CN102234373A - Method for preparing biodegradable polyesteramide through chain extension - Google Patents
Method for preparing biodegradable polyesteramide through chain extension Download PDFInfo
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- CN102234373A CN102234373A CN 201010162519 CN201010162519A CN102234373A CN 102234373 A CN102234373 A CN 102234373A CN 201010162519 CN201010162519 CN 201010162519 CN 201010162519 A CN201010162519 A CN 201010162519A CN 102234373 A CN102234373 A CN 102234373A
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Abstract
The invention discloses a method for preparing biodegradable polyesteramide through chain extension. The method comprises the following steps of: performing melt polycondensation on fatty dibasic acid, dihydric alcohol and diacid/diamine salt or nylon prepolymer; preparing a series of polyesteramide prepolymers simultaneously provided with terminal carboxyl group and terminal hydroxyl group by changing a ratio of the diacid to dihydric alcohol and the content of amide; and performing chain extension by using diacyl di-lactame and 2-oxazolin chain extenders to prepare the biodegradable polyesteramide with the intrinsic viscosity of 0.34-0.85dL/g. The method has the advantages of simple and convenient reaction, high controllability, high efficiency and time saving.
Description
Technical field
The present invention relates to a kind of is the preparation method of the polyesteramide of raw material with aliphatic dibasic acid, dibasic alcohol and two acid diamine salt or nylon performed polymer, relates in particular to a kind of polycondensation, chain extension two-step approach of adopting and prepares the method for limiting viscosity at the high molecular Biodegradable polyester amides of 0.34~0.85dL/g.
Background technology
Polyesteramide (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 energy is given in the existence of ester bond simultaneously again, and it is with a wide range of applications.
The patent DE of Bayer AG 4327024 (1995), WO 9928371 (1999), WO 9935179 (1999) have reported by hexanodioic acid, 1, the polyesteramide of 4-butyleneglycol, hexanolactam or nylon-66 reactant salt synthesizing biological degradable, this product has favorable mechanical performance and biodegradability, and be that trade mark has been produced a series of this type of polyesteramides with BAK, but used preparation method is direct melt-polycondensation, very high to the vacuum tightness requirement, vacuum tightness needs below 0.5mmHg.
Eur Polymer J, 30,1277 (1994) have reported by hexylene glycol, hexanediamine and hexanodioic acid melt phase polycondensation, by changing the ratio of dibasic alcohol and diamine, obtain a series of performance differences, the different polyester-amide copolymer of degradation speed.But with diamine and diacid, glycol polycondensation, under the reaction conditions of condition of high vacuum degree, cause monomer volatilization loss easily, influenced feed ratio, therefore be difficult to obtain high molecular weight polymers.
(synthetic resins and plastics such as domestic Liu's filial piety ripple, 2003,20 (6), 10) with oxyacetic acid and 1,12-12 diamines are raw material preparation diamide two alcohol intermediates earlier, again with the sebacic acid molten polycondensation,, a series of molecular weight, crystallinity, polyesteramide that thermal characteristics is different have been prepared by changing the monomeric charge ratio.But also synthetic by direct polycondensation method, exigent vacuum tightness is to the requirement height of equipment.
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 characteristics and mechanical property obviously do not improve.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of to vacuum tightness and equipment requirements chain extension method high, pollution-free, not easy and simple to handle, with aliphatic dibasic acid, dibasic alcohol and two acid diamine salt or nylon performed polymer is raw material, prepares Biodegradable polyester amides.
