CN111423601B - Preparation method of cross-linked polycaprolactone material - Google Patents
Preparation method of cross-linked polycaprolactone material Download PDFInfo
- Publication number
- CN111423601B CN111423601B CN202010435708.5A CN202010435708A CN111423601B CN 111423601 B CN111423601 B CN 111423601B CN 202010435708 A CN202010435708 A CN 202010435708A CN 111423601 B CN111423601 B CN 111423601B
- Authority
- CN
- China
- Prior art keywords
- polycaprolactone
- cross
- styrene
- acrylonitrile copolymer
- linked
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a preparation method of a cross-linked polycaprolactone material, which comprises the following steps: melting and blending polycaprolactone and styrene-acrylonitrile copolymer, mixing with a cross-linking agent, and melting and blending to obtain polycaprolactone blend particles; pressing the polycaprolactone blend particles to obtain a polycaprolactone sheet; and (3) performing electron beam irradiation on the polycaprolactone sheet to obtain the cross-linked polycaprolactone material. The crystallization speed of the crosslinked polycaprolactone can be obviously inhibited by introducing the styrene-acrylonitrile copolymer; furthermore, the crystallization speed and the crosslinking degree of the crosslinked polycaprolactone material can be further regulated and controlled by regulating the content of the styrene-acrylonitrile copolymer, the content of the crosslinking agent and the irradiation dose.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a cross-linked polycaprolactone material.
Background
Polycaprolactone (PCL) is a novel degradable polymer material. Polycaprolactone has the advantages of good biocompatibility and biodegradability and compatibility with other polymers, so that polycaprolactone is widely applied to various fields of national economy. Polycaprolactone has the characteristics of excellent mechanical property, no toxicity and biocompatibility, and has great application value in the biomedical field such as drug delivery, surgical sutures, porous tissue engineering scaffolds and the like.
It is well known that the crystallization behavior of polymers is closely related to the properties of the polymer. If the crystallization speed is too low and the performance requirement cannot be met within the expected time, the time is consumed, and financial resources, material resources and manpower are wasted; if the crystallization speed is too fast, the actual operation requirements or performance requirements cannot be met. For crosslinked polymers, the crosslink density, molecular weight between crosslinking points, and crosslinking structure have a significant effect on the crystallization of the crosslinked polymer. A small number of crosslinking sites, corresponding to nucleation sites, promote crystallization of the polymer, while excessive crosslinking restricts molecular chain movement resulting in slower crystallization rates. Therefore, how to regulate the crystallization speed of the crosslinked polymer is a crucial research direction.
The cross-linked polycaprolactone product obtained by irradiation with polycaprolactone as the raw material has good shape memory function, can be molded again and has good biodegradability. At present, a method for regulating and controlling the crystallization speed of linear polycaprolactone is reported in documents, but crosslinked polycaprolactone is more complex than linear polycaprolactone, and the crosslinking structure of crosslinked polycaprolactone has an influence on certain regulating and controlling agents and the crystallization speed of crosslinked polycaprolactone, so that the regulation and control of the crystallization speed of the linear polycaprolactone cannot be directly introduced to regulate and control the crystallization speed of the crosslinked polycaprolactone, namely how to regulate and control the crystallization speed of the crosslinked polycaprolactone is not clear. However, too fast a crystallization rate of the crosslinked polycaprolactone results in limited applications. Therefore, slowing down the crystallization rate of the crosslinked polycaprolactone is a practical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a cross-linked polycaprolactone material, and the method can inhibit the crystallization speed of cross-linked polycaprolactone.
In view of the above, the present application provides a method for preparing a cross-linked polycaprolactone material, comprising the following steps:
melting and blending polycaprolactone and styrene-acrylonitrile copolymer, mixing with a cross-linking agent, and melting and blending to obtain polycaprolactone blend particles;
pressing the polycaprolactone blend particles to obtain a polycaprolactone sheet;
and (3) performing electron beam irradiation on the polycaprolactone sheet to obtain the cross-linked polycaprolactone material.
