CN1243037C - Biodegradable triblock polyamide ester and its preparation method - Google Patents
Biodegradable triblock polyamide ester and its preparation method Download PDFInfo
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- CN1243037C CN1243037C CN 03156603 CN03156603A CN1243037C CN 1243037 C CN1243037 C CN 1243037C CN 03156603 CN03156603 CN 03156603 CN 03156603 A CN03156603 A CN 03156603A CN 1243037 C CN1243037 C CN 1243037C
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Abstract
The present invention relates to biodegradable triblock polyesteramide and a preparation method thereof. The formula of the biodegradable triblock polyesteramide contains 30 to 70 parts of dibasic acid, 10 to 70 parts of diamine, 10 to 50 parts of dibasic alcohol, 5 to 70 parts of amide, 0 to 10 parts of branching agent, 0 to 5 parts of antioxidant and 0 to 50 ppm of catalyst. The polymerization and condensation reaction of reaction is carried out under the protection of nitrogen. Reaction temperature is from 140 to 270 DEG C. Vacuum polymerization and condensation reaction is carried out for 4 to 6 hours at the reaction temperature, and the biodegradable triblock polyesteramide can be obtained. The melting point of the biodegradable triblock polyesteramide is from 125 to 135 DEG C. The tensile strength of the biodegradable triblock polyesteramide is from 19 to 28MPa. The breaking elongation of the biodegradable triblock polyesteramide is from 80 to 300%. The biodegradable triblock polyesteramide can be completely degraded under the conditions that pH is equal to 12 and temperature is 80 DEG C. The biodegradable triblock polyesteramide has the following structural formula: [-OC(CH2)4COO(CH2)4O-]m [-OC(CH2)4COHN(CH2)6NH-]n [-OC(CH2)6NH)]p, wherein m is from 30 to 725; n is from 30 to 1160; p is form 10 to 725.
Description
Technical field
The invention belongs to the synthetic field of macromolecular material, relate to a kind of biodegradable three block polyesteramides and preparation method thereof, its product is mainly used in environment-friendly materials and biomedical material.
Background technology
At using polymer magazine (J.Appl.Polym.Sci) 20, the preparation of 975 (1976) the amino-terminated polycaprolactones that disclose and with polyethylene terephthalate (PET) melting state transesterification reaction, obtain the polyesteramide that amido linkage distributes, but this material can not be applied to the material field of biodegradable and environment degradable.
Disclose in the following prior art by hydroxyethanoic acid and aliphatic diamine reaction synthesizing amide dibasic alcohol:
1, biological chemistry (Biological chemistry), PP513-521, E.H.Cordes, ed, Harper ， ﹠amp; Row, NewYork (1966);
2, pharmaceutically acceptable polymer (Polymer in Medicine) 11PP80-85, Echiellini ed, plenumpress, New York (1986);
3, the short life source magazine (E.J.Bioeng) 1,23 (1977) of yeast;
4, biomaterial magazine (J.Biomed.Mater.Res) 16,117 (1982);
5, (Trans, SocBiomater) 6,109 (1983) and 7,210 (1984);
6、(Trans.Fourch?World?Biomaterials?Congress)15，249，408(1922)；
7, (J.Biochim.Biophys) Acta1042,182 (ugly 990);
8, United States Patent (USP) 4,343, and exposure such as 931 (1982) and 4,529,735 (1985) studys biodegradable and problem Bioabsorbable by hydroxyethanoic acid and aliphatic diamine reaction synthesizing amide dibasic alcohol;
But the derivative by research acid amides dibasic alcohol and binary acid prepares biodegradable and polyesteramide bio-absorbable, characterize in detail its structure and performance, and preparation can be used for the medical surgical operating sutures and is applied to biodegradable artificial bone fracture internal fixing device system.Its major defect is:
Because the polyesteramide of these structures is hemicrystalline high molecular polymers, biodegradation rate is difficult to regulate and control, so that bring other side effect, and the higher reason of cost also makes this base polymer can't be widely used in environment protection material field.