The method of preparing biodegradable polyesteramide through chain extension of the present invention; adopt aliphatic dibasic acid, dibasic alcohol and two acid diamine salt or nylon performed polymer to carry out melt phase polycondensation; by changing the diprotic acid and the ratio of dibasic alcohol, the content of acid amides; a series of polyesteramide prepolymers that have end carboxyl and terminal hydroxy group structure have simultaneously been prepared; again with the two lactan of diacyl with the bisoxazoline chainextender carries out chain extension; the Biodegradable polyester amides of preparation limiting viscosity between 0.34~0.85dL/g, concrete steps are as follows:
1) with two acid diamine salt or nylon performed polymer, aliphatic dibasic acid and dibasic alcohol are according to amide content molar fraction 5%~65% in the final polyesteramide, diacid and glycol mol ratio 1.3: 1~1: 1.3, in the presence of catalyzer, in the nitrogen atmosphere, 160~220 ℃ of following synthesis under normal pressure, collect the water that generates and arrive 60~80% of theoretical amount, change reliever again into, progressively reduce pressure with water pump earlier and react 3~4h, it is below the 6mmHg that continuation makes vacuum tightness with the oil pump decompression, reaction 3~4h, till acid number is constant substantially, obtain the polyesteramide prepolymer, wherein, catalyst consumption is 0.005~0.3% of a total monomer weight;
2) with the polyesteramide prepolymer and chainextender bisoxazoline and the two lactan of diacyl that prepare in the step 1), in 180~220 ℃, under protection of nitrogen gas and the normal pressure reaction 1h after, reacted 1~3 hour down in 1~5mmHg again, obtain the Biodegradable polyester amides that limiting viscosity is 0.34~0.85dL/g; Wherein, the consumption of chainextender bisoxazoline is 0.9~10.8% of a polyesteramide prepolymer weight, and the consumption of the two lactan of chainextender diacyl is 0~7.5% of a polyesteramide prepolymer weight.
Wherein, two acid diamine salt described in the step 1) are for having one or more the mixing in the two acid diamine salt shown in the general structure (I):
H
3N
+-R
1-NH
3 +-OOC-R
2-COO
-
(I)
In the following formula: R
1, R
2For-(CH
2)
n-, n=2-12, one or more the mixture that has in nylon salt, decamethylene diammonium adipate, sebacic hexanediamine salt, the sebacic acid decamethylene diamine salt etc. commonly used.
Nylon performed polymer described in the step 1), for having the structure shown in the general formula (II):
In the following formula: R
1, R
2For-(CH
2)
n-, n=2-12; R
3=H, CH
3, C
2H
5, can prepare according to routine techniques, the nylon performed polymer described in the step 1) is nylon-66 performed polymer, nylon-610 performed polymer, nylon-1010 performed polymer etc., end group is carboxyl or ester group.
It is HO (CH that aliphatic dihydroxy alcohol described in the step 1) is selected from general formula
2)
nOH, n=2~6, commonly used have ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1, one or more in 6-hexylene glycol or the glycol ether etc.
The general formula of the diprotic acid described in the step 1) is HOOC (CH
2)
nCOOH, n=0~10, one or more that commonly used is in oxalic acid, Succinic Acid, hexanodioic acid, the sebacic acid etc.
Catalyzer described in the step 1) is one or more mixing in Dibutyltin oxide, stannic oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate or the titanium isopropylate, and preferable amount is 0.005~0.3% of a total monomer weight.
Amide content in the step 1) (molar fraction) is 5%~65%, diprotic acid/dibasic alcohol is 1: 1.3~1.3: 1 (mol than).
The polycondensation temperature is between 160~220 ℃ in the step 1), and temperature is crossed low reaction speed and descended; Too high then prepolymer color burn, side reaction increases.
Step 2) the chainextender bisoxazoline described in is the fragrant Er Yuan of the family oxazoline of Zhi fat family Er Yuan oxazoline or Fang, and general structure is shown in (III):
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 by ortho position, a position or contraposition; The Er Yuan of Zhi fat family oxazoline commonly used has two (2-oxazoline), 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 etc.; The fragrant Er Yuan of the family oxazoline of Fang commonly used comprises 1,2-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) or 3,4-pyridyl-two (2-oxazoline); Wherein, preferred 1,4-phenyl-two (2-oxazoline), 1,4-two (2-oxazoline) butane, 1,2-two (2-oxazoline) ethane or two (2-oxazolines).
Step 2) the two lactan of the chainextender diacyl described in are two lactan of aliphatics diacyl or the two lactan of aromatic series diacyl, and general structure is shown in (IV):
In the formula, m=3~12; R is-(CH
2)
n-, n=0~20 or phenyl ring link to each other 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, the two hexanolactams of N '-hexanedioyl, 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, two hexanolactams of N '-sebacoyl or N, the two laurolactams of N '-sebacoyl; Preferred 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; Preferred N, two hexanolactams of N '-isophthaloyl and N, the two hexanolactams of N '-paraphenylene terephthalamide.
Step 2) consumption of chainextender bisoxazoline is 0.9~10.8% of a polyesteramide prepolymer weight in, and the consumption of the two lactan of chainextender diacyl is 0~7.5% 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.
