CN101974212B - Polycaprolactone/calcium sulfate composite material and preparation method thereof - Google Patents

Polycaprolactone/calcium sulfate composite material and preparation method thereof Download PDF

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CN101974212B
CN101974212B CN 201010522568 CN201010522568A CN101974212B CN 101974212 B CN101974212 B CN 101974212B CN 201010522568 CN201010522568 CN 201010522568 CN 201010522568 A CN201010522568 A CN 201010522568A CN 101974212 B CN101974212 B CN 101974212B
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calcium sulfate
polycaprolactone
minutes
stirred
modified
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CN101974212A (en )
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任力
刘金彦
李国元
王迎军
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华南理工大学
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Abstract

The invention discloses a polycaprolactone/calcium sulfate composite material and a preparation method thereof, belonging to the field of macromolecule modification. The method comprises the following steps: utilizing biosurfactant to carry out surface modification on anhydrous calcium sulfate or calcium sulfate whiskers; and adopting a coprecipitation and mould pressing method to prepare anhydrous calcium sulfate or calcium sulfate whiskers reinforced polycaprolactone composite material. The composite material prepared by the method in the invention has the advantages of high mechanical strength and adjustable performance, thereby laying a foundation for the application thereof.

Description

聚己内酯/硫酸钙复合材料及其制备方法 Polycaprolactone / calcium sulfate composite material and its preparation method

技术领域 FIELD

[0001] 本发明属于高分子改性领域,具体涉及聚己内酯/硫酸钙复合材料及其制备方法。 [0001] The present invention belongs to the field of polymer modification, particularly relates polycaprolactone / sulfated calcium composite material and its preparation method.

背景技术 Background technique

[0002] 聚己内酯具有耐水、耐油,及耐氯化物的性能,且具有较低的熔点(约60°C )与熔体粘度,这使其容易加工成型。 [0002] polycaprolactone having water, oil, and chloride resistance performance and having relatively low melting point (approximately 60 ° C) and melt viscosity, which makes it easy molding process. 聚己内酯因具有生物相容性、生物降解性与低毒性被应用于骨组织工程、药物缓释等领域。 Polycaprolactone due biocompatible, biodegradable and of low toxicity to be applied to tissue engineering, drug release and other fields. 虽然有上述的诸优点,但在实际应用中,聚己内酯的力学强度较低不能满足要求,需要对其进行增强改性。 Although there are various advantages described above, but in practice, the lower mechanical strength of polycaprolactone not meet the requirements, we need to be modified to enhance. [0003] 国内用来增强聚己内酯的主要有磷酸钙盐与羟基磷灰石,但磷酸钙盐的降解速度缓慢,羟基磷灰石在体内基本不会被吸收。 [0003] Polycaprolactone used to enhance domestic mainly calcium phosphate and hydroxyapatite, but slow degradation rate of calcium phosphate, hydroxyapatite is not substantially absorbed in the body. 而聚己内酯由于高结晶度降解很慢,因此,需要加入降解较快的增强组分。 And polycaprolactone degradation due to the high degree of crystallinity is very slow, therefore, the need for rapid degradation of the reinforcing component. 国内关于增强聚己内酯的发明专利较少,中国发明专利CN101693773A采用橡子粉对聚己内酯进行增强改性,但橡子粉的加入影响了聚己内酯的生物相容性与降解性,限制其应用领域。 On enhancing domestic polycaprolactone less patents, Chinese invention patent CN101693773A using acorn powder polycaprolactone-modified enhanced, but the powder was added acorn affect biocompatibility and degradation of polycaprolactone resistance, limiting its applications. 中国发明专利CN1593673A采用熔融共混或模压方法用甲壳素纤维增强聚己内酯,但传统的熔融共混工艺需在高于聚合物熔点的温度下进行,螺杆较强的剪切力与高温会使部分聚己内酯降解,从而影响材料的力学性能。 Chinese Patent No. CN1593673A invention, melt extrusion molding method or reinforced with polycaprolactone chitin fiber, conventional melt blending process should be carried out at a temperature above the melting point of the polymer, a strong shearing force of the screw and high temperature so that part of polycaprolactone degradation, thereby affecting mechanical properties.

发明内容 SUMMARY

[0004] 本发明的目的在于克服上述现有技术的缺点和不足,提供一种聚己内酯/硫酸钙复合材料及其制备方法,使硫酸钙的棒状与晶须结构在加工过程中不被破坏;聚己内酯的强度得到明显提高。 [0004] The object of the present invention is to overcome the above disadvantages and drawbacks of the prior art, there is provided a polycaprolactone / calcium sulfate composite material and its preparation method, the rod-like structure with calcium sulfate whisker is not in the process damage; polycaprolactone strength has been significantly improved.

