CN102643422A - Preparation method for biodegradable aliphatic alternating polyester amide - Google Patents
Preparation method for biodegradable aliphatic alternating polyester amide Download PDFInfo
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Abstract
The invention discloses a preparation method for biodegradable aliphatic alternating polyester amide. According to the preparation method, aliphatic dicarboxylic acid and diamide diol are subjected to melt phase polycondensation to prepare alternating polyester amide prepolymer with terminal carboxyl group and terminal hydroxy group; and diacyl di-lactam and a bisoxazoline chain extender are subjected to joint chain extension to prepare the biodegradable aliphatic alternating polyester amide with the intrinsic viscosity of 0.30-0.59dL/g. The preparation method disclosed by the invention has the characteristics of simple and convenient method, mild conditions, high efficiency and the like and can be used for preparing the biodegradable aliphatic alternating polyester amide with regular structure and favorable crystallinity.
Description
Technical field
The present invention relates to adopt a kind of is the preparation method that the aliphatics of raw material replaces polyesteramide with diprotic acid and diamide glycol, particularly adopts polycondensation, chain extension two-step approach to prepare limiting viscosity replaces polyesteramide in the high biodegradable aliphatics of compound with regular structure, good crystallinity, the molecular weight of 0.30～0.59dL/g method.
Technical background
Aliphatic poly esteramides (PEA) is a kind of novel biodegradable polymer; Compare with aliphatic polyester; Owing to introduce amide group, form hydrogen bond between amide group, make polymkeric substance have better mechanical property and intensity; Material favorable biological degradability ability is given in the existence of ester bond simultaneously again, and it is with a wide range of applications.
(Bayer company) patent WO9942514 such as Timmermann (1999), WO9928371 (1999), DE4327024 (1995), WO9935179 (1999) have reported that direct melt polycondensation prepares the Biodegradable polyester acid amides by diprotic acid, divalent alcohol and diamine and/or hexanolactam etc.This product has favorable mechanical performance and biodegradability, and is that trade mark has been produced a series of this type of polyesteramides with BAK.But in this type of polyesteramide, ester bond and amido linkage are random distribution, and the crystallinity of polymkeric substance is relatively poor or fusing point is lower, and thermotolerance is relatively poor; And used preparation method is direct melt-polycondensation, and very high to the vacuum tightness requirement, vacuum tightness needs below 0.5mmHg.
U.S. Pat 4,343,931 (1982) have reported by oxyacetic acid or lactic acid and the synthetic diamide glycol of aliphatic diamine reaction, and itself and binary acyl chloride reaction are prepared the biodegradable polyester acid amides.But in this reaction because acyl chlorides is too active, perishable reactor drum and environment brought pollution.
(synthetic chemistries such as domestic Liu's filial piety ripple; 1999,7 (4), 354) with oxyacetic acid and 1; 12-12 diamines, caprolactone and hexanediamine reaction be two kinds of diamide two alcohol intermediates of preparation earlier; Carry out melt co-polycondensation reaction according to certain ratio and diprotic acid again,, can obtain a series of molecular weight, polyesteramide that thermomechanical property is different through regulating the ratio of two kinds of diamide glycol.But also synthetic through direct polycondensation method, exigent vacuum tightness is high to the requirement of equipment; And prepare polyesteramide with diprotic acid and diamide glycol direct condensation, under the high temperature high vacuum, cause monomer volatilization loss easily, influenced proportioning raw materials, feed ratio is wayward, therefore is difficult to obtain high molecular weight polymers.
Chinese patent CN 1,310,194A (2001), CN 1; 124,304C (2003), CN 101,020; 746A (2007) has reported with vulcabond Huo bisoxazoline chain extension aliphatic polyester performed polymer and has prepared the high-molecular weight polyesteramide; But the amido linkage content of the polyesteramide of this method preparation is lower, compares with corresponding aliphatic polyester, and thermal property and mechanical property obviously do not improve.
Summary of the invention
The objective of the invention is shortcoming, provide a kind of chain extension method easy and simple to handle to prepare the method that biodegradable aliphatics replaces polyesteramide to random polyesteramide crystallinity and poor mechanical property.The preparation of this method performed polymer is simple, and the chain extending reaction temperature is lower, and the aliphatics of preparation replaces that polyester amide structure is regular, crystallinity and biological degradability are good.