Preferably, the polycaprolactone and the styrene-acrylonitrile copolymer are respectively dried and then melt blended.
Preferably, the method for drying the polycaprolactone comprises the following steps: drying the polycaprolactone in a vacuum drying oven at 40-60 ℃ for 8-24 h;
the method for drying the styrene-acrylonitrile copolymer comprises the following steps: and drying the styrene-acrylonitrile copolymer in a vacuum drying oven at 40-80 ℃ for 8-12 h.
Preferably, the number average molecular weight of the polycaprolactone is 47-186 kg/mol, the weight average molecular weight is 58-1140 kg/mol, and the molecular weight distribution is 1.2-6.6; the content of acrylonitrile in the styrene-acrylonitrile copolymer is 10-38%.
Preferably, the polycaprolactone: styrene-acrylonitrile copolymer: the mass ratio of the cross-linking agent is 100: (0-30): (0.1-6); the mass of the styrene-acrylonitrile copolymer is not 0.
Preferably, the temperature of the melt blending of the polycaprolactone and the styrene-acrylonitrile copolymer is 150-220 ℃, the time is 1-10 min, the melt blending is carried out by adopting an internal mixer, and the rotating speed of a rotor of the internal mixer is 40-90 r/min; and the temperature of the melt blending after the melt blending is mixed with the cross-linking agent is 150-220 ℃, the time is 1-10 min, the melt blending is carried out by adopting an internal mixer, and the rotating speed of a rotor of the internal mixer is 40-90 r/min.
Preferably, the pressing is performed in a laminator, and the pressing specifically comprises: melting at the temperature of 80-120 ℃ for 1-10 min, decompressing for 3-5 times, and maintaining the pressure for 1-20 min.
Preferably, the dose of the electron beam irradiation is 5-150 KGy.
Preferably, based on the polycaprolactone, the content of the styrene-acrylonitrile copolymer is 10-30 wt%, and the dosage of electron beam irradiation is 50-150 KGy; the content of the styrene-acrylonitrile copolymer is less than 10wt% and not equal to 0wt%, and the dosage of electron beam irradiation is 5-20 KGy.
Preferably, the crosslinking agent is triallyl isocyanurate, dicumyl peroxide or trimethylolpropane triacrylate.
The application provides a preparation method of a cross-linked polycaprolactone material, which comprises the steps of firstly, melting and blending polycaprolactone and a styrene-acrylonitrile copolymer, and then mixing the blended materials with a cross-linking agent to obtain polycaprolactone blend particles; then pressing the polycaprolactone blend particles to obtain a polycaprolactone sheet, and finally performing electron beam irradiation on the polycaprolactone sheet to obtain a cross-linked polycaprolactone material; in the process of preparing the cross-linked polycaprolactone material, the styrene-acrylonitrile copolymer is introduced, and the electron beam irradiation mode is adopted, so that the crystallization speed of the cross-linked polycaprolactone material is effectively inhibited.
Drawings
FIG. 1 is a DSC curve of the cross-linked polycaprolactone material prepared in example 1 and example 2 after melting and then cooling at 7.65 deg.C/min;
FIG. 2 is a DSC curve of isothermal crystallization at 38 ℃ of the cross-linked polycaprolactone material prepared in example 1 and example 2;
FIG. 3 is a DSC curve of the cross-linked polycaprolactone material prepared in examples 3 and 4 after melting and then cooling at 7.65 deg.C/min;
FIG. 4 is a DSC curve of isothermal crystallization at 38 ℃ of the cross-linked polycaprolactone material prepared in example 3 and example 4;
FIG. 5 is a differential microscope picture of the cross-linked polycaprolactone materials prepared in examples 4 and 5 at 120 ℃;
FIG. 6 is a DSC curve of the cross-linked polycaprolactone material prepared in examples 5 and 6 after melting and then cooling at 7.65 deg.C/min;
FIG. 7 is a DSC curve of isothermal crystallization at 38 ℃ of the cross-linked polycaprolactone materials prepared in examples 5 and 6.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In order to effectively regulate and control the crystallization speed of the cross-linked polycaprolactone material, the application provides a preparation method of the cross-linked polycaprolactone material, and the preparation method effectively regulates and controls the crystallization speed of the cross-linked polycaprolactone material by introducing styrene-acrylonitrile copolymer (SAN) and irradiating electron beams. Specifically, the embodiment of the invention discloses a preparation method of a cross-linked polycaprolactone material, which comprises the following steps:
melting and blending polycaprolactone and styrene-acrylonitrile copolymer, mixing with a cross-linking agent, and melting and blending to obtain polycaprolactone blend particles;
pressing the polycaprolactone composite granules to obtain a polycaprolactone sheet;
and (3) performing electron beam irradiation on the polycaprolactone sheet to obtain the cross-linked polycaprolactone material.