The Chemicals (Journal of chemistry) 72,867 (1972) discloses the polyesteramide that a kind of L one lactic acid chain connects, and its major defect is:
Because monomer is synthetic comparatively complicated, polymkeric substance shows as the multipolymer of L one lactic acid and poly-L one lactic acid acid amides;
Chinese invention patent 9812899.7 discloses a kind of polyesteramide multipolymer that contains SL one lactic acid, but these polyesteramides is synthetic all comparatively complicated, and be difficult to overcome the generation of side reaction such as transesterify, cause these polymkeric substance or multipolymer darker colour-change to occur;
In addition, Kuhs tstoffee 85 (8), 161 (1996) and United States Patent (USP) 5,644,020 disclose a class diblock polyesteramide fusing point at 125 ℃, its mechanical property and polyethylene are suitable, and in the presence of moisture and soil ulmin, biological degradation fast can take place.
Pofymer, 39 (2), 459 (998) poly adipate succinic acid ester and the hexanodioic acids that disclose a kind of carboxy blocking are raw material, with tetramethylene sulfone is solvent, 200 ℃ with 1.6 di-isocyanates reactions, prepare the polyesteramide elastomerics, but such polyesteramide can not biological degradation;
Chinese invention patent 99115200.X, 00112700.4 and 00112699.7), disclose the preparation method of plasticity biodegradable polyamidoester and multipolymer respectively, all can realize degraded at acid-base condition and coenocorrelation, but in the preparation of these polyesteramides, all use virose diisocyanate resin compound, have it restricted the application scope.
Summary of the invention
The purpose of this invention is to provide a kind of biodegradable three block polyesteramides and preparation method thereof, be characterized in: with diprotic acid, dibasic alcohol, tetravalent alcohol, amides, diamine and tetraprotic acid is raw material, under the organotin catalysis with antioxidant action under, through the body melt polymerization, form biodegradable three block polyesteramides, reach and to adjust the structure of product and the purpose of performance significantly.
The object of the present invention is achieved like this: a kind of biodegradable three block polyesteramides, it is characterized in that: it is to be raw material with diprotic acid, dibasic alcohol, diamine, acid amides, branching agent, antioxidant and catalyzer, through the body melt polymerization, form biodegradable three block polyesteramides, its structural formula is:
[-OC(CH
2)
4COO(CH
2)
4O-]
m[-OC(CH
2)
4COHN(CH
2)
6NH-]
n[-OC(CH
2)
6NH]
p
Wherein m is 30-725; N is 30-1160; P is 10-725.
The present invention also provides a kind of preparation method of biodegradable three block polyesteramides, and it is characterized in that: it comprises the steps:
(1) select materials: the composition of raw materials component is counted with parts by weight:
Diprotic acid 30-70 part, diamine 10-70 part, dibasic alcohol 10-50 part, acid amides 5-70 part, branching agent 0-10 part, antioxidant 0-5 part and catalyzer 0-50ppm.
(2) diprotic acid 30-70 part of described raw material and diamine 10-70 part are joined successively have agitator, in the reactor of thermometer, dropper, reflux exchanger and shielding gas inlet and outlet device, at first nitrogen is imported, and be warmed up to 140-160 ℃, back flow reaction 3 hours;
(3) add di-alcohols 10-50 part, amides 5-70 part, branching agent 0-10 part, antioxidant 0-5 part and catalyzer 0-50ppm, and slowly be warming up to 240-300 ℃ and carry out polyreaction, vacuumized 4 to 6 hours;
(4) discharging again, cooling, pulverizing afterwards obtains biodegradable polyamidoester, under 80 ℃ of vacuum drying ovens, and dry 48 hours, obtain biodegradable three block polyesteramides, its structural formula is as follows:
[-OC(CH
2)
4COO(CH
2)
4O-]
m[-OC(CH
2)
4COHN(CH
2)
6NH-]
n[-OC(CH
2)
6NH]
p
Wherein m is 30-725; N is 30-1160; P is 10-725.