The present invention adopts aliphatic dibasic acid and diamide glycol to carry out melt phase polycondensation; Preparation has the polyesteramide performed polymer of end carboxyl and terminal hydroxy group structure simultaneously; Again with the two lactan of diacyl with the bisoxazoline chainextender is united chain extension, the biodegradable aliphatics of preparation limiting viscosity between 0.30～0.59dL/g replaces polyesteramide.Concrete steps are following:
1) is raw material with diprotic acid and diamide glycol, presses diprotic acid and mix, in the presence of catalyzer with diamide glycol mol ratio 1.00～1.30; In nitrogen atmosphere, under 160～200 ℃, synthesis under normal pressure is collected the water that generates and is arrived 60～80% of theoretical amount; Change reliever again into, progressively reduce pressure with water pump earlier and react 3～4h, continue to use the oil pump decompression to make vacuum tightness as below the 10mmHg; Reaction 3～4h till acid number is constant basically, obtains limiting viscosity at the polyesteramide prepolymer below 0.20; Wherein, catalyst consumption is 0.005～0.3% of a total monomer weight;
2) with the polyesteramide performed polymer for preparing in the step 1); In the presence of catalyzer; With bisoxazoline mixed chain extender chain extension, the chain extension temperature is between 180～220 ℃ with the two lactan of diacyl or carbonyl di-lactame, and first normal pressure is down behind the reaction 1-2h; Under the 5mmHg reduced pressure, reacted 1～4 hour, the biodegradable aliphatics that obtains limiting viscosity and be 0.30～0.59dL/g replaces polyesteramide again; Wherein, in the polyesteramide performed polymer of 100 weight parts, the consumption of chainextender bisoxazoline is 0.9～16 part, and the consumption of the two lactan of chainextender diacyl is 0.05～5.9 part, and wherein, catalyst consumption is 0.005～0.3% of a total monomer weight.
Wherein, the diamide glycol described in the step 1) is for having the structure shown in the general formula (I):
R is-(CH in the formula
2)
n-, n=0～20 wherein.
Diamide glycol described in the step 1) has N; N '-two (2-hydroxyethyl) oxalamide, N; N '-two (2-hydroxyethyl) succinic diamide, N, N '-two (2-hydroxyethyl) glutaramide, N, N '-two (2-hydroxyethyl) adipamide, N; N '-two (2-hydroxyethyl) suberamide, N, one or more in N '-two (2-hydroxyethyl) the sebacoyl amine etc.
The general formula of the diprotic acid described in the step 1) is HOOC (CH
2)
nCOOH, wherein n=0～20.Diprotic acid commonly used is one or more in oxalic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, the sebacic acid.
Step 1), 2) catalyzer described in is one or more mixing in Dibutyltin oxide, White tin oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate, titanium isopropylate or the tosic acid;
Polycondensation temperature described in the step 1) is between 160～200 ℃.Temperature is crossed low reaction speed and is descended, too high then performed polymer color burn, and side reaction increases.
Mol ratio through control diprotic acid and diamide glycol in the step 1) is had the polyesteramide performed polymer of holding carboxyl and terminal hydroxy group simultaneously.The mol ratio of diprotic acid and diamide glycol is lower than at 1.00 o'clock, and the performed polymer terminal hydroxyl content of acquisition can obviously increase, and in follow-up chain extension process, can produce a large amount of hexanolactams and be difficult for removing, and has influenced the raising of molecular weight; The mol ratio of diprotic acid and diamide glycol is higher than at 1.30 o'clock, and the performed polymer molecular weight that obtains is low, and chain extension dosage used during chain extension is big, and the chain extension effect is also bad.Therefore, the mol ratio of diprotic acid and diamide glycol is preferably between 1.00～1.30.
