CN103387668A - Preparation method of aliphatic polyester amide with urea bond - Google Patents
Preparation method of aliphatic polyester amide with urea bond Download PDFInfo
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- CN103387668A CN103387668A CN201210139316XA CN201210139316A CN103387668A CN 103387668 A CN103387668 A CN 103387668A CN 201210139316X A CN201210139316X A CN 201210139316XA CN 201210139316 A CN201210139316 A CN 201210139316A CN 103387668 A CN103387668 A CN 103387668A
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Abstract
The invention relates to a preparation method of aliphatic polyester amide with urea bond, and belongs to the technical field of polyester amide. According to the invention, urea monomer with terminal amino and terminal hydroxyl is subjected to melt polycondensation with aliphatic dicarboxylic acid and glycol. Amide content is changed through changing the ratio of the urea monomer with terminal amino and terminal hydroxyl to the dicarboxylic acid and glycol. With the method, a series of polyester amide prepolymers with the urea bond and with both Polyester amide structures are prepared. Chain-extending is carried out with diacyl bislactam and bisoxazoline chain extender, such that biodegradable polyester amide comprising urea bond is prepared. Characteristic viscosity of the product at 30 DEG C is 0.38-0.72dL/g.
Description
Technical field
The invention belongs to the polyesteramide technical field, the preparation method who relates to a kind of aliphatic polyester amide with the urea key, be specifically related to take aliphatic dibasic acid, dibasic alcohol and with the end aminoterminal carboxylic monomer of urea key as the synthetic aliphatic polyester amide with the urea key of raw material.
Technical background
The Heat stability is good of polyureas, all have good performance aspect tensile strength, modulus, elongation, snappiness, wear-resisting ageing-resistant, protection against corrosion.Polyureas is mainly synthetic by two kinds of methods: 1) isocyanic ester and diamines polymerization; 2) vulcabond and water reactive polymeric.Yeh etc., take polytetrahydrofuran as soft section, obtain hard section of polyureas with MDI and reacting ethylenediamine, have formed the polyurea elastomer with better toughness.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.Traditional polyureas vulcabond toxicity used of synthesizing is very large, has characteristic of concentration and latent in human body, and skin, eyes and respiratory tract are had the intense stimulus effect.
Aliphatic polyester amide (PEA) is a kind of novel biodegradable polymer.Compare with aliphatic polyester,, owing to introducing amide group, form hydrogen bond between amide group, make polymkeric substance have better mechanical property and intensity, the existence of ester bond simultaneously gives again material good biodegradability, and it is with a wide range of applications.US Patent No. 0,065,314(2005) reported with hexanodioic acid, 1,4-butyleneglycol, hexanolactam, hexanediamine are raw material, synthetic a kind of three block biodegradable polyesteramides under the effect of branching agent tetramethylolmethane, this material has good tensile property, elongation at break and biodegradable, but preparation method used is the direct melt polycondensation method, very high to the vacuum tightness requirement, vacuum tightness needs 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 reaction obtain two kinds of diamide glycol, these two kinds of diamide glycol and diprotic acid are carried out Melt polycondensation,, by regulating the ratio of two kinds of diamide glycol, obtain a series of performances differences, the different polyester-amide copolymer of degradation speed.But with diprotic acid and the polycondensation of diamide glycol, feed ratio is wayward, and easily causes monomer volatilization loss under the high temperature high vacuum, has affected proportioning raw materials, therefore is 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) reported the polyesteramide for preparing high molecular with vulcabond Huo bisoxazoline chain extension aliphatic polyester performed polymer, but the amido linkage content of the polyesteramide of this method preparation is lower, with corresponding aliphatic polyester, compares, and thermal characteristics and mechanical property obviously do not improve.
The polyesteramide with the urea key of synthesized of the present invention, compare raw material environmental protection, synthetic route green non-pollution with the synthetic polyureas of tradition.