This diprotic acid is that carbon content is C in the alkyl
2-C
6Diprotic acid.This diamine is that carbon content is C in the alkyl
2-C
6Diamine.This dibasic alcohol is that carbon content is C in the alkyl
2-C
6Dibasic alcohol.This acid amides is that carbon content is C in the alkyl
2-C
8Acid amides.This branching agent is that carbon content is C in the alkyl
1-C
10Tetravalent alcohol, quaternary amine, tetraprotic acid or quaternary acid amides at least a.This antioxidant is an aromatics.This diprotic acid is 1,6 hexanodioic acid.This diamine is 1,6 hexanediamine.This dibasic alcohol is 1,4 butyleneglycol.This acid amides is a hexanolactam.This branching agent is at least a in tetramethylolmethane or the tetraacethyl ethene.This catalyzer is a dibutyl tin laurate.This antioxidant is a triphenyl.
The present invention has following advantage:
1, in the macromolecular structure, main chain is introduced amido linkage, and the wetting ability of polyesteramide and multipolymer thereof is greatly improved, and melt temperature rises, and its processibility, dyeability and hydrolytic deterioration all can be improved.
2, in polymkeric substance, form two kinds of special acid amides links by amides and diamine, make the performance of polyesteramide have protection largely, and be different from prior art, develop another three brand-new block polyesteramides.
3, by adjusting proportion of raw materials, can be in the structure and the performance of inner control polyesteramide product in a big way.
4, raw material sources are abundant, cost is low and product price is lower than biodegradable poly(lactic acid), and polycaprolactone owing to have preferable performance and lower price, is easy to apply, and has remarkable economic efficiency and social benefit.
Further specify below in conjunction with preferred embodiment.
Embodiment
The polyesteramide of biodegradable three blocks of the present invention, it can adopt following monomer is raw material:
1, binary acids: can form the diprotic acid of ester class formation as Succinic Acid (Succinic acid), hexanodioic acid (adipic acid) etc., wherein that best is alkyl carbon content C
2-C
6The binary acids.
2, binary amine: as hexanediamine, butanediamine etc., wherein Zui Jia binary amine is that the alkyl carbon content is C
2-C
6Diamine.
3, alcamines: as compounds such as thanomin or butanolamines.
4, di-alcohols: as ethylene glycol (ethylene glycol), 1,4 butyleneglycol, 1,6 hexylene glycol etc., wherein best is that the alkyl carbon content is C
2-C
6The dibasic alcohol of x.
5, amino acids: as hexosamine (aminocaproic acid) etc.
6, amides: as hexanolactam etc.
7, polyester oligomers: molecular weight is at 200-10, and between 000, terminal group is a hydroxyl.
8, branching agent: be trivalent alcohol or tetravalent alcohol, also or triprotic acid or tetraprotic acid, help rerum natura to improve though add branching agent, biological degradability also can be impaired.
9, catalyzer: catalyzer can be tin-containing catalyst or an acidic catalyst, or even Mg, and the oxide compound of Zn or Ca will help the carrying out that reacts.
10, auxiliary agent: polyesteramide can add suitable adjuvants, to reach the expectation purpose in synthetic or the course of processing, this analog assistant is as antioxidant, organic or inorganic strengthening agent, UV stablizer, pigment or dyestuff, fireproofing agent or flame retardant etc., adding proportion is the 0-50 parts by weight.
The preparation method of biodegradable three block polyesteramides of the present invention is as follows: the composition of raw materials component is counted with parts by weight:
Binary acids 30-70 part, binary amine 10-70 part, di-alcohols 10-50 part, amides 5-70 part, quaternary alcohols 0-10 part, quaternary acids 0-10 part, antioxidant 0-5 part and catalyzer 0-50ppm.