Step 2) bisoxazoline of De described in class chainextender comprises that Zhi fat family Er Yuan oxazoline and the fragrant Er Yuan of the family oxazoline of Fang structure are shown in (II):
R is-(CH in the formula
2)
n-, n=0～20 or be phenyl, pyridyl link to each other Yu the oxazoline ring through ortho position, a position or contraposition mode.The Er Yuan of Zhi fat family oxazoline commonly used comprises: two (2-oxazolines), 1,1-two (2-oxazoline) methane, 1,2-two (2-oxazoline) ethane, 1; 3-two (2-oxazoline) propane, 1,4-two (2-oxazoline) butane, 1,5-two (2-oxazoline) pentane, 1; 6-two (2-oxazoline) hexane, 1,7-two (2-oxazoline) heptane, 1,8-two (2-oxazoline) octane, 1; 9-two (2-oxazoline) nonane, 1; 10-two (2-oxazoline) decane, 1,11-two (2-oxazoline) undecane or 1,12-two (2-oxazoline) dodecyl etc.; The fragrant Er Yuan of the family oxazoline of Fang commonly used comprises: 1, and 2-phenyl-two (2-oxazoline), 1,3-phenyl-two (2-oxazoline), 1; 4-phenyl-two (2-oxazoline), and 2,3-pyridyl-two (2-oxazoline), 2; 4-pyridyl-two (2-oxazoline), 2,5-pyridyl-two (2-oxazoline), 2,6-pyridyl-two (2-oxazoline), 3; 4-pyridyl-two (2-oxazoline) etc., wherein preferred 1,4-phenyl-two (2-oxazoline), 1; 3-phenyl-two (2-oxazoline), 1,4-bisoxazoline butane, 1,2-bisoxazoline ethane or two (2-oxazolines).
Step 2) the two lactams chainextenders of the diacyl described in comprise two lactan of aliphatics diacyl and the two lactan of aromatic series diacyl, shown in the structure (III):
M=3～12 wherein; R is-(CH
2)
n-, n=0～20 or be phenyl ring link to each other with dicarbapentaborane through ortho position, a position or contraposition mode.
Carbonyl di-lactame, structure is shown in (IV):
M=3～12 wherein.
The two lactan of aliphatics diacyl commonly used comprise following: N, the two pyrrolidone of N '-phosphinylidyne, N, the two hexanolactams of N '-phosphinylidyne, N, the two laurolactams of N '-phosphinylidyne; 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; The two hexanolactams of N '-hexanedioyl, N, the two laurolactams of N '-hexanedioyl, N, the two pyrrolidone of N '-azelaoyl nonanedioyl, N; The two hexanolactams of N '-azelaoyl nonanedioyl, N, the two laurolactams of N '-azelaoyl nonanedioyl, N, the two pyrrolidone of N '-sebacoyl, N; Two hexanolactams of N '-sebacoyl or N, the two laurolactams of N '-sebacoyl etc., wherein the most frequently used preferred N; The two hexanolactams of N '-phosphinylidyne, N, two hexanolactams of N '-succinyl and N, the two hexanolactams of N '-hexanedioyl.
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; Two hexanolactams of N '-paraphenylene terephthalamide or N, the two laurolactams of N '-paraphenylene terephthalamide etc.The two preferred N of lactan of wherein the most frequently used aromatic series diacyl, two hexanolactams of N '-isophthaloyl and N, the two hexanolactams of N '-paraphenylene terephthalamide.
The consumption of chainextender bisoxazoline is 0.9～14.6% of a polyesteramide prepolymer weight, and the consumption of the two lactan of chainextender diacyl is 0～5.9% of a polyesteramide prepolymer weight.The consumption of chainextender is crossed when hanging down, and chain extending reaction is incomplete, the chain extension weak effect; When too high, cost is too high, and the chain extension effect is variation on the contrary.
Chain extending reaction carried out under normal pressure 1-2 hour earlier, back chain extension in being lower than the depressurized system of 5mmHg, and the chain extending reaction temperature is between 160～220 ℃.Temperature is low, and the activity of chainextender is not easy to display, and chain extending reaction is slow; Temperature is high, and the easy thermolysis of polymkeric substance, thermooxidizing are serious, and the product color is darker, and follows ester-amide exchange reaction, makes the regularity variation of polymkeric substance, crystallinity deterioration.
Effect of the present invention:
The present invention has the polyesteramide performed polymer of end carboxyl and terminal hydroxy group simultaneously through diprotic acid and diamide glycol polycondensation preparation; Utilize the two lactan reactions of its terminal hydroxy group and diacyl; Utilize the reaction of its end carboxyl and Er Yuan oxazoline; Realize the mixing chain extension of performed polymer, obtain the high-molecular weight biodegradable fatty and replace polyesteramide.With the two lactan and 1 of adipyl, 4-phenyl-two (2-oxazoline) is a chainextender, and the structure of resulting polymers is following:
M=0～20, n=0～10, x is the number of repeat unit of polyesteramide performed polymer.