Step 2) chain extending reaction carries out between 180~220 ℃ in, and the chain extending reaction temperature is low, and the activity of chainextender is lower, and chain extending reaction is slow, weak effect; Temperature is too high, and thermolysis, thermooxidizing etc. take place polymkeric substance easily, and the chain extension effect is relatively poor, and the product color is darker.Suitable chain extension temperature is between 180~220 ℃.
Effect of the present invention:
The present invention is by dibasic alcohol, diprotic acid and two acid diamine salt or the synthetic polyesteramide prepolymer that has end carboxyl and terminal hydroxy group structure simultaneously of nylon performed polymer polycondensation; utilize the two lactan reactions of its terminal hydroxy group and diacyl afterwards, utilize end carboxyl and the reaction of Er Yuan oxazoline; realize the chain extension of prepolymer, obtain high-molecular weight Biodegradable polyester acid amides.The reaction of the two lactan of the terminal hydroxy group of prepolymer and diacyl is expressed as follows:
The hexanolactam that forms distils in vacuum system and removes.
Hold carboxyl Yu the reaction of bisoxazoline can be expressed as follows:
The final polyester amide structure that forms is as follows:
n=0-12;m=2-12;x=35~95mol%;y=5~65mol%。R
1, R
2For-(CH
2)
n-, n=2-12 wherein, chainextender shared ratio in structure is very low, can not consider its influence.
Amide content (molar fraction) surpasses 65%, and the biological degradability of polymkeric substance descends; Be lower than 5%, the character of polymkeric substance is near aliphatic polyester, and its improved performance is not obvious.
1) the prepared prepolymer of the present invention, the preparation of prepolymer that is entirely terminal hydroxy group or end carboxyl with two ends is compared, and react easy, easy to control, efficiently, save time.
2) amount ranges of diprotic acid, dibasic alcohol changes the amount ratio of the two than broad in the reaction of preparation prepolymer, can obtain to have the prepolymer of different terminal hydroxy group and content of carboxyl end group; Regulate the amount ratio of raw material, can make the polyesteramide of different amido linkages and ester bond content.
3) chain extending reaction mild condition of the present invention, temperature low (being less than or equal to 220 ℃), side reaction are few; speed of response is fast, efficient; by bisoxazoline and the two lactan chainextender couplings of diacyl; the end carboxyl and the terminal hydroxy group of polyesteramide prepolymer are fully reacted; chain extension is effective, and the polyesteramide limiting viscosity of preparation can reach 0.85dL/g.
The invention will be further described below in conjunction with embodiment.
Embodiment
When embodiment 1~10 measured polymer property viscosity, solvent was a dimethyl sulfoxide (DMSO); When embodiment 11~13 measures the polymer property viscosity, solvent be between-cresols.
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 example.
Embodiment 1
1) preparation of polyesteramide prepolymer (PEA): take by weighing 20 portions of nylon-66 salt with parts by weight; 23.0 part hexanodioic acid; 13.5 part 1; the 4-butyleneglycol; 0.16 part tin protochloride and 0.06 part of phosphorous acid; under nitrogen protection; be warmed up to 200 ℃ gradually from 160 ℃ and carry out polycondensation; collect to generate the water yield 70~80% after; use reliever instead; progressively reduce pressure with water pump earlier and react 3~4h; reduce pressure with oil pump again; make pressure reduce to 6mmHg; continue reaction 3~4h 190~210 ℃ of temperature ranges, obtaining limiting viscosity is 0.14dL/g; acid number is 29.4mgKOH/g; hydroxyl value is the PEA prepolymer of 3.6mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1; 2.8 parts of 4-phenyl-two (2-oxazoline), N; 0.55 part of the two hexanolactam of N '-hexanedioyl; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1 hour; 5mmHg depressurized system internal reaction 1 hour, the limiting viscosity of resulting polymers was 0.71dL/g then.
Embodiment 2
1) preparation of polyesteramide prepolymer (PEA): take by weighing 12.9 portions of nylon-66 salt, 23.0 parts of hexanodioic acids, 13.5 part 1 with parts by weight, 4-butyleneglycol, 0.15 part of tin protochloride and 0.05 part of phosphorous acid, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.09dL/g, and acid number is that 35.4mgKOH/g, hydroxyl value are the PEA prepolymer of 10.1mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1; 3.4 parts of 4-phenyl-two (2-oxazoline), N; 1.5 parts of the two hexanolactams of N '-hexanedioyl; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1.5 hours; 4mmHg depressurized system internal reaction 1.5 hours, the limiting viscosity of resulting polymers was 0.37dL/g then.
