CN113754996A - Modification method of poly (epsilon-caprolactone) and modified poly (epsilon-caprolactone) material - Google Patents
Modification method of poly (epsilon-caprolactone) and modified poly (epsilon-caprolactone) material Download PDFInfo
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- CN113754996A CN113754996A CN202111102528.6A CN202111102528A CN113754996A CN 113754996 A CN113754996 A CN 113754996A CN 202111102528 A CN202111102528 A CN 202111102528A CN 113754996 A CN113754996 A CN 113754996A
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- Prior art keywords
- epsilon
- caprolactone
- poly
- calcium hexahydrophthalate
- hexahydrophthalate
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention belongs to the field of new materials, and particularly relates to a modification method of poly (epsilon-caprolactone) and a modified poly (epsilon-caprolactone) material. The invention uses calcium hexahydrophthalate as a nucleating agent to improve the crystallization rate, and specifically comprises the following steps: mixing calcium hexahydrophthalate and poly (epsilon-caprolactone) or mixing calcium hexahydrophthalate with poly (epsilon-caprolactone) in the form of master batch; then, obtaining a poly (epsilon-caprolactone) material with high crystallization speed by banburying, extrusion or injection molding processing methods; wherein the dosage of the calcium hexahydrophthalate is 0.01-3.00 wt% of the mass of the poly (epsilon-caprolactone). The present invention also includes modified poly (epsilon-caprolactone) materials. The invention can obviously improve the crystallization temperature of the poly (epsilon-caprolactone), accelerate the crystallization rate of the poly (epsilon-caprolactone), improve the processing efficiency of the poly (epsilon-caprolactone) and reduce the production cost.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a modification method of poly (epsilon-caprolactone) and a modified poly (epsilon-caprolactone) material.
Background
Poly (epsilon-caprolactone) is an aliphatic polyester with biocompatibility and biodegradability, and is widely concerned in the fields of tissue engineering, drug sustained release, degradable packaging and the like. However, poly (. epsilon. -caprolactone) itself has problems such as slow crystallization rate and low crystallinity, which are disadvantageous for its processing and molding, and also limit its application in the above-mentioned fields.
For crystalline polymers, the addition of nucleating agents that promote the nucleation of macromolecules is an important method for accelerating the crystallization rate of materials and adjusting the crystalline structure. The advantages of convenient use, no change of polymer processing technology and the like are achieved, so that the polymer is widely concerned. It has been reported that the introduction of various fillers including carbon nanomaterials, silicate materials, polysaccharide materials, etc. into poly (. epsilon. -caprolactone) can exert not only the unexpected effect of reinforcing fillers but also the effect of nucleating agents to accelerate the crystallization of poly (. epsilon. -caprolactone) more or less. As a result of further studies, it was found that these reinforcing fillers can induce the poly (. epsilon. -caprolactone) to undergo epiphytic crystallization and thus improve the properties of the article. However, the above filler has a limited effect of promoting the crystallization of poly (. epsilon. -caprolactone), and the dispersibility thereof is not easy. So far, no commercial PCL efficient nucleating agent is reported, and the preparation of poly (epsilon-caprolactone) material with high crystallization speed still has difficulty. Therefore, the development of poly (epsilon-caprolactone) materials with high crystallization speed is of great significance.
Disclosure of Invention
The invention provides a modification method of poly (epsilon-caprolactone) and a modified poly (epsilon-caprolactone) material aiming at the problem of slow crystallization rate of the poly (epsilon-caprolactone).
The material is a mixture of poly (epsilon-caprolactone) and calcium hexahydrophthalate, wherein the dosage of the calcium hexahydrophthalate is 0.01-3.00 wt% of the mass of the poly (epsilon-caprolactone).
The modification method of the poly (epsilon-caprolactone) material provided by the invention uses calcium hexahydrophthalate as a nucleating agent, can greatly improve the crystallization rate, and comprises the following specific steps:
firstly, mixing calcium hexahydrophthalate with poly (epsilon-caprolactone) or mixing calcium hexahydrophthalate with poly (epsilon-caprolactone) in a master batch mode, and then obtaining a poly (epsilon-caprolactone) material with a high crystallization speed by processing methods such as banburying, extrusion, injection molding and the like;
or directly adding anhydrous calcium hexahydrophthalate into a reaction kettle for producing poly (epsilon-caprolactone), and granulating to obtain a corresponding product.
In the invention, the dosage of the calcium hexahydrophthalate is 0.01-3.00 wt% of the mass of the poly (epsilon-caprolactone).