Summary of the invention:
The objective of the invention is for the deficiencies in the prior art, the synthetic method of a kind of chain extension pollution-free, easy and simple to handle preparation with the polyesteramide of urea key is provided.The method raw material cheaply is easy to get, and the performed polymer preparation is simple.
the present invention adopts the standby aliphatic polyester amide that contains the urea key of chain extension legal system, employing is with urea monomer and the aliphatic dibasic acid of end amino and terminal hydroxy group, dibasic alcohol carries out melt phase polycondensation, by changing urea monomer and the diprotic acid of and terminal hydroxy group amino with end, the ratio of dibasic alcohol is regulated amide content, prepared the performed polymer of a series of whiles with the polyesteramide with the urea key of end carboxyl and terminal hydroxy group structure, again with the two lactan of diacyl with the bisoxazoline chainextender carries out chain extension, 30 ℃ of Biodegradable polyester amides that contain the urea key between 0.38 ~ 0.72dL/g of preparation limiting viscosity, concrete steps comprise as follows:
1) in 160 ℃ of dimethyl formamide (DMF) solution that will be dissolved with the 2-oxazolidone are added drop-wise to the DMF solution of diamines, dripped afterreaction 5 hours, cooling, obtain an end with amino, the end monomer that contains the urea key with hydroxyl;
2) with the monomer that contains the urea key for preparing in step 1), with aliphatic dihydroxy alcohol and diprotic acid melt phase polycondensation, take the urea key as two amido linkages, mol ratio according to amido linkage and ester bond in final formation polymkeric substance is (0.1～0.5): (0.9～0.5), amido linkage and ester bond sum are 1, total (monomer+dibasic alcohol that contains the urea key) is 1:(1.0～1.4 with the mol ratio of diprotic acid), carry out polymerization, and the phosphorous acid that adds total monomer weight 0.2% is as stablizer, under catalyzer exists, in nitrogen atmosphere, 160～210 ℃ of lower synthesis under normal pressure, collect the water that generates and arrive 60～80% of theoretical amount, change again Depressor response into, first with water pump decompression step by step reaction 2.5h, it is below 5mmHg that continuation makes vacuum tightness with the oil pump decompression, reaction 3h, until acid number is constant, obtain the performed polymer with the polyesteramide of urea key, wherein catalyst levels is 0.05～0.3wt% of total monomer weight,
3) with step 2) in the performed polymer of the polyesteramide with the urea key of preparation, with chainextender bisoxazoline and the two lactan of diacyl, catalyzer tin protochloride and tosic acid, at N
2, in 200 ℃ of synthesis under normal pressure 1.5 hours, then reacted under the 1-5mm mercury column 2.5～9 hours under protection, obtain the Biodegradable polyester amides with the urea key; Wherein, in the performed polymer of the polyesteramide with the urea key of 100 weight parts, the consumption of the two lactan of chainextender diacyl is that 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 end described in step 1) is with amino, the end monomer that contains the urea key with hydroxyl, for having the structure shown in logical formula I:
N=2 in following formula～12;
The general formula of the aliphatic diamine described in step 1) is NH
2(CH
2)
nNH
2, n=2～12, one or both that commonly used is in quadrol, propylene diamine, butanediamine, hexanediamine, octamethylenediamine etc.
The general formula of the aliphatic dibasic acid step 2) is HOOC (CH
2)
mCOOH, m=2～10, one or both that commonly used is in hexanodioic acid, suberic acid, sebacic acid etc.
Step 2) it is HO (CH that the aliphatic dihydroxy alcohol described in is selected from general formula
2)
xOH, x=2～6, commonly used have ethylene glycol, 1,3-PD, BDO, 1, one or more in 6-hexylene glycol or glycol ether etc.