In the process of preparing the cross-linked polycaprolactone material, firstly, polycaprolactone and styrene-acrylonitrile copolymer are melted and blended, and the polycaprolactone and the styrene-acrylonitrile copolymer (SAN) are fully mixed in the process; drying polycaprolactone and SAN first prior to melt blending by: drying the polycaprolactone in a vacuum drying oven at 40-60 ℃ for 8-24 h; the method for drying the styrene-acrylonitrile copolymer comprises the following steps: and drying the styrene-acrylonitrile copolymer in a vacuum drying oven at 40-80 ℃ for 8-12 h. The melt blending is carried out by adopting an internal mixer, the melt blending temperature is 150-220 ℃, the time is 1-10 min, and the rotating speed of a rotor of the internal mixer is 40-90 r/min. According to the invention, the mixture after melt blending is mixed with a cross-linking agent and melt blended to obtain the polycaprolactone blend particles. In the process, the temperature of the melt blending is 150-220 ℃, the time is 1-10 min, the melt blending is carried out by adopting an internal mixer, and the rotating speed of a rotor of the internal mixer is 40-90 r/min. The parameters related to the above two melt blending processes may be the same or different, and there is no particular limitation in this application. The cross-linking agent is selected from triallyl isocyanurate, dicumyl peroxide or trimethylolpropane triacrylate. The polycaprolactone: styrene-acrylonitrile copolymer: the mass ratio of the cross-linking agent is 100: (0-30): (0.1-6); the mass of the styrene-acrylonitrile copolymer is not 0; the addition of SAN further increases the crystallization rate of polycaprolactone more significantly. Meanwhile, SAN has good mechanical properties and can improve the modulus and strength of the cross-linked polycaprolactone material.
Pressing the polycaprolactone composite granules to obtain a polycaprolactone sheet; the pressing is a technical means well known to those skilled in the art, and the present application is not particularly limited thereto. The pressing is carried out in a film pressing machine, and the pressing specifically comprises the following steps: melting at the temperature of 80-120 ℃ for 1-10 min, decompressing for 3-5 times, and maintaining the pressure for 1-20 min. The application is right the thickness of polycaprolactone sheet does not have special restriction, as long as electron beam irradiation can be penetrable the thickness all can, can be the millimeter level, also can be centimetre level.
According to the invention, finally, the polycaprolactone sheet is subjected to electron beam irradiation to obtain a cross-linked polycaprolactone material; in the process, the linear polycaprolactone is crosslinked through electron beam irradiation to obtain a crosslinked polycaprolactone material; the crosslinked structure affects the crystallization rate of the crosslinked polycaprolactone. The irradiation dose of the electron beam is 5-150 KGy; in order to enable the crosslinked polycaprolactone to have better crosslinking degree and practical application value, the SAN radiation resistance requires to increase the irradiation dose, so that the sample with more SAN content (10-30%) achieves the crosslinking degree similar to the sample with less SAN content (0-10% is not equal to 0 but not equal to 10%); wherein the irradiation dose of the sample with high SAN content (10-30%) is 50-150 KGy, and the irradiation dose of the sample with low SAN content (0-10% is not equal to 0 and not equal to 10%) is 5-20 KGy. If the irradiation dose is too low, the density of the cross-linked structure is low, a small amount of cross-linked points serve as nucleation points, and the chain motion is not influenced, so that the crystallization speed of the cross-linked polycaprolactone can be accelerated; if the irradiation dose is high, the crosslinking density is high, and the chain motion is severely limited, the crystallization speed of the crosslinked polycaprolactone can be inhibited.