In the present invention, the poly (. epsilon. -caprolactone) may be pure poly (. epsilon. -caprolactone) or a blend comprising poly (. epsilon. -caprolactone) as a main component and other polymers.
In the invention, the calcium hexahydrophthalate can be calcium hexahydrophthalate hydrate containing crystal water, and can also be anhydrous calcium hexahydrophthalate without crystal water; but preferably anhydrous calcium hexahydrophthalate with removal of water of crystallization. Compared with the crystal hydrate of calcium hexahydrophthalate, the calcium hexahydrophthalate with the crystal water removed can improve the crystallization rate of poly (epsilon-caprolactone) more obviously under the same addition amount.
The calcium hexahydrophthalate of the present invention can be synthesized by the method disclosed in patent CN 1500117 a. Typical embodiments are as follows: 4.81g of calcium hydroxide (0.65 mol) and 10.00 g of hexahydrophthalic anhydride (0.65 mol) are added into 40ml of deionized water, stirred for 5h at 50 ℃, and then collected by suction filtration to obtain a white product, and the white product is obtained after the deionized water is fully washed and dried overnight.
Drying is carried out at low temperature and the product obtained is usually calcium hexahydrophthalate hydrate containing water of crystallization. However, when the heat treatment is carried out at a higher temperature, the crystal water is removed to obtain anhydrous calcium hexahydrophthalate free of crystal water. When the drying temperature is below 120 ℃, as in usual drying times, the product obtained is usually a crystalline hydrate of calcium hexahydrophthalate; when the drying temperature is higher than 140 ℃, the obtained product is calcium hexahydrophthalate with crystal water removed.
The invention also relates to modified poly (epsilon-caprolactone) obtained by the modification method.
Compared with the prior art, the invention has the beneficial effects that:
1. the crystallization speed of poly (epsilon-caprolactone) is obviously improved by introducing calcium hexahydrophthalate;
2. the calcium hexahydrophthalate has small addition amount, good dispersibility and strong capability of improving the crystallization rate of poly (epsilon-caprolactone);
3. the method has the advantages of simple preparation process, low production cost, less pollution and easy large-scale industrial production.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Preparation of a sample: 0.05% by weight of calcium hexahydrophthalate freed from water of crystallization was added to the poly (. epsilon. -caprolactone) pellets (CAPA 6500 produced by Cystotto, Sweden), and the mixture was melt-blended at 80 ℃ by means of an internal mixer to prepare a sample. Under the conditions described above, a control sample of poly (. epsilon. -caprolactone) having the same processing history but without the addition of a nucleating agent was prepared.
The invention utilizes a Mettler DSC1 thermal analyzer to measure the crystallization peak temperature (T) of poly (epsilon-caprolactone)c). The program settings were as follows: under the nitrogen atmosphere, the temperature of the sample is raised from room temperature to 80 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 5 min to eliminate the thermal history, then the temperature is reduced to room temperature at the cooling rate of 10 ℃/min, the cooling crystallization curve is recorded, and the T of the sample is obtainedc. The determination result shows that the T of the poly (epsilon-caprolactone) can be converted by introducing 0.05 weight percent of calcium hexahydrophthalate of which the crystal water is removedcThe increase is 3.9 ℃.
Example 2
Otherwise, the procedure of example 1 was repeated, except that the amount of calcium hexahydrophthalate freed of crystal water was 0.1% by weight. The crystallization results show that 0.1 wt% of the above calcium hexahydrophthalate freed of water of crystallization can incorporate T of poly (. epsilon. -caprolactone)cThe increase was 4.7 ℃.
Example 3
Otherwise, the procedure of example 1 was repeated, except that the amount of calcium hexahydrophthalate freed of crystal water was 0.2% by weight. The crystallization results show that 0.1 wt% of the above calcium hexahydrophthalate freed of water of crystallization can incorporate T of poly (. epsilon. -caprolactone)cThe increase is 5.2 ℃.
Example 4
The other example is the same as example 1, but a crystalline hydrate of calcium hexahydrophthalate is added. Crystallization determination results showed that the introduction of 0.05 wt% calcium hexahydrophthalate crystalline hydrate resulted in the incorporation of T of poly (. epsilon. -caprolactone)cThe increase is 1.0 ℃.
Example 5
The procedure is as in example 4, except that the crystalline hydrate of calcium hexahydrophthalate is added in an amount of 0.1% by weight. Crystallization determination results showed that the introduction of 0.1 wt% calcium hexahydrophthalate crystalline hydrate resulted in the incorporation of T of poly (. epsilon. -caprolactone)cThe increase is 1.2 ℃.
Example 6
The procedure is as in example 4, except that the crystalline hydrate of calcium hexahydrophthalate is added in an amount of 0.2% by weight. Crystallization determination results showed that the introduction of 0.2 wt% calcium hexahydrophthalate crystalline hydrate resulted in the incorporation of T of poly (. epsilon. -caprolactone)cThe increase is 1.7 ℃.
Example 7
The procedure of example 1 was repeated except that 0.05% by weight of the crystal water-removed calcium hexahydrophthalate was added to poly (. epsilon. -caprolactone) by means of a twin-screw extruder to conduct extrusion granulation. The determination of the crystallization results shows that 0.05% by weight of calcium hexahydrophthalate freed from water of crystallization can convert the T of poly (. epsilon. -caprolactone)cThe increase is 3.7 ℃.
Example 8
The other example is the same as example 7, but a crystalline hydrate of calcium hexahydrophthalate is added. Crystallization measurements showed that the T of poly (. epsilon. -caprolactone) can be converted by adding 0.05% by weight of a crystalline hydrate of calcium hexahydrophthalatecThe increase is 0.9 ℃.
Claims (4)
1. A modification method of poly (epsilon-caprolactone) is characterized in that calcium hexahydrophthalate is used as a nucleating agent to improve the crystallization rate, and the method comprises the following specific steps:
firstly, mixing calcium hexahydrophthalate and poly (epsilon-caprolactone) or mixing calcium hexahydrophthalate with poly (epsilon-caprolactone) in the form of master batch;
then, obtaining a poly (epsilon-caprolactone) material with high crystallization speed by banburying, extrusion or injection molding processing methods;
or directly adding anhydrous calcium hexahydrophthalate into a reaction kettle for producing the poly (epsilon-caprolactone), and granulating to obtain a modified poly (epsilon-caprolactone) material;
wherein the dosage of the calcium hexahydrophthalate is 0.01-3.00 wt% of the mass of the poly (epsilon-caprolactone).
2. The method for modifying poly (epsilon-caprolactone) according to claim 1, wherein the calcium hexahydrophthalate is calcium hexahydrophthalate hydrate containing crystal water or anhydrous calcium hexahydrophthalate free of crystal water.
3. The method of modifying poly (epsilon-caprolactone) of claim 1, wherein the poly (epsilon-caprolactone) is a blend comprising poly (epsilon-caprolactone) predominantly in combination with other polymers.
4. A poly (epsilon-caprolactone) material obtainable by the modification process of claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111102528.6A CN113754996A (en) | 2021-09-20 | 2021-09-20 | Modification method of poly (epsilon-caprolactone) and modified poly (epsilon-caprolactone) material |
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|---|---|---|---|
| CN202111102528.6A CN113754996A (en) | 2021-09-20 | 2021-09-20 | Modification method of poly (epsilon-caprolactone) and modified poly (epsilon-caprolactone) material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1500117A (en) * | 2001-03-29 | 2004-05-26 | Metalsalts of hexahydrophthalic acid as nucleating additives for crystalline thermoplatics | |
| CN101268132A (en) * | 2005-08-09 | 2008-09-17 | 美利肯公司 | Film and method of making film |
| CA2870027A1 (en) * | 2014-11-07 | 2016-05-07 | Matthew Zaki Botros | Blow molding composition and process |
| CN106519612A (en) * | 2016-11-15 | 2017-03-22 | 扬州大学 | Nucleation method of polycaprolactone |
-
2021
- 2021-09-20 CN CN202111102528.6A patent/CN113754996A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1500117A (en) * | 2001-03-29 | 2004-05-26 | Metalsalts of hexahydrophthalic acid as nucleating additives for crystalline thermoplatics | |
| CN101268132A (en) * | 2005-08-09 | 2008-09-17 | 美利肯公司 | Film and method of making film |
| CA2870027A1 (en) * | 2014-11-07 | 2016-05-07 | Matthew Zaki Botros | Blow molding composition and process |
| CN106519612A (en) * | 2016-11-15 | 2017-03-22 | 扬州大学 | Nucleation method of polycaprolactone |
Non-Patent Citations (1)
| Title |
|---|
| 张进兵: "聚ε-己内酯/石墨烯纳米复合材料的制备、结构与性能", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20211207 |