Step 2) catalyzer described in is one or more mixing in Dibutyltin oxide, stannic oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate or titanium isopropylate;
Chainextender bisoxazoline described in step 3) comprises Zhi fat family Er Yuan oxazoline or the fragrant Er Yuan of the family 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, be connected Yu the oxazoline ring by ortho position, a position or contraposition;
The two lactan of chainextender diacyl described in step 3) comprise 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 aliphatics diacyl commonly used comprise: N, the two pyrrolidone of N '-oxalyl, N, the two hexanolactams of N '-oxalyl, N, the two laurolactams of N '-oxalyl, N, the two pyrrolidone of N '-succinyl, N, the two hexanolactams of N '-succinyl, N, the two laurolactams of N '-succinyl, N, the two pyrrolidone of N '-glutaryl, N, the two hexanolactams of N '-glutaryl, N, the two laurolactams of N '-glutaryl, N, the two pyrrolidone of N '-hexanedioyl, N, N '-adipoyl biscaprolactamate, N, the two laurolactams of N '-hexanedioyl, N, the two pyrrolidone of N '-azelaoyl, N, the two hexanolactams of N '-azelaoyl, N, the two laurolactams of N '-azelaoyl, N, the two pyrrolidone of N '-sebacoyl, N, the two hexanolactams of N '-sebacoyl or N, two 11 lactan of N '-sebacoyl, preferred N, the two hexanolactams of N '-succinyl and N, N '-adipoyl biscaprolactamate.
N commonly used, the two lactan of N '-aromatic series diacyl comprise: N, the two pyrrolidone of N '-phthalyl, N, the two hexanolactams of N '-phthalyl, N, the two laurolactams of N '-phthalyl, N, the two pyrrolidone of N '-isophthaloyl, N, the two hexanolactams of N '-isophthaloyl, N, the two laurolactams of N '-isophthaloyl, N, the two pyrrolidone of N '-paraphenylene terephthalamide, N, N '-terephthaloylbiscapro-lactamate or N, the two laurolactams of N '-paraphenylene terephthalamide; Preferred N, the two hexanolactams of N '-isophthaloyl and N, N '-terephthaloylbiscapro-lactamate.
In 100 parts of performed polymers of the polyesteramide with the urea key of parts by weight, 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, the chain extension weak effect; When too high, cost is too high, and the chain extension effect is variation also.
In step 3), the optimal temperature of chain extending reaction is 180～220 ℃, and the chain extending reaction temperature is too low, and the activity of chainextender is lower, and chain extending reaction carries out slowly and weak effect; The side reactions such as thermolysis, thermooxidizing easily occur in excess Temperature, polymkeric substance, and the chain extension effect is poor, and the product color is darker.
Advantage of the present invention and effect thereof:
The present invention is by 2-oxazolidone and aliphatie diamine reaction; preparation is with the urea monomer of end amino and terminal hydroxy group; then urea monomer and aliphatic diacid, glycol reaction; generation is with the performed polymer of the polyesteramide of urea key; this performed polymer contains end carboxyl and terminal hydroxy group simultaneously; utilize afterwards the two lactan reactions of its terminal hydroxy group and diacyl; utilize its end carboxyl and the reaction of Er Yuan oxazoline; realize the chain extension of prepolymer; obtain the polyesteramide with the urea key of the biodegradable of high molecular, the limiting viscosity of 30 ℃ of left and right is 0.38 ~ 0.72dL/g.The reaction of the two lactan of the terminal hydroxy group of prepolymer and diacyl is expressed as follows:
The hexanolactam that forms distils and removes in vacuum system.
Hold carboxyl Yu the reaction of bisoxazoline can be expressed as follows:
The polymer molecule formula of the final polyesteramide with the urea key that forms is as follows:
N=2 ~ 12 wherein, m=2 ~ 10, x=2 ~ 6,, because chainextender shared ratio in structure is very low, can not consider its impact.
1) the prepared performed polymer of the present invention, needn't require two ends to be entirely terminal hydroxy group or end carboxyl, by the common chain extension of two yuan of oxazolines and the two lactan of diacyl; obtain the polymkeric substance of high molecular; this method has mild condition, and raw material cheaply is easy to get, the advantages such as environmental protection.