Embodiment 3
1) preparation of polyesteramide prepolymer (PEA): take by weighing 7.5 portions of nylon-66 salt, 23.0 parts of hexanodioic acids, 13.5 part 1 with parts by weight, 4-butyleneglycol, 0.13 part of tin protochloride and 0.04 part of phosphorous acid, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.13dL/g, and acid number is that 32.9mgKOH/g, hydroxyl value are the PEA prepolymer of 2.4mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1; 3.2 parts of 4-phenyl-two (2-oxazoline), N; 0.36 part of the two hexanolactam of N '-hexanedioyl; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1.5 hours; 6mmHg depressurized system internal reaction 1.5 hours, the limiting viscosity of resulting polymers was 0.40dL/g then.
Embodiment 4
1) preparation of polyesteramide prepolymer (PEA): take by weighing 3.3 portions of nylon-66 salt, 23.0 parts of hexanodioic acids, 13.5 part 1 with parts by weight, 4-butyleneglycol, 0.12 part of tin protochloride and 0.04 part of phosphorous acid, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.10dL/g, and acid number is that 30.0mgKOH/g, hydroxyl value are the PEA prepolymer of 2.3mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1; 2.9 parts of 4-phenyl-two (2-oxazoline), N; 0.35 part of the two hexanolactam of N '-hexanedioyl; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1.5 hours; 2mmHg depressurized system internal reaction 1.5 hours, the limiting viscosity of resulting polymers was 0.41dL/g then.
Embodiment 5
1) preparation of polyesteramide prepolymer (PEA): take by weighing 20 portions of nylon-66 salt, 24.1 parts of hexanodioic acids, 13.5 part 1 with parts by weight, 4-butyleneglycol, 0.17 part of tin protochloride and 0.06 part of phosphorous acid, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.15dL/g, and acid number is that 41.2mgKOH/g, hydroxyl value are the PEA prepolymer of 7.5mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1; 4.0 parts of 4-phenyl-two (2-oxazoline), N; 1.1 parts of the two hexanolactams of N '-hexanedioyl; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1.5 hours; 2mmHg depressurized system internal reaction 1.5 hours, the limiting viscosity of resulting polymers was 0.45dL/g then.
Embodiment 6
1) preparation of polyesteramide prepolymer (PEA): take by weighing 20 portions of nylon-66 salt, 21.9 parts of hexanodioic acids, 13.5 part 1 with parts by weight, 4-butyleneglycol, 0.17 part of tin protochloride and 0.06 part of phosphorous acid, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.23dL/g, and acid number is that 19.9mgKOH/g, hydroxyl value are the PEA prepolymer of 4.3mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1; 1.9 parts of 4-phenyl-two (2-oxazoline), N; 0.67 part of the two hexanolactam of N '-hexanedioyl; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1 hour; 2mmHg depressurized system internal reaction 1 hour, the limiting viscosity of resulting polymers was 0.50dL/g then.
Embodiment 7
1) preparation of polyesteramide prepolymer (PEA): take by weighing 20 portions of nylon-66 salt, 23.0 parts of hexanodioic acids, 14.2 part 1 with parts by weight, 4-butyleneglycol, 0.17 part of tin protochloride and 0.06 part of phosphorous acid, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.18dL/g, and acid number is that 20.1mgKOH/g, hydroxyl value are the PEA prepolymer of 21.4mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1; 1.9 parts of 4-phenyl-two (2-oxazoline), N; 3.2 parts of the two hexanolactams of N '-hexanedioyl; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1 hour; 3mmHg depressurized system internal reaction 1 hour, the limiting viscosity of resulting polymers was 0.52dL/g then.
Embodiment 8
1) preparation of polyesteramide prepolymer (PEA): reactant consumption, other condition and embodiment 2 step 1) are identical, and composite character viscosity is 0.12dL/g, and acid number is that 34.3mgKOH/g, hydroxyl value are the PEA prepolymer of 3.1mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1; 3.3 parts of 4-phenyl-two (2-oxazoline), N; 0.47 part of the two hexanolactam of N '-hexanedioyl; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1 hour; 4mmHg depressurized system internal reaction 1 hour, the limiting viscosity of resulting polymers was 0.40dL/g then.