The two lactan reactions of terminal hydroxy group and diacyl can be represented as follows:
The hexanolactam that forms distils in vacuum system and removes.
End carboxyl and the reaction of Er Yuan oxazoline can be represented as follows:
The present invention carries out melt phase polycondensation according to the mol ratio of diprotic acid and diamide glycol in 1.00～1.30 scopes, preparation polyesteramide performed polymer; Residual terminal hydroxy group and end carboxyl in the performed polymer can be respectively and two lactan of diacyl or the reaction of Er Yuan oxazoline, realize chain extension, obtain high molecular weight polymers; And can be different according to the content of end-group structure, regulate the consumption of two kinds of chainextenders, reach good chain extension effect, proportion of raw materials is easier to control.This method is easier, efficient, save time.
Embodiment
The present invention utilizes diprotic acid and diamide glycol polycondensation preparation to have the alternately polyesteramide performed polymer of end carboxyl and terminal hydroxy group simultaneously; Through the associating chain extension of Er Yuan oxazoline and the two lactan chainextenders of diacyl, the biodegradable fatty of preparation limiting viscosity between 0.30～0.59dL/g replaces polyesteramide again.The limiting viscosity of polymkeric substance is with N, and N '-N and DMSO 99.8MIN. (volume ratio is 1: 1) mixed solvent is measured.
According to above-mentioned embodiment, enumerate below preferably that embodiment is elaborated to the present invention, but realization of the present invention is not limited to following instance.
Embodiment 1: the preparation that gathers hexanodioic acid oxamide diol ester performed polymer (PEA-1): with 50 parts of hexanodioic acids of parts by weight, 46.3 parts of N, N '-two (2-hydroxyethyl) oxalamide, 0.05% tindichloride are under nitrogen protection; Carry out polycondensation from 160 ℃, collect generate the water yield 70～80% after, use reliever instead; Progressively reduce pressure with water pump earlier and react 2h; With the oil pump decompression, make pressure reduce to 7mmHg again, continue reaction 3～4h 160～180 ℃ of TRs; Till acid number was constant basically, obtaining limiting viscosity was that 0.08dL/g, acid number are that 54.27mgKOH/g, hydroxyl value are the PEA-1 performed polymer of 11.53mgKOH/g.
100 parts of PEA-1 performed polymers of parts by weight with above-mentioned preparation; Add 3.5 parts of N, two hexanolactams of N '-hexanedioyl, 10.4 part 1,4-phenyl-two (2-oxazoline) chainextender; And the Catalyzed by p-Toluenesulfonic Acid agent of 0.1 part of tindichloride and 0.05 part; Under nitrogen protection in 200 ℃ of synthesis under normal pressure 1.5 hours, oil pump decompression (pressure 5mmHg) reaction 3 hours, the biodegradable aliphatics of preparing limiting viscosity and be 0.50dL/g replaces polyesteramide.
Embodiment 2: the preparation that gathers hexanodioic acid oxamide diol ester performed polymer (PEA-2): with 50 parts of hexanodioic acids of parts by weight, 50.2 parts of N, N '-two (2-hydroxyethyl) oxalamide, 0.1% tindichloride are under nitrogen protection; Carry out polycondensation from 160 ℃, collect generate the water yield 70～80% after, use reliever instead; Progressively reduce pressure with water pump earlier and react 2h; With the oil pump decompression, make pressure reduce to 7mmHg again, continue reaction 3～4h 160～180 ℃ of TRs; Till acid number was constant basically, obtaining limiting viscosity was that 0.10dL/g, acid number are that 47.09mgKOH/g, hydroxyl value are the PEA-2 performed polymer of 11.27mgKOH/g.
100 parts of PEA-2 performed polymers of parts by weight with above-mentioned preparation; Add 3.4 parts of N, two hexanolactams of N '-hexanedioyl, 9.1 part 1,4-phenyl-two (2-oxazoline) chainextender; And the Catalyzed by p-Toluenesulfonic Acid agent of 0.2 part of tindichloride and 0.05 part; Under nitrogen protection in 200 ℃ of synthesis under normal pressure 1.5 hours, oil pump decompression (pressure 5mmHg) reaction 3 hours, the biodegradable aliphatics of preparing limiting viscosity and be 0.43dL/g replaces polyesteramide.