2), by regulating the ratio of urea monomer and diprotic acid, dibasic alcohol, can control the ratio of ester bond and amido linkage in polymkeric substance, to make the polymkeric substance of the polyesteramide with the urea key of different amido linkages and ester bond content.Particularly adopt polycondensation, chain extension two-step approach to prepare the method with the biodegradable polyamidoester of urea key, the limiting viscosity of prepared aliphatic polyester amide with the urea key is 0.38～0.72dL/g's at 30 ℃.
The invention will be further described below in conjunction with embodiment.
Embodiment:
The present invention utilizes the 2-oxazolidone and aliphatie diamine is amino with end by the mol ratio ring-opening reaction preparation of 1:1 and the urea monomer of terminal hydroxy group; prepare performed polymer with aliphatic dibasic acid, dibasic alcohol through melt phase polycondensation again; by the associating chain extension of Er Yuan oxazoline and the two lactan chainextenders of diacyl, the preparation limiting viscosity is the biodegradable polyesteramide that contains the urea key between 0.38～0.72dL/g 30 ℃ of left and right.
The molecular weight of polymkeric substance characterizes by measuring limiting viscosity, take m-cresol as solvent, measures.According to above-described embodiment, the present invention is described in detail below to enumerate preferably embodiment, but realization of the present invention is not limited to following instance.The intrinsic viscosity of following examples is for to record at 30 ℃.
Embodiment 1:
1) preparation of end aminoterminal hydroxyurea monomer (HAU): 39.6 parts of octamethylenediamines are dissolved in 50ml DMF (DMF), are warmed up to 160 ℃; Take by weight 60.4 parts of 2-oxazolidones and be dissolved in 50ml DMF, and be added drop-wise in above-mentioned octamethylenediamine solution; Drip rear continuation reaction 5 hours, cool to room temperature, the adularescent solid is separated out, and decompress filter obtains white solid, through surveying hydroxyl value, is 487.05mgKOH/g, and its molecular weight 230.36 is consistent with theoretical molecular 231.
2) with the preparation of the polyesteramide performed polymer of urea key: with parts by weight, take 69.3 parts of the HAU monomers that prepare in step 1), 145.6 parts of sebacic acid, 1, 27.1 parts of 4-butyleneglycols, 0.48 part, phosphorous acid, 0.24 part of tin protochloride, under the protection of nitrogen, be warming up to 160 ℃, slowly be warmed up to 200 ℃ in 2 hours, then use reliever instead, first with water pump decompression step by step reaction 2.5 hours, be decompressed to 3mmHg reaction 3 hours with oil pump again, 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) take step 2 with parts by weight) in 71.1 parts of the PrePEAU prepolymers of preparation; 1; 7.8 parts of 4-phenyl-two (2-oxazoline), 7.2 parts of adipoyl biscaprolactamates; 0.043 part of 0.17 part of catalyzer tin protochloride and tosic acid; under the protection of nitrogen in 200 ℃ of synthesis under normal pressure 1.5 hours; then 2mmHg depressurized system internal reaction 8.3 hours, the limiting viscosity of resulting polymers was 0.72dL/g.
Embodiment 2:
1) with the preparation of the polyesteramide performed polymer of urea key: 11.6 parts of HAU monomers that take step 1) preparation in embodiment 1 with parts by weight, 141.6 parts of sebacic acid, 1, 58.6 parts of 4-butyleneglycols, 0.42 part, phosphorous acid, 0.21 part of tin protochloride, under the protection of nitrogen, be warming up to 160 ℃, slowly be warmed up to 200 ℃ in 2 hours, then use reliever instead, first with water pump decompression step by step reaction 2.5 hours, be decompressed to 3mmHg reaction 3 hours with oil pump again, 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) take step 2 with parts by weight) 51.5 parts of the PrePEAU prepolymers of preparation; 1; 3.9 parts of 4-phenyl-two (2-oxazoline), 4.9 parts of adipoyl biscaprolactamates; 0.003 part of 0.12 part of catalyzer tin protochloride and tosic acid under the protection of nitrogen in 200 ℃ of synthesis under normal pressure 1.5 hours; then 2mmHg depressurized system internal reaction 4.3 hours, the limiting viscosity of resulting polymers was 0.38dL/g.