In the process of preparing the cross-linked polycaprolactone material, the SAN content, the electron beam irradiation dose and the content of the cross-linking agent can jointly determine the cross-linked structure of the cross-linked polycaprolactone material, and the cross-linked density of the cross-linked polycaprolactone material is regulated and controlled (if the cross-linked density is too low, the strength of the cross-linked polycaprolactone in a molten state is not enough, and the use requirement cannot be met).
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the cross-linked polycaprolactone material provided by the present invention, and the scope of the present invention is not limited by the following examples.
The polycaprolactone used in the examples below was a commercial PCL, a linear polycaprolactone manufactured by Pasteur, Sweden under the designation 6500. The styrene-acrylonitrile copolymer is a styrene-acrylonitrile copolymer produced by Ningbo Taiwan under the trademark NF 2200. The specific formulations of the crosslinked polycaprolactone materials prepared in examples 1-6 are shown in Table 1.
Example 1
Placing the PCL granules and the SAN granules in a vacuum drier at 40 ℃ and 80 ℃ respectively for drying for 12 h; melting and blending the dried PCL and SAN in an internal mixer at 200 ℃ and 40rpm according to the mass ratio of 100:0 for 2min, then adding 1.75% of cross-linking agent TAIC, continuing to melt and blend for 3min, discharging to obtain polycaprolactone blend particles; pressing the blend granules into a sheet with the thickness of 1mm in a film pressing machine, wherein the film pressing temperature is 120 ℃, melting is carried out for 2min, pressure is released for 3 times, and pressure is maintained for 1min under 10 MPa; and (3) putting the pressed sheet into a polyethylene bag, and irradiating by using electron beams with the irradiation dose of 20KGy to obtain the cross-linked polycaprolactone material.
Example 2
The preparation process is the same as example 1, except that: the mass ratio of PCL to SAN was 95:5, and the irradiation dose was 50 KGy.
FIG. 1 is a DSC curve of the cross-linked polycaprolactone material prepared in example 1 and example 2 after melting and then cooling at 7.65 deg.C/min; the crystallization peak temperature corresponding to the cooling curve in the figure is an important index for reflecting the crystallization behavior of polycaprolactone, and the crystallization peak temperature of the cross-linked polycaprolactone material prepared in example 2 (with 5% of SAN added) is lower than that of the cross-linked polycaprolactone material prepared in example 1 (with pure PCL), which indicates that the crystallization speed of the cross-linked polycaprolactone can be reduced by adding SAN.
FIG. 2 is a DSC curve of isothermal crystallization at 38 ℃ of the cross-linked polycaprolactone materials prepared in examples 1 and 2; the isothermal crystallization test shows that the adding of SAN obviously prolongs the isothermal crystallization time of the cross-linked PCL material, and further proves that SAN plays a role in inhibiting the crystallization speed of the cross-linked polycaprolactone in the polycaprolactone material with the same cross-linking degree.
Example 3
The preparation process is the same as example 1, except that: the mass ratio of PCL to SAN was 95:5, and the irradiation dose was 20 KGy.
Example 4
The preparation process is the same as example 1, except that: the mass ratio of PCL to SAN was 90:10, and the irradiation dose was 50 KGy.