Embodiment 3 gathers the preparation of sebacic acid oxamide diol ester performed polymer (PEA-3): with 50 parts of sebacic acid of parts by weight, 33.47 parts of N, N '-two (2-hydroxyethyl) oxalamide, 0.1% tindichloride are under nitrogen protection; Carry out polycondensation from 170 ℃, collect generate the water yield 70～80% after, use reliever instead; Progressively reduce pressure with water pump earlier and react 2h; With the oil pump decompression, make pressure reduce to 7mmHg again, continue reaction 3～4h 170～180 ℃ of TRs; Till acid number was constant basically, obtaining limiting viscosity was that 0.20dL/g, acid number are that 48.77mgKOH/g, hydroxyl value are the PEA-3 performed polymer of 3.91mgKOH/g.
PEA-3 performed polymer 100 parts by weight with embodiment 3 preparations; Add 1.2 weight part N; The two hexanolactams of N '-hexanedioyl, 9.6 weight parts 1,4-phenyl-two (2-oxazoline) chainextender, under the nitrogen protection in 200 ℃ of synthesis under normal pressure 1.5 hours; Oil pump decompression (pressure 2mmHg) reaction 3 hours, the biodegradable aliphatics of preparing limiting viscosity and be 0.44dL/g replaces polyesteramide.
Embodiment 4 gathers the preparation of sebacic acid oxamide diol ester performed polymer (PEA-4): with 50 parts of sebacic acid of parts by weight, 33.47 parts of N, and N '-two (2-hydroxyethyl) oxalamide, 0.1% tindichloride; Under nitrogen protection, carry out polycondensation from 160 ℃, collect generate the water yield 70～80% after; Use reliever instead, progressively reduce pressure with water pump earlier and react 2h, reduce pressure with oil pump again; Make pressure reduce to 7mmHg; Continue reaction 3～4h 160～170 ℃ of TRs, till acid number was constant basically, obtaining limiting viscosity was that 0.10dL/g, acid number are that 75.84mgKOH/g, hydroxyl value are the PEA-4 performed polymer of 21.51mgKOH/g.
PEA-4 performed polymer 100 parts by weight with embodiment 4 preparations; Add 5 weight part N; The two hexanolactams of N '-hexanedioyl, 15 weight parts 1,4-phenyl-two (2-oxazoline) chainextender, under the nitrogen protection in 200 ℃ of synthesis under normal pressure 1.5 hours; Oil pump decompression (pressure 2mmHg) reaction 3 hours, the biodegradable aliphatics of preparing limiting viscosity and be 0.30dL/g replaces polyesteramide.
Embodiment 5 gathers the preparation of hexanodioic acid adipamide diol ester performed polymer (PEA-5): with 50 parts of hexanodioic acids of parts by weight, 66.3 parts of N, N '-two (2-hydroxyethyl) adipamide is under nitrogen protection; Carry out polycondensation from 160 ℃, collect generate the water yield 70～80% after, use reliever instead; Progressively reduce pressure with water pump earlier and react 2h; With the oil pump decompression, make pressure reduce to 7mmHg again, continue reaction 3～4h 160～180 ℃ of TRs; Till acid number was constant basically, obtaining limiting viscosity was that 0.12dL/g, acid number are that 62.17mgKOH/g, hydroxyl value are the PEA-5 performed polymer of 0mgKOH/g.
100 parts of PEA-5 performed polymers of parts by weight with embodiment 5 preparations; Add 12 part 1; 4-phenyl-two (2-oxazoline) chainextender, and 0.1 part tindichloride catalyzer, under nitrogen protection in 200 ℃ of synthesis under normal pressure 1.5 hours; Oil pump decompression (pressure 5mmHg) reaction 3 hours, the biodegradable aliphatics of preparing limiting viscosity and be 0.59dL/g replaces polyesteramide.