Embodiment 9
Take by weighing 50 parts of the PEA prepolymers of the preparation of step 1) among the embodiment 8 with parts by weight; 1; 3.6 parts of 4-phenyl-two (2-oxazoline), N; 0.47 part of the two hexanolactam of N '-paraphenylene terephthalamide; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1 hour; 4mmHg depressurized system internal reaction 1 hour, the limiting viscosity of resulting polymers was 0.41dL/g then.
Embodiment 10
Take by weighing 50 parts of the PEA prepolymers of the preparation of step 1) among the embodiment 8 with parts by weight; 1; 3.3 parts of 4-phenyl-two (2-oxazoline), N; 0.47 part of the two hexanolactam of N '-paraphenylene terephthalamide; under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1.5 hours; 4mmHg depressurized system internal reaction 1.5 hours, the limiting viscosity of resulting polymers was 0.43dL/g then.
Embodiment 11
1) preparation of nylon performed polymer: take by weighing 100 portions of nylon-610 salt, 31.8 parts of sebacic acid, 0.40 part of phosphorous acid with parts by weight; under nitrogen protection; be warmed up to 200 ℃ gradually from 160 ℃ and carry out polycondensation; reaction times is 4h, and synthetic acid number is that 111.0mgKOH/g, hydroxyl value are the NYLON610 performed polymer of 0mgKOH/g.
2) preparation of polyesteramide prepolymer (PEA): 50 parts, 12.7 parts hexanodioic acids of NYLON610 performed polymer, 13.4 part 1 of taking by weighing step 1) preparation with parts by weight, 4-butyleneglycol, 0.23 part of tin protochloride, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.39dL/g, and acid number is that 29.4mgKOH/g, hydroxyl value are the PEA prepolymer of 0mgKOH/g.
3) take by weighing step 2 with parts by weight) 50 parts of the PEA prepolymers of preparation; 1,2.8 parts of 4-phenyl-two (2-oxazoline), under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 0.5 hour; at 1mmHg depressurized system internal reaction 10min, the limiting viscosity of resulting polymers is 0.85dL/g then.
Embodiment 12
1) preparation of nylon performed polymer: reactant consumption, other condition and embodiment 11 step 1) are identical, and synthetic acid number is that 120.0mgKOH/g, hydroxyl value are the NYLON610 prepolymer of 4.7mgKOH/g.
2) preparation of polyesteramide prepolymer (PEA): 50 parts, 53.2 parts hexanodioic acids of NYLON610 performed polymer, 40.2 part 1 of taking by weighing step 1) preparation with parts by weight, 4-butyleneglycol, 0.43 part of tin protochloride, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.33dL/g, and acid number is that 17.6mgKOH/g, hydroxyl value are the PEA prepolymer of 1mgKOH/g.
3) take by weighing step 2 with parts by weight) 50 parts of the PEA prepolymers of preparation; 1; 1.7 parts of 4-phenyl-two (2-oxazoline); N; 0.15 part of the two hexanolactam of N '-hexanedioyl; in 200 ℃ of synthesis under normal pressure 1.5 hours, at 1mmHg depressurized system internal reaction 1.5min, the limiting viscosity of resulting polymers was 0.51dL/g then under protection of nitrogen gas.
Embodiment 13
1) preparation of polyesteramide prepolymer (PEA): 50 parts, 1.4 parts hexanodioic acids of NYLON610 performed polymer, 6.7 part 1 of taking by weighing embodiment 11 step 1) preparations with parts by weight, 4-butyleneglycol, 0.17 part of tin protochloride, other conditions and embodiment 1 step 1) are identical, composite character viscosity is 0.31dL/g, and acid number is that 20.4mgKOH/g, hydroxyl value are the PEA prepolymer of 0mgKOH/g.
2) take by weighing 50 parts of the PEA prepolymers of step 1) preparation with parts by weight; 1,2.0 parts of 4-phenyl-two (2-oxazoline), under protection of nitrogen gas in 200 ℃ of synthesis under normal pressure 1.5 hours; at 1mmHg depressurized system internal reaction 1.5min, the limiting viscosity of resulting polymers is 0.66dL/g then.