FIG. 3 is a DSC curve of the cross-linked polycaprolactone material prepared in examples 3 and 4 after melting and then cooling at 7.65 deg.C/min; the crystallization peak temperature of the cross-linked polycaprolactone material prepared in example 4 (with 10% SAN added) was 21.6 deg.C, which is less than the crystallization peak temperature of 26.3 deg.C in example 3 (with 5% SAN added), indicating that the crystallization rate of the cross-linked polycaprolactone is slower with increasing SAN content.
FIG. 4 is a DSC curve of isothermal crystallization at 38 ℃ of the cross-linked polycaprolactone materials prepared in examples 3 and 4; the more SAN content added, the slower the crystallization rate of the crosslinked polycaprolactone can be found by isothermal crystallization testing.
Example 5
Example 5 was prepared according to the same procedure as example 1. The difference is that the mass ratio of PCL to SAN is 95:5, and the content of the cross-linking agent is 0.5%.
FIG. 5 is a difference microscope picture at 120 ℃ of examples 4 and 5, wherein the left side shows no phase separation at 120 ℃ and shows that PCL and SAN are completely compatible in the cross-linked polycaprolactone material, and the right side shows no phase separation, further showing that PCL and SAN are compatible in the cross-linked polycaprolactone material.
Example 6
The preparation process is the same as example 1, except that: the mass ratio of PCL to SAN is 90:10, the content of cross-linking agent is 0.5%, and the irradiation dose is 50 KGy.
FIG. 6 is a DSC curve of the cross-linked polycaprolactone material prepared in examples 5 and 6 after melting and then cooling at 7.65 deg.C/min; the crystallization peak temperature of the cross-linked polycaprolactone material prepared in example 6 (with 10% SAN added) was 23.1 deg.C, which is 28.0 deg.C higher than the crystallization peak temperature of example 5 (with 5% SAN added), indicating that the crystallization rate of the cross-linked polycaprolactone is slower with increasing SAN content.
FIG. 7 is a DSC curve of isothermal crystallization at 38 ℃ of the cross-linked polycaprolactone materials prepared in examples 5 and 6.
Comparative example 1
The preparation process is the same as example 1, except that: the mass ratio of PCL to SAN is 90:10, the content of cross-linking agent is 1.75%, and the irradiation dose is 20 KGy.
TABLE 1 formulation and gel content data table for preparing crosslinked polycaprolactone materials in examples 1-6
TABLE 2 statistical table of thermal performance indexes of the cross-linked polycaprolactone materials prepared in examples 1-6
Comparing example 1 with example 2, example 3 with example 4, and example 5 with example 6 in table 1, it is known that after adding SAN, the irradiation dose needs to be increased to make the gel content similar to the sample with less SAN content due to the radiation resistance of SAN. As shown in Table 1, when 10% SAN and 1.75% TAIC were added and the irradiation dose was 20KGy, the gel content was 0%, indicating that a polycaprolactone material having a certain degree of crosslinking could be obtained by further increasing the irradiation dose.
As is clear from examples 1 and 2, examples 3 and 4, and examples 5 and 6 in Table 2, the crystallization temperature and crystallinity of the sample containing a large amount of SAN were lowered, indicating that SAN inhibited the crystallization of crosslinked polycaprolactone; as can be seen from examples 2, 3 and 5 in Table 2, the crystallization temperature decreases with increasing gel content, indicating that this range of crosslinking density acts as an inhibitor of the crystallization of the crosslinked polycaprolactone.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A preparation method of a cross-linked polycaprolactone material comprises the following steps:
melting and blending polycaprolactone and styrene-acrylonitrile copolymer, mixing with a cross-linking agent, and melting and blending to obtain polycaprolactone blend particles;
pressing the polycaprolactone blend particles to obtain a polycaprolactone sheet;
performing electron beam irradiation on the polycaprolactone sheet to obtain a cross-linked polycaprolactone material;
the polycaprolactone: styrene-acrylonitrile copolymer: the mass ratio of the cross-linking agent is 100: (0-30): (0.1-6); the mass of the styrene-acrylonitrile copolymer is not 0;
based on the polycaprolactone, the content of the styrene-acrylonitrile copolymer is 10-30 wt%, and the dosage of electron beam irradiation is 50-150 KGy; the content of the styrene-acrylonitrile copolymer is less than 10wt% and not equal to 0wt%, and the dosage of electron beam irradiation is 5-20 KGy.