Embodiment 6 gathers the preparation of hexanodioic acid adipamide diol ester performed polymer (PEA-6): with 50 parts of hexanodioic acids of parts by weight, 66.3 parts of N, and N '-two (2-hydroxyethyl) adipamide, 0.1% tindichloride; Under nitrogen protection, carry out polycondensation from 160 ℃, collect generate the water yield 70～80% after; Use reliever instead, progressively reduce pressure with water pump earlier and react 2h, reduce pressure with oil pump again; Make pressure reduce to 7mmHg; Continue reaction 3～4h 160～180 ℃ of TRs, till acid number was constant basically, obtaining limiting viscosity was that 0.12dL/g, acid number are that 66.41mgKOH/g, hydroxyl value are the PEA-6 performed polymer of 3.47mgKOH/g.
100 parts of PEA-6 performed polymers of parts by weight with embodiment 6 preparations; Add 1 part of N; The two hexanolactams of N '-hexanedioyl, 13 part 1,4-phenyl-two (2-oxazoline) chainextender, under nitrogen protection in 200 ℃ of synthesis under normal pressure 1.5 hours; Oil pump decompression (pressure 5mmHg) reaction 3 hours, the biodegradable aliphatics of preparing limiting viscosity and be 0.51dL/g replaces polyesteramide.
Embodiment 7 gathers the preparation of sebacic acid adipamide diol ester performed polymer (PEA-7): with 50 parts of sebacic acid of parts by weight, 44.2 parts of N, and N '-two (2-hydroxyethyl) adipamide, catalyzer is 0.05% tindichloride; Under nitrogen protection, carry out polycondensation from 160 ℃, collect generate the water yield 70～80% after; Use reliever instead, progressively reduce pressure with water pump earlier and react 2h, reduce pressure with oil pump again; Make pressure reduce to 7mmHg; Continue reaction 3～4h 160～180 ℃ of TRs, till acid number was constant basically, obtaining limiting viscosity was that 0.09dL/g, acid number are that 71.38mgKOH/g, hydroxyl value are the PEA-7 performed polymer of 0mgKOH/g.
100 parts of PEA-7 performed polymers of parts by weight with embodiment 7 preparations; Add 14 part 1; 4-phenyl-two (2-oxazoline) chainextender, and 0.1 part tindichloride catalyzer, under nitrogen protection in 200 ℃ of synthesis under normal pressure 1.5 hours; Oil pump decompression (pressure 5mmHg) reaction 3 hours, the biodegradable aliphatics of preparing limiting viscosity and be 0.44dL/g replaces polyesteramide.
Embodiment 8: with 100 parts of PEA-7 performed polymers of parts by weight of embodiment 7 preparations; Add 14 part 1; 4-phenyl-two (2-oxazoline) chainextender, and 0.05 part tindichloride catalyzer, under nitrogen protection in 200 ℃ of synthesis under normal pressure 1.5 hours; Oil pump decompression (pressure 5mmHg) reaction 3 hours, the biodegradable aliphatics of preparing limiting viscosity and be 0.48dL/g replaces polyesteramide.
Claims (5)
1. one kind prepares the method that biodegradable aliphatics replaces polyesteramide through the chain extension method, comprises through melt phase polycondensation preparation polyesteramide performed polymer alternately, uses the chainextender chain extension again, obtains the alternative polyesteramide, it is characterized in that, may further comprise the steps:
1) being raw material with diprotic acid and diamide glycol, is 1.00～1.30 ratio in diprotic acid and diamide glycol mol ratio, in the presence of catalyzer, carries out the normal pressure polycondensation earlier; Temperature of reaction is collected the water that generates and is arrived 60～80% of theoretical amount between 160～200 ℃, changes reliever again into; Respectively with water pump and oil pump decompression 3～4h; Until be reacted to acid number constant basically till, used vacuum tightness is below 10mmHg, acquired character viscosity has the alternately polyesteramide performed polymer of terminal hydroxy group and end carboxyl in below 0.20; Wherein, catalyst consumption is 0.005～0.3% of a total monomer weight;
2) with the polyesteramide performed polymer for preparing in the step 1); In the presence of catalyzer; With bisoxazoline mixed chain extender chain extension, the chain extension temperature was carried out under normal pressure 1-2 hour earlier between 160～220 ℃ with the two lactan of diacyl or carbonyl di-lactame; Under the decompression state of 1～5mmHg, reacted 1-4 hour again, prepare limiting viscosity biodegradable fatty between 0.30～0.59dL/g and replace polyesteramide; Wherein, in the polyesteramide performed polymer of 100 weight parts, the consumption of chainextender bisoxazoline is 0.9～16 part, and the consumption of the two lactan of chainextender diacyl is 0.05～5.9 part, and wherein, catalyst consumption is 0.005～0.3% of a total monomer weight.