Claims (6)
1. the method for preparing biodegradable polyesteramide through chain extension of the present invention is characterized in that, the Biodegradable polyester amides of preparation limiting viscosity between 0.34~0.85dL/g, and concrete steps are as follows:
1) with two acid diamine salt or nylon performed polymer, aliphatic dibasic acid and dibasic alcohol are according to amide content molar fraction 5%~65% in the final polyesteramide, diacid and glycol mol ratio 1.3: 1~1: 1.3, in the presence of catalyzer, in the nitrogen atmosphere, 160~220 ℃ of following synthesis under normal pressure, collect the water that generates and arrive 60~80% of theoretical amount, change reliever again into, progressively reduce pressure with water pump earlier and react 3~4h, it is below the 6mmHg that continuation makes vacuum tightness with the oil pump decompression, reaction 3~4h, till acid number is constant substantially, obtain the polyesteramide prepolymer, wherein, catalyst consumption is 0.005~0.3% of a total monomer weight;
2) with the polyesteramide prepolymer and chainextender bisoxazoline and the two lactan of diacyl that prepare in the step 1), in 180~220 ℃, under protection of nitrogen gas and the normal pressure reaction 1h after, reacted 1~3 hour down in 1~5mmHg again, obtain the Biodegradable polyester amides that limiting viscosity is 0.34~0.85dL/g; Wherein, the consumption of chainextender bisoxazoline is 0.9~10.8% of a polyesteramide prepolymer weight, and the consumption of the two lactan of chainextender diacyl is 0~7.5% of a polyesteramide prepolymer weight;
Wherein, two acid diamine salt described in the step 1) are for having one or more the mixing in the two acid diamine salt shown in the general structure (I):
H
3N
+-R
1-NH
3 +-OOC-R
2-COO
-
(I)
In the following formula: R
1, R
2For-(CH
2)
n-, n=2-12;
Nylon performed polymer described in the step 1), for having the structure shown in the general formula (II):
In the following formula: R
1, R
2For-(CH
2)
n-, n=2-12; R
3=H, CH
3, C
2H
5
It is HO (CH that aliphatic dihydroxy alcohol described in the step 1) is selected from general formula
2)
nOH, n=2~6;
The general formula of the diprotic acid described in the step 1) is HOOC (CH
2)
nCOOH, n=0~10;
Catalyzer described in the step 1) is one or more mixing in Dibutyltin oxide, stannic oxide, tin protochloride, zinc oxide, zinc acetate, tetrabutyl titanate or the titanium isopropylate;
Step 2) the chainextender bisoxazoline described in is the fragrant Er Yuan of the family oxazoline of Zhi fat family Er Yuan oxazoline or Fang, general structure shown in (III),
R is-(CH in the formula
2)
n-, n=0~20, or phenyl or pyridyl link to each other Yu the oxazoline ring by ortho position, a position or contraposition;
Step 2) the two lactan of the chainextender diacyl described in are two lactan of aliphatics diacyl or the two lactan of aromatic series diacyl, and general structure is shown in (IV):
In the formula, m=3~12; R is-(CH
2)
n-, n=0~20, or phenyl ring link to each other with dicarbapentaborane by ortho position, a position or contraposition.
2. according to the preparation method of claim 1, it is characterized in that the nylon performed polymer described in the step 1) is nylon-66 performed polymer, nylon-610 performed polymer, nylon-1010 performed polymer, end group is carboxyl or ester group.
3. according to the preparation method of claim 1, it is characterized in that the dibasic alcohol described in the step 1) is an ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1, one or more in 6-hexylene glycol or the glycol ether etc.
4. according to the preparation method of claim 1, it is characterized in that the diprotic acid described in the step 1) is one or more in oxalic acid, Succinic Acid, hexanodioic acid, the sebacic acid etc.
5. according to the preparation method of claim 1, it is characterized in that, step 2) the chainextender bisoxazoline described in is that Er Yuan oxazoline has two (2-oxazoline), 1,2-two (2-oxazoline) ethane, 1,4-two (2-oxazoline) butane, 1,4-phenyl-two (2-oxazoline), 1,3-phenyl-two (2-oxazoline).
6. the two lactan of the chainextender diacyl step 2) are N, the two hexanolactams of N '-succinyl, N, the two hexanolactams of N '-hexanedioyl, N, two hexanolactams of N '-isophthaloyl or N, the two hexanolactams of N '-paraphenylene terephthalamide.
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