared in step 1) is taken with parts by weight; 1; 4-phenyl-bis-(2-oxazoline) 3.6 parts, adipoyl biscaprolactamate 4.2 parts; catalyzer tin protochloride 0.13 part and tosic acid 0.034 part; in 200 DEG C of synthesis under normal pressure 1.5 hours under the protection of nitrogen; then react 2.8 hours in 2mmHg depressurized system, the limiting viscosity of resulting polymers is 0.62dL/g.
Embodiment 5:
1) with the preparation of the polyesteramide performed polymer of urea key: take HAU monomer 46.2 parts prepared by step 1) in embodiment 1 with parts by weight, sebacic acid 111.2 parts, 1, 4-butyleneglycol 31.5 parts, 0.38 part, phosphorous acid, tin protochloride 0.19 part, under the protection of nitrogen, be warming up to 160 DEG C, 200 DEG C are slowly warmed up in 2 hours, then reliever is used instead, first react 2.5 hours with water pump decompression step by step, be decompressed to 3mmHg with oil pump again and react 3 hours, obtaining limiting viscosity is 0.23dL/g, acid number is 25.6mgKOH/g, hydroxyl value is the PrePEAU performed polymer of 5.4mgKOH/g.
2) the PrePEAU prepolymer 50.1 parts prepared in step 1) is taken with parts by weight; 1; 4-phenyl-bis-(2-oxazoline) 2.4 parts, adipoyl biscaprolactamate 0.8 part; catalyzer tin protochloride 0.11 part and tosic acid 0.027 part; in 200 DEG C of synthesis under normal pressure 1.5 hours under the protection of nitrogen; then react 9 hours in 2mmHg depressurized system, the limiting viscosity of resulting polymers is 0.50dL/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.
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