[0005] 本发明的目的通过下述方案实现: [0005] The object of the present invention is achieved by the following scheme:

[0006] 聚己内酯/硫酸钙复合材料,该材料的组成主要为:聚己内酯5g〜19g、硫酸钙Ig 〜15g0 [0006] Polycaprolactone / calcium sulfate composite, the composition of the material is mainly: polycaprolactone 5g~19g, calcium sulfate Ig ~15g0

[0007] 所述硫酸钙为经过表面改性的无水硫酸钙或硫酸钙晶须;改性剂采用卵磷脂、鼠李糖脂、脂肽中的一种或者一种以上。 The [0007] calcium sulfate anhydrous calcium sulfate or calcium sulfate whiskers surface-modified; modifiers of lecithin A rhamnolipid, lipopeptide or one or more.

[0008] 上述聚己内酯/硫酸钙复合材料的制备方法,如下步骤: [0008] The method of preparing the composite material of calcium polycaprolactone / sulfuric acid, the following steps:

[0009] (I)共沉淀法制备聚己内酯与硫酸钙复合材料 [0009] (I) prepared by coprecipitation with calcium sulfate polycaprolactone Composites

[0010] 称取16g聚己内酯在50〜60°C恒温水浴中搅拌I小时使其完全溶解于四氢呋喃中;称取2. 4g硫酸钙,在常温下搅拌50分钟使其均匀分散于四氢呋喃中;将聚己内酯的四氢呋喃溶液倒入硫酸钙的四氢呋喃悬浮液中混合,常温下磁子搅拌2h ;超声15min后,再搅拌2小时;快速倒入盛有750ml无水乙醇的烧杯中,析出白色沉淀物;用无水乙醇反复清洗沉淀物;于35〜50°C真空干燥箱中干燥I天,得到粉状的聚己内酯与硫酸钙的共混物; [0010] Weigh 16g of polycaprolactone was stirred at 50~60 ° C water bath I hour and completely dissolved in tetrahydrofuran; 2. 4g weighed calcium sulfate, stirred at room temperature for 50 minutes uniformly dispersed in tetrahydrofuran ; and polycaprolactone tetrahydrofuran solution was poured into a suspension of calcium sulfate were mixed in tetrahydrofuran at room temperature a magnetic stirring 2H; after sonication 15min, stirred for 2 hours; quickly poured in a beaker of 750ml of anhydrous ethanol, a white precipitate; the precipitate was washed with ethanol again; at 35~50 ° C vacuum oven drying I days to obtain a powdery polycaprolactone and a blend of calcium sulfate;

[0011] (2)聚己内酯与无水硫酸钙复合材料的模压成型 [0011] (2) molded with polycaprolactone composite anhydrous calcium sulfate

[0012] 将共沉淀法制备的共混物在70〜75°C下预热45分钟使其完全熔融,在15MPa下热压5分钟,多次排气,然后于常温、15MPa冷压3分钟,开模取样。 [0012] The co-precipitated blend prepared by preheating at 70~75 ° C 45 minutes to completely melt, the hot pressing at 15MPa for 5 minutes, repeatedly evacuated and then at room temperature, cold 15MPa 3 minutes , to open mold. [0013] 上述方法中,所述硫酸钙为经过表面改性的无水硫酸钙或硫酸钙晶须, [0013] In the above method, the calcium sulfate is surface modified calcium sulfate or anhydrous calcium sulfate whisker,