Embodiment 3:
1) with the preparation of the polyesteramide performed polymer of urea key: 23.1 parts of HAU monomers that take step 1) preparation in embodiment 1 with parts by weight, 131.5 parts of sebacic acid, 1, 49.5 parts of 4-butyleneglycols, 0.41 part, phosphorous acid, 0.20 part of tin protochloride, under the protection of nitrogen, be warming up to 160 ℃, slowly be warmed up to 200 ℃ in 2 hours, then use reliever instead, first with water pump decompression step by step reaction 2.5 hours, be decompressed to 3mmHg reaction 3 hours with oil pump again, 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) take 50.9 parts of the PrePEAU prepolymers that prepare in step 1) with parts by weight; 1; 3.1 parts of 4-phenyl-two (2-oxazoline), 6.9 parts of adipoyl biscaprolactamates; 0.003 part of 0.12 part of catalyzer tin protochloride and tosic acid; under the protection of nitrogen in 200 ℃ of synthesis under normal pressure 1.5 hours; then 2mmHg depressurized system internal reaction 2.5 hours, the limiting viscosity of resulting polymers was 0.57dL/g.
Embodiment 4:
1) with the preparation of the polyesteramide performed polymer of urea key: 11.6 parts of HAU monomers that take step 1) preparation in embodiment 1 with parts by weight, 40.5 parts of sebacic acid, 1, 13.5 parts of 4-butyleneglycols, 0.13 part, phosphorous acid, 0.066 part of tin protochloride, under the protection of nitrogen, be warming up to 160 ℃, slowly be warmed up to 200 ℃ in 2 hours, then use reliever instead, first with water pump decompression step by step reaction 2.5 hours, be decompressed to 3mmHg reaction 3 hours with oil pump again, 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) take 59.3 parts of the PrePEAU prepolymers that prepare in step 1) with parts by weight; 1; 3.6 parts of 4-phenyl-two (2-oxazoline), 4.2 parts of adipoyl biscaprolactamates; 0.034 part of 0.13 part of catalyzer tin protochloride and tosic acid; under the protection of nitrogen in 200 ℃ of synthesis under normal pressure 1.5 hours; then 2mmHg depressurized system internal reaction 2.8 hours, the limiting viscosity of resulting polymers was 0.62dL/g.
Embodiment 5:
1) with the preparation of the polyesteramide performed polymer of urea key: 46.2 parts of HAU monomers that take step 1) preparation in embodiment 1 with parts by weight, 111.2 parts of sebacic acid, 1, 31.5 parts of 4-butyleneglycols, 0.38 part, phosphorous acid, 0.19 part of tin protochloride, under the protection of nitrogen, be warming up to 160 ℃, slowly be warmed up to 200 ℃ in 2 hours, then use reliever instead, first with water pump decompression step by step reaction 2.5 hours, be decompressed to 3mmHg reaction 3 hours with oil pump again, 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) take 50.1 parts of the PrePEAU prepolymers that prepare in step 1) with parts by weight; 1; 2.4 parts of 4-phenyl-two (2-oxazoline), 0.8 part of adipoyl biscaprolactamate; 0.027 part of 0.11 part of catalyzer tin protochloride and tosic acid; under the protection of nitrogen in 200 ℃ of synthesis under normal pressure 1.5 hours; then 2mmHg depressurized system internal reaction 9 hours, the limiting viscosity of resulting polymers was 0.50dL/g.