2. The method according to claim 1, wherein the polycaprolactone and the styrene-acrylonitrile copolymer are dried and then melt-blended.
3. The preparation method according to claim 2, wherein the polycaprolactone is dried by a method comprising: drying the polycaprolactone in a vacuum drying oven at 40-60 ℃ for 8-24 h;
the method for drying the styrene-acrylonitrile copolymer comprises the following steps: and drying the styrene-acrylonitrile copolymer in a vacuum drying oven at 40-80 ℃ for 8-12 h.
4. The preparation method according to claim 1, wherein the polycaprolactone has a number average molecular weight of 47 to 186kg/mol, a weight average molecular weight of 58 to 1140kg/mol, and a molecular weight distribution of 1.2 to 6.6; the content of acrylonitrile in the styrene-acrylonitrile copolymer is 10-38%.
5. The preparation method according to claim 1, wherein the melt blending temperature of the polycaprolactone and the styrene-acrylonitrile copolymer is 150-220 ℃, the time is 1-10 min, the melt blending is carried out by adopting an internal mixer, and the rotating speed of a rotor of the internal mixer is 40-90 r/min; and the temperature of the melt blending after the melt blending is mixed with the cross-linking agent is 150-220 ℃, the time is 1-10 min, the melt blending is carried out by adopting an internal mixer, and the rotating speed of a rotor of the internal mixer is 40-90 r/min.
6. The method according to claim 1, wherein the pressing is performed in a laminator, the pressing being in particular: melting at the temperature of 80-120 ℃ for 1-10 min, decompressing for 3-5 times, and maintaining the pressure for 1-20 min.
7. The method according to claim 1, wherein the crosslinking agent is triallyl isocyanurate or trimethylolpropane triacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010435708.5A CN111423601B (en) | 2020-05-21 | 2020-05-21 | Preparation method of cross-linked polycaprolactone material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010435708.5A CN111423601B (en) | 2020-05-21 | 2020-05-21 | Preparation method of cross-linked polycaprolactone material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111423601A CN111423601A (en) | 2020-07-17 |
| CN111423601B true CN111423601B (en) | 2021-07-06 |
Family
ID=71555243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010435708.5A Active CN111423601B (en) | 2020-05-21 | 2020-05-21 | Preparation method of cross-linked polycaprolactone material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111423601B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116693835B (en) * | 2023-07-04 | 2024-05-03 | 湖南聚仁新材料股份公司 | Polycaprolactone for radiation crosslinking, preparation method thereof and radiation crosslinking method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012000992A1 (en) * | 2010-06-29 | 2012-01-05 | Basf Se | Process for improving the flow properties of polymer melts |
| CN103709692A (en) * | 2013-11-18 | 2014-04-09 | 北京市射线应用研究中心 | Poly epsilon-caprolactone/poly (beta-hydroxybutyrate-valerate) blend membrane and preparation method thereof |
| CN107043525A (en) * | 2017-06-07 | 2017-08-15 | 扬州大学 | The preparation method of polycaprolactone/cellulose composite material of controllable polycaprolactone crystallization |
-
2020
- 2020-05-21 CN CN202010435708.5A patent/CN111423601B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012000992A1 (en) * | 2010-06-29 | 2012-01-05 | Basf Se | Process for improving the flow properties of polymer melts |
| CN103709692A (en) * | 2013-11-18 | 2014-04-09 | 北京市射线应用研究中心 | Poly epsilon-caprolactone/poly (beta-hydroxybutyrate-valerate) blend membrane and preparation method thereof |
| CN107043525A (en) * | 2017-06-07 | 2017-08-15 | 扬州大学 | The preparation method of polycaprolactone/cellulose composite material of controllable polycaprolactone crystallization |