[0014] (I)无水硫酸I丐的表面改性:称取0. 75g卵磷脂溶于220ml无水乙醇中,于30〜35°C下搅拌5小时,抽滤5次直至杂质除去。 [0014] (I) I hack surface-modified anhydrous sulfuric acid: Weigh 0. 75g of lecithin was dissolved in 220ml absolute ethanol was stirred at 30~35 ° C 5 hours 5 times until an impurity was removed by suction filtration. 然后加入15g硫酸钙,搅拌30分钟超声10分钟,再搅拌30分钟;用无水乙醇抽滤,清洗5次;在真空干燥箱中45°C下干燥20小时后得到表面改性的无水硫酸钙。 15g of calcium sulfate was then added, stirred for 30 minutes sonicated for 10 minutes, then stirred for 30 minutes; absolute ethanol with suction, washed 5 times; surface-modified drying 20 hours at 45 ° C in a vacuum oven sulfate anhydrous calcium. [0015] (2)硫酸钙晶须的表面改性:称取0. 75g卵磷脂溶于220ml无水乙醇中,于30〜35°C下搅拌5小时,抽滤5次直至杂质除去。 [0015] (2) a surface-modified calcium sulfate whiskers: Weigh 0. 75g of lecithin was dissolved in 220ml absolute ethanol was stirred at 30~35 ° C 5 hours 5 times until an impurity was removed by suction filtration. 然后加入15g硫酸钙晶须,搅拌30分钟超声10分钟,再搅拌30分钟;用无水乙醇抽滤,清洗5次;在真空干燥箱中45°C下干燥20小时后得到表面改性的硫酸钙晶须。 Was then added 15g of calcium sulfate whiskers, stirred for 30 minutes sonicated for 10 minutes, then stirred for 30 minutes; absolute ethanol with suction, washed 5 times; surface-modified drying 20 hours at 45 ° C in a vacuum oven sulfate calcium whiskers.

[0016] 所述无水硫酸钙或硫酸钙晶须表面改性所采用的改性剂还包括鼠李糖脂或者脂肽中的一种或者一种以上。 The modifier [0016] anhydrous calcium sulfate or calcium sulfate whiskers used in surface modification further comprises one or rhamnolipid lipopeptide or one or more.

[0017] 本发明聚己内酯/硫酸钙复合材料可应用于骨修复。 Polyhexamethylene invention [0017] The lactone / calcium sulfate composite bone repair material can be applied.

[0018] 本发明与现有技术相比,优点及效果在于,采用本发明聚己内酯/硫酸钙复合材料的制备方法,使硫酸钙的棒状与晶须结构在加工过程中不被破坏,聚己内酯的强度得到明显提高;在整个工艺过程中,不会使聚己内酯降解;本发明工艺简单,为其在临床应用领域广泛。 [0018] Compared with the prior art, advantages and effects that the present invention is polycaprolactone / preparation of a composite material of calcium sulfate, and the rod-like structure of calcium sulphate whiskers is not destroyed in the process, polycaprolactone strength has been significantly improved; the entire process, without degrading polycaprolactone; simple process of the present invention, in its broad clinical applications.

[0019] 硫酸钙具有高强度、低毒性,生物相容性好等优点,采用硫酸钙粉体与晶须改性聚己内酯,可同时提高聚己内酯的强度与韧性。 [0019] Calcium sulfate has high strength, low toxicity, good biocompatibility, etc., using calcium powder body and sulfate whisker modified polycaprolactone, can improve the strength and toughness of polycaprolactone simultaneously. 硫酸钙的降解速度较快,加入后,可改善聚己内酯降解较慢的不足。 Faster degradation rate of calcium sulphate, after addition of, polycaprolactone improves slow degradation is insufficient. 另外,一般工业用表面活性剂相比,生物活性表面活性剂具有无毒、生物相容性等优点,采用卵磷脂等生物活性表面活性剂对硫酸钙粉体与晶须改性可提高粉体与晶须表面的亲油值,使硫酸钙粉体及晶须与聚己内酯的界面粘结力增大,提高复合材料的力学性能,但复合材料却不会因具有毒性而受到应用限制。 Further, as compared with the general industrial surfactants, biologically active non-toxic surfactants, biocompatibility, etc., the use of biological surface active agents such as lecithin, and whiskers of calcium powder sulfate body modification may improve the powder and lipophilic values ​​whisker surface, so that the body of sulfuric acid and calcium powder interfacial adhesion whiskers polycaprolactone is increased, to improve the mechanical properties of the composites, but the composite material has not been applied because of its toxicity limits .

[0020] 采用硫酸钙晶须与聚己内酯复合则显现出明显的优点。 [0020] The calcium sulfate whiskers with polycaprolactone compound is demonstrable advantages. 硫酸钙晶须本身具有良好的生物相容性,能在体内降解吸收。 Calcium sulfate whisker itself has good biocompatibility and can be degraded and absorbed in vivo. 而且硫酸钙晶须结构类似于短玻璃纤维的结构,加入到聚己内酯中,可以有效提高材料的模量和冲击强度,而同时提高材料刚性与韧性是大部分粉体材料增强效果难以达到的。 And a structure similar to calcium sulfate whisker short glass fibers was added to the polycaprolactone, can effectively increase the modulus and impact strength, while increasing the material stiffness and toughness enhancing effect is most difficult to achieve a powder material of. 因此,本专利采用了硫酸钙晶须作为聚己内酯的增强基体。 Thus, this patent uses a CSW as polycaprolactone reinforcing matrix.