But with above-mentioned thing degrade the used raw material binary acids of three block polyesteramides and binary amine join successively have agitator, in the reactor of thermometer, dropper, reflux exchanger and shielding gas inlet and outlet device, at first nitrogen is imported, and be warmed up to 140-160 ℃ of back flow reaction 3 hours;
Add di-alcohols 10-50 part, amides 5-70 part, quaternary alcohols 0-10 part, quaternary acids 0-10 part, antioxidant 0-5 part and catalyzer 0-50ppm, and slowly be warming up to 240 ℃, vacuumized 4 to 6 hours;
Discharging again, cooling, pulverizing afterwards obtains biodegradable polyamidoester, descends dry 48 hours 80 ℃ of vacuum drying ovens, obtains biodegradable three block polyesteramides, and its structural formula is as follows:
[-OC(CH
2)
4COO(CH
2)
4O-]
m[-OC(CH
2)
4COHN(CH
2)
6NH-]
n[-OC(CH
2)
6NH?]
p
Wherein m is 30-725; N is 30-1160; P is 10-725.
Below be concrete synthetic example of the present invention:
Example 1
With raw materials used hexanodioic acid 1040 grams of above-mentioned biodegradable three block polyesteramides, after the hexanediamine 410 gram weighings, join respectively have agitator, in the reactor of thermometer, dropper, reflux exchanger and shielding gas inlet and outlet device, feed nitrogen temperature to 140-160 ℃, back flow reaction 3 hours;
Weighing adds butyleneglycol 345 grams, caprolactam 100 grams, tetramethylolmethane 2 grams, triphenyl 0.2 gram respectively again, and dibutyl tin laurate 0.2 gram slowly is warmed up to 240 ℃ again, vacuumizes 4 to 6 hours, obtains biodegradable three block polyesteramides.
The tensile strength 28Mpa of injection standard sample, elongation at break 132%, modulus 498Mpa is can realize degrading fully under 12 and 80 ℃ the condition at PH.
Example 2
After raw material hexanodioic acid 1040 gram of above-mentioned biodegradable three block polyesteramides, hexanediamine 410 gram weighings, join respectively have agitator, in the reactor of thermometer, dropper, reflux exchanger and shielding gas inlet and outlet device, feed nitrogen and be warmed up to 140-160 ℃, back flow reaction 3 hours;
Weighing adds butyleneglycol 345 grams, hexanolactam 200 grams, tetramethylolmethane 2 grams, triphenyl 0.2 gram, dibutyl tin laurate 0.2 gram respectively again, slowly is warmed up to 240 ℃ again, vacuumizes 4 to 6 hours, obtains biodegradable three block polyesteramides.
The tensile strength 23Mpas of injection standard sample, elongation at break 118%, modulus 432Mpa is under 12 and 80 ℃ at PH, can realize degrading fully.
Example 3
With raw materials used adipic acid 1040 grams of above-mentioned biodegradable three block polyesteramides, hexanediamine 410 grams, add respectively after the weighing and have in the reactor of agitator, thermometer, dropper, reflux exchanger and shielding gas inlet and outlet device, feed nitrogen and also be warmed up to 140-160 ℃ of back flow reaction 3 hours;
Weighing adds butyleneglycol 345 grams, hexanolactam 350 grams, tetramethylolmethane 2 grams, dibutyl tin laurate 0.2 gram, triphenyl 0,2 grams respectively again, slowly be warmed up to 240 ℃, vacuumized 4 to 6 hours, and can obtain tool biological degradation three block polyesteramides.
The tensile strength 20Mpa of injection standard sample, elongation at break 298%, modulus 534Mpa is can realize degrading fully under 12 and 80 ℃ the condition at PH.
Example 4
Repeat the experiment of example 3, but branching agent changes by tetraacethyl ethene 0.2 gram and replace, other conditions are identical with example 3, so do not repeat, can obtain three block polyesteramides.
The tensile strength of injection standard sample is 24Mpa, and elongation at break is 228%, and modulus 443Mpa is can realize degrading fully under 12 and 80 ℃ the condition at PH.
Example 5
Repeat the experiment of example 3, but branching agent changes by tetramethylolmethane 0.1 gram and tetraacethyl ethene 0.1 gram and replace, other conditions are identical with example 3, so do not repeat, can obtain three block polyesteramides.
The tensile strength 25Mpa of injection standard sample, elongation at break 248%, modulus 468Mpa is can realize degrading fully under 12 and 80 ℃ the condition at PH.