Claims (6)
1. the preparation method with the aliphatic polyester amide of urea key, is characterized in that, comprises the following steps:
1) in 160 ℃ of dimethyl formamide (DMF) solution that will be dissolved with the 2-oxazolidone are added drop-wise to the DMF solution of diamines, dripped afterreaction 5 hours, cooling, obtain an end with amino, the end monomer that contains the urea key with hydroxyl;
2) with the monomer that contains the urea key for preparing in step 1), with aliphatic dihydroxy alcohol and diprotic acid melt phase polycondensation, take the urea key as two amido linkages, mol ratio according to amido linkage and ester bond in final formation polymkeric substance is (0.1～0.5): (0.9～0.5), amido linkage and ester bond sum are 1, total (monomer+dibasic alcohol that contains the urea key) is 1:(1.0～1.4 with the mol ratio of diprotic acid), carry out polymerization, and the phosphorous acid that adds total monomer weight 0.2% is as stablizer, under catalyzer exists, in nitrogen atmosphere, 160～210 ℃ of lower synthesis under normal pressure, collect the water that generates and arrive 60～80% of theoretical amount, change again Depressor response into, first with water pump decompression step by step reaction 2.5h, it is below 5mmHg that continuation makes vacuum tightness with the oil pump decompression, reaction 3h, until acid number is constant, obtain the performed polymer with the polyesteramide of urea key, wherein catalyst levels is 0.05～0.3wt% of total monomer weight,
3) with step 2) in the performed polymer of the polyesteramide with the urea key of preparation, with chainextender bisoxazoline and the two lactan of diacyl, catalyzer tin protochloride and tosic acid, at N
2, in 200 ℃ of synthesis under normal pressure 1.5 hours, then reacted under the 1-5mm mercury column 2.5～9 hours under protection, obtain the Biodegradable polyester amides with the urea key; Wherein, in the performed polymer of the polyesteramide with the urea key of 100 weight parts, the consumption of the two lactan of chainextender diacyl is that 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 end described in step 1) is with amino, the end monomer that contains the urea key with hydroxyl, for having the structure shown in logical formula I:
N=2 in following formula～12;
The general formula of the aliphatic diamine described in step 1) is NH
2(CH
2)
nNH
2, n=2～12,
The general formula of the aliphatic dibasic acid step 2) is HOOC (CH
2)
mCOOH, m=2～10,
Step 2) it is HO (CH that the aliphatic dihydroxy alcohol described in is selected from general formula
2)
xOH, x=2～6,
Step 2) catalyzer described in is Dibutyltin oxide, stannic oxide, tin protochloride, zinc oxide, vinegar
One or more mixing in acid zinc, tetrabutyl titanate or titanium isopropylate;
Chainextender bisoxazoline described in step 3) comprises Zhi fat family Er Yuan oxazoline or the fragrant Er Yuan of the family 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, be connected Yu the oxazoline ring by ortho position, a position or contraposition;
The two lactan of chainextender diacyl described in step 3) comprise 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.
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 ethylene glycol, 1,3-PD, BDO, 1, one or more in 6-hexylene glycol or glycol ether.
5. according to the method for claim 1, it is characterized in that, what the bisoxazoline of De described in step 3) chainextender was commonly used has 1,4-phenyl-two (2-oxazoline), 1,3-phenyl-two (2-oxazoline), 1,4-two (2-oxazoline) butane, 1,2-two (2-oxazoline) ethane or two (2-oxazolines).
6., according to the method for claim 1, it is characterized in that, the two lactan of aliphatics diacyl are N, the two hexanolactams of N '-succinyl or N, N '-adipoyl biscaprolactamate; N, the two lactan of N '-aromatic series diacyl are N, the two hexanolactams of N '-isophthaloyl or N, N '-terephthaloylbiscapro-lactamate.
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| 李红微等: "缩聚-扩链法合成脂肪族聚酯酰胺", 《北京化工大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752059A (en) * | 2022-04-19 | 2022-07-15 | 西北大学 | Preparation method of high molecular weight aliphatic polyester amide |
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