附图说明 BRIEF DESCRIPTION

[0021] 图I为本发明实施例I的无水硫酸钙增强聚己内酯复合材料的扫描电子显微镜照片。 [0021] FIG anhydrous calcium sulfate present I Example I enhanced scanning electron micrograph polycaprolactone composite material of the present invention.

[0022] 图2为本发明实施例2的硫酸钙晶须增强聚己内酯复合材料的扫描电子显微镜照片。 [0022] FIG. 2 CSW Example 2 Enhanced scanning electron micrograph of polycaprolactone composite material of the present invention.

[0023] 图3为本发明实施例3的改性无水硫酸钙增强聚己内酯复合材料的扫描电子显微镜照片。 [0023] FIG. 3 Modified Example 3 of anhydrous calcium sulfate embodiment enhanced scanning electron micrograph of polycaprolactone composite material of the present invention.

[0024] 图4为本发明实施例4的改性硫酸钙晶须增强聚己内酯复合材料的扫描电子显微镜照片。 [0024] FIG. 4 modified calcium sulfate whiskers of Example 4 enhanced scanning electron micrograph of polycaprolactone composite material of the present invention.

[0025] 图5为本发明实施例5的改性硫酸钙晶须增强聚己内酯复合材料的扫描电子显微镜照片。 [0025] FIG 5 modified calcium sulfate whiskers Example 5 Enhanced scanning electron micrograph of polycaprolactone composite material of the present invention. 具体实施方式 Detailed ways

[0026] 下面结合实施例及附图对本发明作进一步详细说明,但本发明的实施方式不限于此。 [0026] further below in conjunction with the accompanying drawings and the detailed description of embodiments of the present invention will be, but the embodiment of the present invention is not limited thereto.

[0027] 实施例I [0027] Example I

[0028] (I)共沉淀法制备聚己内酯与无水硫酸钙复合材料 [0028] (I) prepared by coprecipitation of polycaprolactone with anhydrous calcium sulfate composite

[0029] 称取16g聚己内酯在58°C恒温水浴中搅拌I小时使其完全溶解于四氢呋喃中;称取2. 4g无水硫酸钙粉末,在常温下搅拌50分钟使其均匀分散于四氢呋喃中;将聚己内酯的四氢呋喃溶液倒入无水硫酸钙的四氢呋喃悬浮液中混合,常温下磁子搅拌2h ;超声15min后,再搅拌2小时;快速倒入正在超声中、盛有750ml无水乙醇的烧杯中,析出白色沉淀物;用无水乙醇反复清洗沉淀物;于45°C真空干燥箱中干燥I天,得到粉状的聚己内酯与无水硫酸钙的混合物。 [0029] Weigh 16g of polycaprolactone was stirred at 58 ° C water bath I hour and completely dissolved in tetrahydrofuran; Weigh 2. 4g anhydrous calcium sulphate powder was stirred at room temperature for 50 minutes uniformly dispersed in tetrahydrofuran; polycaprolactone tetrahydrofuran solution of calcium sulphate anhydrous tetrahydrofuran was poured into the suspension mixed at room temperature a magnetic stirring 2H; after sonication 15min, stirred for 2 hours; is quickly poured ultrasound, filled with 750ml absolute ethanol in a beaker, a white precipitate; washed repeatedly with ethanol precipitate; 45 ° C for I day dried in a vacuum oven, to obtain a powdery mixture of polycaprolactone with anhydrous calcium sulfate.

[0030] (2)聚己内酯与无水硫酸钙复合材料的模压成型 [0030] (2) molded with polycaprolactone composite anhydrous calcium sulfate

[0031] 将共沉淀法制备的共混物在75°C下预热45分钟使其完全熔融,在15MPa下热压5分钟,多次排气,然后于常温、15MPa冷压3分钟,开模取样(160 X 10 X 4mm3)。 [0031] The co-precipitated blend prepared by preheating at 75 ° C 45 minutes to completely melt, the hot pressing at 15MPa for 5 minutes, repeatedly evacuated and then at room temperature, cold 15MPa for 3 minutes, open sampling mold (160 X 10 X 4mm3).

[0032] 实施例2 [0032] Example 2

[0033] (I)共沉淀法制备聚己内酯与硫酸钙晶须复合材料 [0033] (I) prepared by coprecipitation of polycaprolactone with calcium sulfate whisker composites

[0034] 称取16g聚己内酯在50°C恒温水浴中搅拌I小时使其完全溶解于四氢呋喃中;称取2. 4g的改性无水硫酸钙粉末,在常温下搅拌50分钟使其均匀分散于四氢呋喃中;将聚己内酯的四氢呋喃溶液倒入硫酸钙晶须的四氢呋喃悬浮液中混合,常温下磁子搅拌2h ;超声15min后,再搅拌2小时;快速倒入正在超声中、盛有750ml无水乙醇的烧杯中,析出白色沉淀物;用无水乙醇反复清洗沉淀物;于351:真空干燥箱中干燥I天,得到粉状的聚己内酯与硫酸钙晶须的混合物。 [0034] Weigh 16g of polycaprolactone was stirred 50 ° C and water bath I hour and completely dissolved in tetrahydrofuran; modified anhydrous calcium sulfate weighed 2. 4g of powder was stirred 50 minutes at room temperature, it uniformly dispersed in tetrahydrofuran; the CSW in tetrahydrofuran mixed suspension of tetrahydrofuran was poured into a polycaprolactone, a magnetic stirring at room temperature 2H; after sonication 15min, stirred for 2 hours; is quickly poured ultrasound, beaker containing 750ml of anhydrous ethanol, a white precipitate; washed repeatedly with ethanol precipitate; to 351: I day vacuum oven dried to give a mixture of polycaprolactone and calcium sulfate powdery whiskers .

[0035] (2)聚己内酯与改性硫酸钙晶须复合材料的模压成型 [0035] (2) molded with polycaprolactone-modified calcium sulfate whisker composites

[0036] 将共沉淀法制备的共混物在70°C下预热45分钟使其完全熔融,在15MPa下热压5分钟,多次排气,然后于常温、15MPa冷压3分钟,开模取样(160 X 10 X 4mm3)。 [0036] The co-precipitated blend prepared by preheating at 70 ° C 45 minutes to completely melt, the hot pressing at 15MPa for 5 minutes, repeatedly evacuated and then at room temperature, cold 15MPa for 3 minutes, open sampling mold (160 X 10 X 4mm3).

[0037] 实施例3 [0037] Example 3

[0038] (I)无水硫酸钙的表面改性 [0038] The surface modification (I) of anhydrous calcium sulfate

[0039] 称取0. 75g卵磷脂溶于220ml无水乙醇中,于35°C下搅拌5小时,抽滤5次直至杂质除去。 [0039] Weigh 0. 75g of lecithin was dissolved in 220ml absolute ethanol was stirred at 35 ° C 5 hours 5 times until an impurity was removed by suction filtration. 然后加入15g硫酸钙,搅拌30分钟,超声10分钟,再搅拌30分钟;用无水乙醇抽滤,清洗5次;在真空干燥箱中50°C下干燥20小时后得到表面改性的无水硫酸钙。 15g of calcium sulfate was then added, stirred for 30 minutes, sonicated for 10 minutes and then stirred for 30 minutes; absolute ethanol with suction, washed five times; after vacuum drying cabinet at 50 ° C for 20 hours to obtain surface-modified anhydrous Calcium sulfate.

[0040] (2)共沉淀法制备聚己内酯与改性无水硫酸钙复合材料 [0040] (2) Coprecipitation with polycaprolactone-modified anhydrous calcium sulfate composite SYSTEM

[0041] 称取16g聚己内酯在60°C恒温水浴中搅拌I小时使其完全溶解于四氢呋喃中;称取2. 4g的改性无水硫酸钙粉末,在常温下搅拌50分钟使其均匀分散于四氢呋喃中;将聚己内酯的四氢呋喃溶液倒入无水硫酸钙的四氢呋喃悬浮液中混合,常温下磁子搅拌2h ;超声15min后,再搅拌2小时;快速倒入正在超声中、盛有750ml无水乙醇的烧杯中,析出白色沉淀物;用无水乙醇反复清洗沉淀物;于301:真空干燥箱中干燥I天,得到粉状的聚己内酯与改性无水硫酸钙的混合物。 [0041] Weigh 16g of polycaprolactone was stirred at 60 ° C water bath I hour and completely dissolved in tetrahydrofuran; modified anhydrous calcium sulfate weighed 2. 4g of powder was stirred 50 minutes at room temperature, it uniformly dispersed in tetrahydrofuran; polycaprolactone tetrahydrofuran solution was poured into calcium sulfate anhydrous tetrahydrofuran was mixed at room temperature a magnetic stirring 2H; after sonication 15min, stirred for 2 hours; is quickly poured ultrasound, beaker containing 750ml of anhydrous ethanol, a white precipitate; washed repeatedly with ethanol precipitate; to 301: I was dried in a vacuum oven days, to obtain a powdery polycaprolactone-modified with anhydrous calcium sulfate mixture.

[0042] (3)聚己内酯与改性无水硫酸钙复合材料的模压成型 [0042] (3) molded with polycaprolactone-modified anhydrous calcium sulfate Composites

[0043] 将共沉淀法制备的共混物在71°C下预热45分钟使其完全熔融,在15MPa下热压5分钟,多次排气,然后于常温、15MPa冷压3分钟,开模取样(160 X 10 X 4mm3) [0043] The co-precipitated blend prepared by preheating at 71 ° C 45 minutes to completely melt, the hot pressing at 15MPa for 5 minutes, repeatedly evacuated and then at room temperature, cold 15MPa for 3 minutes, open sampling mold (160 X 10 X 4mm3)

[0044] 实施例4 [0044] Example 4

[0045] (I)硫酸钙晶须的表面改性 [0045] The surface modification (I) of the calcium sulfate whisker

[0046] 称取0. 75g卵磷脂溶于220ml无水乙醇中,于35°C下搅拌5小时,抽滤5次直至杂质除去。 [0046] Weigh 0. 75g of lecithin was dissolved in 220ml absolute ethanol was stirred at 35 ° C 5 hours 5 times until an impurity was removed by suction filtration. 然后加入15g硫酸钙晶须,搅拌30分钟,超声10分钟,再搅拌30分钟;用无水乙醇抽滤,清洗5次;在真空干燥箱中45°C下干燥20小时后得到表面改性的硫酸钙晶须。 Was then added 15g of calcium sulfate whiskers, stirred for 30 minutes, sonicated for 10 minutes and then stirred for 30 minutes; absolute ethanol with suction, washed 5 times; surface-modified drying 20 hours at 45 ° C in a vacuum oven calcium sulfate whiskers.

[0047] (2)共沉淀法制备聚己内酯与改性硫酸钙晶须复合材料 [0047] (2) co-caprolactone-modified calcium sulfate whisker and composite precipitation of poly Method

[0048] 称取16g聚己内酯在55°C恒温水浴中搅拌I小时使其完全溶解于四氢呋喃中;称取2. 4g的改性硫酸钙晶须,在常温下搅拌50分钟使其均匀分散于四氢呋喃中;将聚己内酯的四氢呋喃溶液倒入改性硫酸钙晶须的四氢呋喃悬浮液中混合,常温下磁子搅拌2h ;超声15min后,再搅拌2小时;快速倒入正在超声中、盛有750ml无水乙醇的烧杯中,析出白色沉淀物;用无水乙醇反复清洗沉淀物;于451:真空干燥箱中干燥I天,得到粉状的聚己内酯与改性硫酸钙晶须的混合物。 [0048] Weigh 16g of polycaprolactone was stirred at 55 ° C water bath I hour and completely dissolved in tetrahydrofuran; weighed modified calcium sulfate whiskers 2. 4g stirred at room temperature for 50 minutes homogeneously dispersed in tetrahydrofuran; tetrahydrofuran solution was poured into a polycaprolactone-modified calcium sulfate whiskers tetrahydrofuran was mixed at room temperature a magnetic stirring 2H; after sonication 15min, stirred for 2 hours; ultrasound is quickly poured , a beaker of 750ml of anhydrous ethanol, a white precipitate; washed repeatedly with ethanol precipitate; to 451: I was dried in a vacuum oven days, to obtain a powdery polycaprolactone-modified with calcium sulfate crystals to be a mixture.

[0049] (3)聚己内酯与改性硫酸钙晶须复合材料的模压成型 [0049] (3) molded with polycaprolactone-modified calcium sulfate whisker composites

[0050] 将共沉淀法制备的共混物在70°C下预热45分钟使其完全熔融,在15MPa下热压5分钟,多次排气,然后于常温、15MPa冷压3分钟,开模取样(160 X 10 X 4mm3)。 [0050] The co-precipitated blend prepared by preheating at 70 ° C 45 minutes to completely melt, the hot pressing at 15MPa for 5 minutes, repeatedly evacuated and then at room temperature, cold 15MPa for 3 minutes, open sampling mold (160 X 10 X 4mm3).

[0051] 实施例5 [0051] Example 5

[0052] (I)硫酸钙晶须的表面改性 [0052] The surface modification (I) of the calcium sulfate whisker

[0053] 称取0. 75g卵磷脂溶于220ml无水乙醇中,于35°C下搅拌5小时,抽滤5次直至杂质除去。 [0053] Weigh 0. 75g of lecithin was dissolved in 220ml absolute ethanol was stirred at 35 ° C 5 hours 5 times until an impurity was removed by suction filtration. 然后加入15g硫酸钙晶须,搅拌30分钟,超声10分钟,再搅拌30分钟;用无水乙醇抽滤,清洗5次;在真空干燥箱中45°C下干燥20小时后得到表面改性的硫酸钙晶须。 Was then added 15g of calcium sulfate whiskers, stirred for 30 minutes, sonicated for 10 minutes and then stirred for 30 minutes; absolute ethanol with suction, washed 5 times; surface-modified drying 20 hours at 45 ° C in a vacuum oven calcium sulfate whiskers.

[0054] (2)共沉淀法制备聚己内酯与改性硫酸钙晶须复合材料 [0054] (2) co-caprolactone-modified calcium sulfate whisker and composite precipitation of poly Method

[0055] 称取16g聚己内酯在60°C恒温水浴中搅拌I小时使其完全溶解于四氢呋喃中;称取4g的改性硫酸钙晶须,在常温下搅拌50分钟使其均匀分散于四氢呋喃中;将聚己内酯的四氢呋喃溶液倒入改性硫酸钙晶须的四氢呋喃悬浮液中混合,常温下磁子搅拌2h ;超声15min后,再搅拌2小时;快速倒入正在超声中、盛有750ml无水乙醇的烧杯中,析出白色沉淀物;用无水乙醇反复清洗沉淀物;于401:真空干燥箱中干燥I天,得到粉状的聚己内酯与改性硫酸钙晶须的混合物。 [0055] Weigh 16g of polycaprolactone was stirred at 60 ° C water bath I hour and completely dissolved in tetrahydrofuran; modified calcium sulfate whiskers weighed 4g stirred at room temperature for 50 minutes uniformly dispersed in tetrahydrofuran; tetrahydrofuran solution was poured into a polycaprolactone-modified calcium sulfate whiskers tetrahydrofuran was mixed at room temperature a magnetic stirring 2H; after sonication 15min, stirred for 2 hours; is quickly poured ultrasound, Sheng beaker with 750ml of anhydrous ethanol, a white precipitate; washed repeatedly with ethanol precipitate; to 401: I was dried in a vacuum oven days, to obtain a powdery polycaprolactone-modified calcium sulfate whiskers with mixture.

[0056] (3)聚己内酯与改性硫酸钙晶须复合材料的模压成型 [0056] (3) molded with polycaprolactone-modified calcium sulfate whisker composites

[0057] 将共沉淀法制备的共混物在73°C下预热45分钟使其完全熔融,在15MPa下热压5分钟,多次排气,然后于常温、15MPa冷压3分钟,开模取样(160 X 10 X 4mm3)。 [0057] The co-precipitated blend prepared by preheating at 73 ° C 45 minutes to completely melt, the hot pressing at 15MPa for 5 minutes, repeatedly evacuated and then at room temperature, cold 15MPa for 3 minutes, open sampling mold (160 X 10 X 4mm3).

[0058] 下表为:实施例I〜5纯聚己内酯与复合材料力学性能 [0058] The following table: pure polycaprolactone and Mechanical Properties Example embodiments I~5

[0059] [0059]

Figure CN101974212BD00071

[0060] 上述实施例仅为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。 [0060] The above-described embodiments are merely preferred embodiments of the present invention, but the embodiments of the present invention is not limited to the above embodiments, any other changes made to the spirit and principle of the present invention without departing from the next, modifications, substitutions , combined, simplified, should be equivalent replacement method, it is included within the scope of the present invention.

Claims (3)

  1. 1.聚己内酯/硫酸钙复合材料的制备方法,其特征在于如下步骤: (1)共沉淀法制备聚己内酯与硫酸钙复合材料称取16g聚己内酯在50〜60°C恒温水浴中搅拌I小时使其完全溶解于四氢呋喃中;称取2. 4g硫酸钙,在常温下搅拌50分钟使其均匀分散于四氢呋喃中;将聚己内酯的四氢呋喃溶液倒入硫酸钙的四氢呋喃悬浮液中混合,常温下磁子搅拌2h ;超声15min后,再搅拌2小时;快速倒入盛有750ml无水乙醇的烧杯中,析出白色沉淀物;用无水乙醇反复清洗沉淀物;于35〜50°C真空干燥箱中干燥I天,得到粉状的聚己内酯与硫酸钙的共混物; (2)聚己内酯与无水硫酸钙复合材料的模压成型将共沉淀法制备的共混物在70〜75°C下预热45分钟使其完全熔融,在15MPa下热压5分钟,多次排气,然后于常温、15MPa冷压3分钟,开模取样。 1. Polycaprolactone / preparation of composite calcium sulfate, characterized by the steps of: (1) Preparation of total polycaprolactone and composite precipitation of calcium sulfate was weighed 16g of polycaprolactone at 50~60 ° C constant temperature water bath was stirred for I hour and completely dissolved in tetrahydrofuran; 2. 4g weighed calcium sulfate, stirred for 50 minutes at room temperature in tetrahydrofuran homogeneously dispersed; polycaprolactone tetrahydrofuran solution was poured into calcium sulfate in tetrahydrofuran the suspension was mixed at room temperature a magnetic stirring 2H; after sonication 15min, stirred for 2 hours; quickly poured in a beaker of 750ml of anhydrous ethanol, a white precipitate; washed repeatedly with ethanol precipitate; 35 ~50 ° C vacuum drying oven I days to obtain a powdery polycaprolactone and a blend of calcium sulphate; (2) a polycaprolactone with anhydrous calcium sulfate molded composites prepared co-precipitate preheating a blend of at 70~75 ° C 45 minutes to completely melt, the hot pressing at 15MPa for 5 minutes, repeatedly evacuated and then at room temperature, cold 15MPa for 3 minutes to open mold.
  2. 2.根据权利要求I所述的制备方法,其特征在于,所述硫酸钙为经过表面改性的无水硫Ifef丐或硫Ifef丐晶须; 所述经过表面改性的无水硫酸钙按如下方法制备:称取0. 75g卵磷脂溶于220ml无水乙醇中,于35°C下搅拌5小时,抽滤5次直至杂质除去;然后加入15g硫酸钙,搅拌30分钟超声10分钟,再搅拌30分钟;用无水乙醇抽滤,清洗5次;在真空干燥箱中45°C下干燥20小时后得到表面改性的无水硫酸钙; 所述经过表面改性的硫酸钙晶须按如下方法制备:称取0. 75g卵磷脂溶于220ml无水乙醇中,于35°C下搅拌5小时,抽滤5次直至杂质除去;然后加入15g硫酸钙晶须,搅拌30分钟超声10分钟,再搅拌30分钟;用无水乙醇抽滤,清洗5次;在真空干燥箱中45°C下干燥20小时后得到表面改性的硫酸钙晶须。 The production method according to claim I, wherein the calcium sulfate is subjected to surface-modified anhydrous sulfur or sulfur Ifef Ifef Hack Hack whiskers; a surface modified by anhydrous calcium sulfate It was prepared as follows: Weigh 0. 75g of lecithin was dissolved in 220ml absolute ethanol was stirred at 35 ° C 5 hours 5 times until an impurity was removed by suction filtration; 15g calcium sulphate was then added, stirred for 30 minutes sonicated for 10 minutes, then stirred for 30 minutes; absolute ethanol with suction, washed five times; to obtain the surface-modified anhydrous calcium sulfate drying 20 hours at 45 ° C in a vacuum oven; the surface modified calcium sulfate whiskers by It was prepared as follows: Weigh 0. 75g of lecithin was dissolved in 220ml absolute ethanol was stirred at 35 ° C 5 hours 5 times until an impurity was removed by suction filtration; then add 15g of calcium sulfate whiskers, stirred for 30 min 10 min of ultrasonication , stirring for 30 minutes; absolute ethanol with suction, washed 5 times; surface-modified calcium sulfate whiskers after drying 20 hours at 45 ° C in a vacuum oven.
  3. 3.根据权利要求2所述的制备方法,其特征在于,所述经过表面改性的无水硫酸钙或硫酸钙晶须所采用的改性剂还包括鼠李糖脂或者脂肽中的一种或者一种以上。 3. The production method according to claim 2, wherein the surface modified modifier anhydrous calcium sulfate or calcium sulfate whiskers employed further comprises a rhamnolipid of the lipopeptide or or one or more species.
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