Non-Patent Citations (4)
| Title |
|---|
| Effect of electron beam irradiation on the crystallization of silk fibroin fiber‐reinforced poly(ε‐caprolactone) biocomposites;Qiao Xiuying et al.;《POLYMER INTERNATIONAL》;20091124;第59卷(第4期);第447-455页 * |
| Structural and morphological changes in Poly(caprolactone)/poly(vinyl chloride) blends caused by UV irradiation;Martins-Franchetti et al.;《JOURNAL OF MATERIALS SCIENCE》;20071116;第43卷(第3期);第1063-1069页 * |
| 电子束辐照对高分子共混物力学性能与三重形状记忆性能的影响;伍贤友;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20200215;B016-15 * |
| 聚己内酯（PCL）/苯乙烯丙烯-腈共聚物（SAN）共混体系相容性研究进展;杨慧娴;《改性塑料》;20030630;第32卷(第3期);第46-51页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111423601A (en) | 2020-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022037349A1 (en) | Toughening degradable polyglycolic acid composition, and toughening degradable polyglycolic acid material and preparation method therefor and use thereof | |
| JP4870354B2 (en) | Curable thermoplastic elastomer blend, process for its production and use thereof | |
| Nerkar et al. | Melt compounded blends of short and medium chain-length poly-3-hydroxyalkanoates | |
| HU183546B (en) | Process for preparing a combined substance containing a thermoplastic material, a fibrous polymeric skeleton substance of natural origin and an insaturated polyester | |
| EP1090068A1 (en) | Soft propylene polymer blend with high melt strength | |
| EP3820941B1 (en) | A grafted polylactic acid | |
| CN111423601B (en) | Preparation method of cross-linked polycaprolactone material | |
| Meng et al. | Morphology, rheological and thermal properties of the melt blends of poly (phthalazinone ether ketone sulfone) with liquid crystalline copolyester | |
| Yavarpanah et al. | Evaluating the effect of hydroxyapatite nanoparticles on morphology, thermal stability and dynamic mechanical properties of multicomponent blend systems based on polylactic acid/Starch/Polycaprolactone | |
| CN102558638A (en) | Positive temperature coefficient material, preparation method thereof and thermistor containing positive temperature coefficient material | |
| Bian et al. | Synthesis of multi-arm poly (L-lactide) and its modification on linear polylactide | |
| CN105504698A (en) | Heat-resistance liquid crystal polyester resin compound and preparation method thereof | |
| CN110540710A (en) | Thermal-aging-resistant polypropylene nano composite material and preparation method thereof | |
| CN111533999A (en) | Ultrahigh melt index polypropylene material and preparation method and application thereof | |
| CN111978685B (en) | Biomedical thermoplastic vulcanized rubber and preparation method thereof | |
| KR101139654B1 (en) | Blending compatibilization method of biodegradable polymers | |
| CN113999418A (en) | Polyvinyl alcohol material with multistage anisotropy as well as preparation method and application thereof | |
| CN115850783A (en) | Low-density toughened polypropylene foam material composition, low-density toughened polypropylene foam material and preparation method thereof | |
| Huang et al. | Soy protein‐based nanocomposites reinforced by supramolecular nanoplatelets assembled from pluronic polymers/β‐cyclodextrin pseudopolyrotaxanes | |
| CN115322303B (en) | Composition for preparing polyglycolic acid material, preparation method and application thereof | |
| CN115490896B (en) | Waterproof heat-resistant, ultraviolet-resistant and antibacterial multifunctional polyvinyl alcohol biodegradable film and preparation method thereof | |
| EP1654320B1 (en) | Irradiated butene-1 polymer compositions | |
| JPH01315454A (en) | Highly crosslinked polymer particle and production thereof | |
| SU1214683A1 (en) | Method of producing polymer composition | |
| JPS58173145A (en) | Production of modified propylene/ethylene block copolymer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |