CN100556642C - The regulate and control method of aliphatic poly adipic acid fourth diester material degradation performance - Google Patents
The regulate and control method of aliphatic poly adipic acid fourth diester material degradation performance Download PDFInfo
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- CN100556642C CN100556642C CNB2007101002273A CN200710100227A CN100556642C CN 100556642 C CN100556642 C CN 100556642C CN B2007101002273 A CNB2007101002273 A CN B2007101002273A CN 200710100227 A CN200710100227 A CN 200710100227A CN 100556642 C CN100556642 C CN 100556642C
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Abstract
The present invention relates to the regulate and control method of biodegradated polymer materal degradation property, particularly the regulate and control method of aliphatic poly adipic acid fourth diester (PBA) material degradation performance.Regulate the degradation rate of PBA sample by the relative amount of alpha-crystal and two kinds of crystal of β crystal among the control PBA.The invention discloses three kinds of approach that realize crystalline content control: the rate of temperature fall of the temperature of control isothermal crystal, control nonisothermal crystallization or by three kinds of methods of control annealing time.By changing the relative amount of the crystal of different structure in the PBA material, reached the purpose of regulation and control PBA material degradation speed.Method of the present invention provides a kind of new thinking and selection for the degradation property of regulation and control aliphatic polyester, and has that technology is simple, easy operating, is easy to the characteristics that realize aborning.
Description
Technical field
The present invention relates to the regulate and control method of biodegradated polymer materal degradation property, particularly the regulate and control method of aliphatic poly adipic acid fourth diester (PBA) material degradation performance.
Technical background
Because the characteristic that biodegradated polymer materal has excellent biological compatibility and can be decomposed by body fluid, enzyme and microorganism in human body, in soil and the seawater is so have important application prospects in medical science and environmental protection field.In order to satisfy in actual the use, must regulate and control the degradation rate of macromolecular material effectively according to the requirement of using to the diversified requirement of macromolecular material degradation property.
Current people mainly adopt two kinds of methods to regulate and control the degradation property of macromolecular material.A kind of is to regulate and control degradation property by the chemical constitution and the composition that change macromolecular material, aliphatic polyester such as the method preparation of adopting copolymerization, poly-(succinic acid fourth diester-co-adipic acid fourth diester) copolymer (PBSA), by regulating two kinds of components contents, reach the purpose of regulation and control degradation rate.But by changing chemical constitution and forming the method for regulating degradation rate, owing to the production technology and the reaction condition that relate to complexity, thereby this regulate and control method is comparatively complicated.
Another kind method is by changing the physical arrangement that processing conditions and heat-treat condition change macromolecular material, as degree of crystallinity, crystalline size etc., and the variation of these structures has very big influence to the macromolecule degradation property, thereby obtains having the macromolecular material of different degradation rates.This is a kind of method very easily, has obtained using widely.
Many aliphatic polyesters have polymorphism, but polycrystalline structure does not but cause people's attention to the influence of macromolecular material degradation property.Polymorphism is meant a certain specific macromolecule, owing to the difference of crystallization condition or heat-treat condition, has two or more crystal structure.We find under study for action, the sample degradation rate difference of different crystal forms.For example, poly-adipic acid fourth diester (PBA) has two kinds of crystal formations, and the β crystal is the metastable crystal formation of thermodynamics, can change thermodynamically stable alpha-crystal into after the The high temperature anneal, but alpha-crystal has than β crystal degradation rate (Gan, Z. faster; Kuwabara, K.; Abe, H.; Iwata, T.; Doi, Y.The role of polymorphic crystal structure and morphology inenzymatic degradation of melt-crystallized poly (butylene adipate) films.PolymDegrad Stab 2005; 87:191～9.).Therefore, we imagine, and for the aliphatic polyester with polycrystalline structure, regulate the content of various crystal formations by changing processing technology and heat-treat condition, are a kind of new approaches of regulation and control macromolecular material degradation property.
Summary of the invention
The regulate and control method that the purpose of this invention is to provide a kind of aliphatic polyester material degradation performance, the especially regulate and control method of aliphatic poly adipic acid fourth diester degradation property.On the basis that does not change the high polymer material chemical structure, come the degradation rate of controlled material by the relative amount of regulating the macromolecule polycrystalline, this method has overcome by the process complexity of chemical method regulation and control macromolecular material degradation rate and by changing the limitation of degree of crystallinity and crystalline size regulation and control degradation rate, enrich the physical method of regulation and control macromolecular material degradation property, enlarged the application of macromolecular material.
The regulate and control method of aliphatic poly adipic acid fourth diester material degradation performance of the present invention is by the temperature of the isothermal crystal of controlling poly-adipic acid fourth diester (PBA) or by the rate of temperature fall of control nonisothermal crystallization or by three kinds of methods of control annealing time, the relative amount of alpha-crystal and β crystal structure in poly-adipic acid fourth two ester materials of regulation and control, thereby the degradation rate of poly-adipic acid fourth two ester materials of regulation and control.
Temperature of gathering the isothermal crystal of adipic acid fourth diester by control of the present invention obtains having alpha-crystal and β crystal structure and the different polyester sample of relative amount, realizes that the regulate and control method of poly-adipic acid fourth diester material degradation performance is:
To gather adipic acid fourth diester 70～80 ℃ of abundant fusions down, employing is cooled to a certain temperature that is in 27～31 ℃ of scopes more than or equal to the rate of temperature fall of 200 ℃/min, constant temperature at least 1 hour, the degradation rate that the material of preparation alpha-crystal and β crystal coexistence, gained contain the polyester material of alpha-crystal and β crystal structure simultaneously depends on the relative amount of two kinds of crystal formations.
In temperature was 27～31 ℃ of scopes, the content of alpha-crystal was along with the rising of temperature is elevated to 80% by 0.
Described rate of temperature fall is preferably 200 ℃/min～300 ℃/min.
With the polymer fusion, be cooled to a certain temperature range with rate of temperature fall more than or equal to 200 ℃/min, constant temperature at least 1 hour, the polycrystalline sample that preparation has different relative amounts and structure is realized the regulation and control of degradation rate.
The rate of temperature fall that passes through the nonisothermal crystallization of the poly-adipic acid fourth diester of control of the present invention obtains having alpha-crystal and β crystal structure and the different polyester sample of relative amount, realizes that the regulate and control method of poly-adipic acid fourth diester material degradation performance is:
To gather adipic acid fourth diester 70～80 ℃ of abundant fusions down, adopting rate of temperature fall then is that the interior poly-adipic acid fourth diester of rate of temperature fall cooling of 8～30 ℃/min scope is to room temperature, the polyester material that obtains contains alpha-crystal and two kinds of crystal formations of β crystal, and poly-adipic acid fourth diester degradation rate changes with the difference of two kinds of crystal formation content.
In rate of temperature fall is 8～30 ℃/min scope, the content of alpha-crystal along with rate of temperature fall reduce be elevated to 60% by 10%.
With the polymer fusion, with specific rate of temperature fall cooling, this rate of temperature fall scope is 8～30 ℃/min, and preparation has polycrystalline structure and the different PBA sample of relative amount, can realize the regulation and control of degradation rate.
Annealing time by the poly-adipic acid fourth diester of control of the present invention obtains having alpha-crystal and β crystal structure and the different polyester sample of relative amount, realizes that the regulate and control method of poly-adipic acid fourth diester material degradation performance is:
To gather adipic acid fourth diester 70～80 ℃ of abundant fusions down, and adopt the rate of temperature fall more than or equal to 200 ℃/min to be cooled to 27 ℃, constant temperature at least 1 hour prepares pure β crystalline material; Utilize pure β crystal can be transformed into the characteristic of the more stable alpha-crystal of thermodynamics, poly-adipic acid fourth two ester materials that will have pure β crystal structure, annealed 1～72 hour down at 40～49 ℃, the polyester sample that can be contained alpha-crystal and β crystal simultaneously, regulate and control the relative amount of two kinds of crystal formations by the control annealing time, thereby realize the degradation rate regulation and control.
In 1～72 hour scope, the content of alpha-crystal is along with the prolongation of annealing time is elevated to 60% by 0.
Described rate of temperature fall is preferably 200 ℃/min～300 ℃/min.
Adopt β crystal annealing time difference in a certain temperature range of PBA, obtain having concurrently alpha-crystal and β crystal and two kinds of samples that crystalline content is different, can realize the regulation and control of degradation rate.
The present invention has provided the regulate and control method of a kind of regulation and control aliphatic poly adipic acid fourth diester (PBA) degradation property, regulates the degradation rate of PBA sample by the relative amount of alpha-crystal and two kinds of crystal of β crystal among the control PBA.The present invention has provided three kinds of approach that realize crystalline content control: the rate of temperature fall of the temperature of control isothermal crystal, control nonisothermal crystallization or by three kinds of methods of control annealing time.By changing the relative amount of the crystal of different structure in the PBA material, reached the purpose of regulation and control PBA material degradation speed.Method of the present invention provides a kind of new thinking and selection for the degradation property of regulation and control aliphatic polyester, and has that technology is simple, easy operating, is easy to the characteristics that realize aborning.
The specific embodiment
Below will the invention will be further elaborated by specific embodiment, its objective is better understanding content of the present invention, illustrated embodiment does not limit protection scope of the present invention.
Embodiment 1. regulates the content of different structure crystal in the PBA sample by controlling the isothermal crystal temperature, regulates degradation rate
With the fusion 3 minutes on the hot platforms of 75 degree of PBA sample, adopt the rate of temperature fall of 260 ℃/min, be cooled to 27 ℃, 28 ℃, 29 ℃, 30 ℃ and 31 ℃ respectively, behind the constant temperature 1 hour, detect the PBA sample with wide-angle x-ray diffraction, detection shows α and two kinds of crystal formation coexistences of β, calculates the content that can learn two kinds of crystal by swarming and changes with crystallization temperature is different, and data see Table 1.Degradation experiment proves that the degradation rate of polyester material is accelerated with the increase of alpha-crystal content, degradation rate the results are shown in Table 1.The alpha-crystal that table 1 forms behind the isothermal crystal under different temperatures for PBA and the relative amount of β crystal and corresponding degradation rate.
Table 1
Embodiment 2. regulates different crystal structural content in the PBA sample by the rate of temperature fall of control nonisothermal crystallization, the regulation and control degradation rate
With the fusion 3 minutes on the hot platforms of 75 degree of PBA sample, adopt the rate of temperature fall of 10 ℃/min, 15 ℃/min and 20 ℃/min to be cooled to room temperature respectively, detect the PBA sample with wide-angle x-ray diffraction, detection shows α and two kinds of crystal formation coexistences of β, alpha-crystal changes with rate of temperature fall is different with the β crystalline content in the sample, and data see Table 2.Degradation experiment proves that the degradation rate of polyester material is accelerated with the increase of alpha-crystal content, thereby regulates and control the relative amount of polycrystalline by changing rate of temperature fall, can reach the purpose of regulation and control degradation rate, and degradation rate the results are shown in Table 2.The alpha-crystal that table 2 forms behind nonisothermal crystallization under the different rate of temperature fall for PBA and the relative amount of β crystal and corresponding degradation rate.
Table 2
Embodiment 3. regulates the crystalline content of two kinds of structures in the sample by different annealing times, thus the degradation rate of regulation and control polyester material
With the fusion 3 minutes on 80 ℃ hot platform of PBA sample, be cooled to 25 ℃ with the rate of temperature fall of 200 ℃/min, constant temperature obtained pure β crystal in 1 hour.Distinguish annealing in process 1 hour and 5 hours then on the hot platforms of 47 degree, wherein part β crystalline transformation is an alpha-crystal, according to the result of wide-angle x-ray diffraction, calculates the wherein relative amount of the crystal of different structure, the results are shown in Table 3.Degradation experiment proves, the sample of annealing 5 hours is owing to have more alpha-crystal content than 1 hour sample of annealing, thereby has degradation rate faster, the results are shown in Table 3.Table 3 is at the β crystal of the PBA that 25 ℃ of isothermal crystals form relative amount and the degradation rate at 47 ℃ of annealing crystal of two kinds of structures after 1 hour and 5 hours.
Table 3
Claims (6)
1. the regulate and control method of an aliphatic poly adipic acid fourth diester material degradation performance, it is characterized in that: this method is by the temperature of the isothermal crystal of controlling poly-adipic acid fourth diester or by the rate of temperature fall of control nonisothermal crystallization or by three kinds of methods of control annealing time, the relative amount of alpha-crystal and β crystal structure in poly-adipic acid fourth two ester materials of regulation and control, thereby the degradation rate of poly-adipic acid fourth two ester materials of regulation and control;
Described temperature of gathering the isothermal crystal of adipic acid fourth diester by control, realize that the regulate and control method of poly-adipic acid fourth diester material degradation performance is:
To gather adipic acid fourth diester 70～80 ℃ of abundant fusions down, employing is cooled to a certain temperature that is in 27～31 ℃ of scopes more than or equal to the rate of temperature fall of 200 ℃/min, constant temperature at least 1 hour, the degradation rate that the material of preparation alpha-crystal and β crystal coexistence, gained contain the polyester material of alpha-crystal and β crystal structure simultaneously depends on the relative amount of two kinds of crystal formations;
Described by controlling the rate of temperature fall of the nonisothermal crystallization that gathers adipic acid fourth diester, realize that the regulate and control method of poly-adipic acid fourth diester material degradation performance is:
To gather adipic acid fourth diester 70～80 ℃ of abundant fusions down, adopting rate of temperature fall then is that the interior poly-adipic acid fourth diester of rate of temperature fall cooling of 8～30 ℃/min scope is to room temperature, the polyester material that obtains contains alpha-crystal and two kinds of crystal formations of β crystal, and poly-adipic acid fourth diester degradation rate changes with the difference of two kinds of crystal formation content;
Described annealing time by the poly-adipic acid fourth diester of control, realize that the regulate and control method of poly-adipic acid fourth diester material degradation performance is:
To gather adipic acid fourth diester 70～80 ℃ of abundant fusions down, and adopt the rate of temperature fall more than or equal to 200 ℃/min to be cooled to 27 ℃, constant temperature at least 1 hour prepares pure β crystalline material; Poly-adipic acid fourth two ester materials that will have pure β crystal structure, annealed 1～72 hour down at 40～49 ℃, the polyester sample that is contained alpha-crystal and β crystal is simultaneously regulated and control the relative amount of two kinds of crystal formations by the control annealing time, thereby realizes the degradation rate regulation and control.
2. method according to claim 1, it is characterized in that: in the temperature of gathering the isothermal crystal of adipic acid fourth diester by control, realize in the regulate and control method of poly-adipic acid fourth diester material degradation performance, in temperature was 27～31 ℃ of scopes, the content of alpha-crystal was along with the rising of temperature is elevated to 80% by 0.
3. method according to claim 1 is characterized in that: the temperature at the isothermal crystal by the poly-adipic acid fourth diester of control, realize in the regulate and control method of poly-adipic acid fourth diester material degradation performance that described rate of temperature fall is 200 ℃/min～300 ℃/min.
4. method according to claim 1, it is characterized in that: at the rate of temperature fall that gathers the nonisothermal crystallization of adipic acid fourth diester by control, realize in the regulate and control method of poly-adipic acid fourth diester material degradation performance, in rate of temperature fall is 8～30 ℃/min scope, the content of alpha-crystal along with rate of temperature fall reduce be elevated to 60% by 10%.
5. method according to claim 1, it is characterized in that: at annealing time by the poly-adipic acid fourth diester of control, realize in the regulate and control method of poly-adipic acid fourth diester material degradation performance that in 1～72 hour scope, the content of alpha-crystal is along with the prolongation of annealing time is elevated to 60% by 0.
6. method according to claim 1 is characterized in that:, realize in the regulate and control method of poly-adipic acid fourth diester material degradation performance that described rate of temperature fall is 200 ℃/min～300 ℃/min at the annealing time by the poly-adipic acid fourth diester of control.
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| CN106042534B (en) * | 2016-05-26 | 2017-10-13 | 陕西科技大学 | Nylon 6 weave cotton cloth regulation and control poly adipate succinic acid ester polymorphic structures preparation method |
| CN106496966B (en) * | 2016-10-28 | 2018-08-07 | 陕西科技大学 | A kind of preparation method of degradable poly adipate succinic acid ester/potassium bromide composite material |
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| The role of polymorphic crystal structure andmorphologyinenzymatic degradation of melt-crystallized poly(butyleneadipate) films. Zhihua Gan, Kazuhiro Kuwabara, Hideki Abe, TadahisaIwata, Yoshiharu Doi.Polymer Degradation and Stability,No.87. 2005 * |
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