Wherein, the diamide glycol described in the step 1) is for having the structure shown in the general formula (I):
R is-(CH in the formula
2)
n-, n=0～20 wherein;
The general formula of the aliphatic dibasic acid described in the step 1) is HOOC (CH
2)
nCOOH, n=0～10;
Step 1), 2) catalyzer described in is one or more mixing in Dibutyltin oxide, White tin oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate, titanium isopropylate or the tosic acid;
Step 2) the chainextender bisoxazoline described in comprises Zhi fat family Er Yuan oxazoline or the fragrant Er Yuan of the family oxazoline of Fang, and its general structure is shown in (II):
R is-(CH in the formula
2)
n-, wherein n=0～20 or be phenyl or pyridyl link to each other Yu the oxazoline ring through ortho position, a position or contraposition;
Step 2) the two lactan of the chainextender diacyl described in comprise two lactan of aliphatics diacyl or the two lactan of aromatic series diacyl, and general structure is shown in (III):
In the formula, m=3～12; R is-(CH
2)
n-, n=0～20 or phenyl ring link to each other with dicarbapentaborane through ortho position, a position or contraposition;
Carbonyl di-lactame, structure is shown in (IV):
M=3～12 wherein.
2. method according to claim 1 is characterized in that, the preferred N of diamide glycol described in the step 1); N '-two (2-hydroxyethyl) oxalamide, N; N '-two (2-hydroxyethyl) succinic diamide, N, N '-two (2-hydroxyethyl) glutaramide, N, N '-two (2-hydroxyethyl) adipamide, N; N '-two (2-hydroxyethyl) suberamide, N, one or more in N '-two (2-hydroxyethyl) the sebacoyl amine.
3. according to the said method of claim 1, it is characterized in that one or more in the preferred oxalic acid of the diprotic acid described in the step 1), Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid or the sebacic acid.
4. according to the said method of claim 1, it is characterized in that step 2) used Er Yuan oxazoline chainextender preferred 1; 4-phenyl-two (2-oxazoline), 1; 3-phenyl-two (2-oxazoline), 1,4-bisoxazoline butane, 1,2-bisoxazoline ethane or two (2-oxazolines).
5. method according to claim 1; It is characterized in that step 2) the used two preferred N of lactan chainextender of diacyl, the two hexanolactams of N '-succinyl, N; The two hexanolactams of N '-hexanedioyl, N; The two hexanolactams of N '-phosphinylidyne, N, the two hexanolactams of N '-isophthaloyl, N, the two hexanolactams of N '-paraphenylene terephthalamide.
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| CN2011100415631A Pending CN102643422A (en) | 2011-02-21 | 2011-02-21 | Preparation method for biodegradable aliphatic alternating polyester amide |
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| CN103881086A (en) * | 2012-12-22 | 2014-06-25 | 北京化工大学 | Biodegradable alternate polyesteramide preparation method |
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| CN104558564A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Chain extender, and preparation method and application of chain extender |
| CN111349233A (en) * | 2020-03-04 | 2020-06-30 | 东华大学 | Biodegradable alternating aliphatic polyester amide and preparation method thereof |
| US11578207B2 (en) | 2018-01-23 | 2023-02-14 | Solutia Inc. | Interlayers comprising polyesteramide compositions |
| CN116515290A (en) * | 2023-06-01 | 2023-08-01 | 安徽中纤新材料有限公司 | Antistatic glass fiber-PA double 6 composite material and preparation method thereof |
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| CN111349233B (en) * | 2020-03-04 | 2021-10-26 | 东华大学 | Biodegradable alternating aliphatic polyester amide and preparation method thereof |
| CN116515290A (en) * | 2023-06-01 | 2023-08-01 | 安徽中纤新材料有限公司 | Antistatic glass fiber-PA double 6 composite material and preparation method thereof |
| CN116515290B (en) * | 2023-06-01 | 2023-11-07 | 安徽中纤新材料有限公司 | Antistatic glass fiber-PA double 6 composite material and preparation method thereof |
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