Claims (15)
1, a kind of biodegradable three block polyesteramides, it is characterized in that: it is to be raw material with diprotic acid, dibasic alcohol, diamine, acid amides, branching agent, antioxidant and catalyzer, through the body melt polymerization, form biodegradable three block polyesteramides, its structural formula is:
[-OC(CH
2)
4COO(CH
2)
4O-]
m[-OC(CH
2)
4COHN(CH
2)
6NH-]
n[-OC(CH
2)
6NH]
p
Wherein m is 30-725; N is 30-1160; P is 10-725.
2, a kind of preparation method of biodegradable three block polyesteramides, it is characterized in that: it comprises the steps:
(1) select materials: the composition of raw materials component is counted with parts by weight:
Diprotic acid 30-70 part, diamine 10-70 part, dibasic alcohol 10-50 part, acid amides 5-70 part, branching agent 0-10 part, antioxidant 0-5 part and catalyzer 0-50ppm;
(2) diprotic acid 30-70 part of described raw material and diamine 10-70 part are joined successively have agitator, in the reactor of thermometer, dropper, reflux exchanger and shielding gas inlet and outlet device, at first nitrogen is imported, and be warmed up to 140-160 ℃, back flow reaction 3 hours;
(3) add dibasic alcohol 10-50 part, acid amides 5-70 part, branching agent 0-10 part, antioxidant 0-5 part and catalyzer 0-50ppm, and slowly be warming up to 240-300 ℃ and carry out polyreaction, vacuumized 4 to 6 hours;
(4) discharging again, cooling, pulverizing afterwards obtains biodegradable polyamidoester, descends dry 48 hours 80 ℃ of vacuum drying ovens, obtains biodegradable three block polyesteramides, and its structural formula is as follows:
[-OC(CH
2)
4COO(CH
2)
4O-]
m[-OC(CH
2)
4COHN(CH
2)
6NH-]
n[-OC(CH
2)
6NH]
p
Wherein m is 30-725; N is 30-1160; P is 10-725.
3, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this diprotic acid is that carbon content is C in the alkyl
2-C
6Diprotic acid.
4, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this diamine is that carbon content is C in the alkyl
2-C
6Diamine.
5, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this dibasic alcohol is that carbon content is C in the alkyl
2-C
6Dibasic alcohol.
6, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this acid amides is that carbon content is C in the alkyl
2-C
8Acid amides.
7, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this branching agent is that carbon content is C in the alkyl
1-C
10Tetravalent alcohol, quaternary amine, tetraprotic acid or quaternary acid amides at least a.
8, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this antioxidant is an aromatics.
9, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this diprotic acid is 1,6 hexanodioic acid.
10, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this diamine is 1,6 hexanediamine.
11, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this dibasic alcohol is 1,4 butyleneglycol.
12, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this acid amides is a hexanolactam.
13, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this branching agent is at least a in tetramethylolmethane or the tetraacethyl ethene.
14, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this catalyzer is a dibutyl tin laurate.
15, the preparation method of biodegradable three block polyesteramides according to claim 2 is characterized in that: this antioxidant is a triphenyl.
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|---|---|---|---|
| CN 03156603 CN1243037C (en) | 2003-09-05 | 2003-09-05 | Biodegradable triblock polyamide ester and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156603 CN1243037C (en) | 2003-09-05 | 2003-09-05 | Biodegradable triblock polyamide ester and its preparation method |
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|---|---|
| CN1590432A CN1590432A (en) | 2005-03-09 |
| CN1243037C true CN1243037C (en) | 2006-02-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479127B (en) * | 2014-12-12 | 2016-10-19 | 东华大学 | A kind of caprolactam hydrating polymer and hydrolytic polymerization method thereof |
| CN108102091A (en) * | 2016-11-25 | 2018-06-01 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable polyamide and preparation method thereof |
| CN114672017B (en) * | 2022-04-19 | 2023-02-21 | 西北大学 | Method for preparing aliphatic polyester amide from ethylene glycol |
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