KR20150007600A

KR20150007600A - Manufacturing method of organic／inorganic complex based on calcium solution

Info

Publication number: KR20150007600A
Application number: KR20130081768A
Authority: KR
Inventors: 조성백; 안응모; 이수정; 장희동
Original assignee: 한국지질자원연구원
Priority date: 2013-07-11
Filing date: 2013-07-11
Publication date: 2015-01-21

Abstract

The present invention relates to a method for producing an organic-inorganic hybrid material derived from a calcium solution, and more particularly, to a method for producing a calcium-based organic-inorganic hybrid material by mixing a limestone with a strong acid, Preparing a mixed solution by sequentially dissolving a dispersant, a calcium solution, a catalyst, and an organosilicon compound in a solvent; Gelling and aging the mixed solution to produce a wet gel; Drying the wet gel and subjecting it to a first heat treatment to produce amorphous calcium silicate; And a step of mixing the prepared calcium silicate with a polymer matrix in an oil-based ball mill, followed by compression molding and a second heat treatment to prepare an organic-inorganic hybrid material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a calcium-

The present invention relates to a method for producing a calcium-based organic-inorganic hybrid material.

Our skeleton consists of 206 bones. These bones support our bodies, protect important organs such as the brain and internal organs, as well as allowing them to move independently, allowing a variety of exercises. In recent years, there has been an increase in cases of bone tissue damage due to diseases such as osteoporosis and automobile accidents due to the progress of the aging society. Materials for repairing such damaged bone tissue have been studied for a long time. Alumina (Al ₂ O ₃ ), stainless steel, or titanium (Ti), which are materials showing hydrophilicity without eluting harmful components in the body, have been used for this purpose.

However, since these materials do not chemically bond directly to the bones of a living body, the surfaces of the materials are made porous or irregularly formed to enhance the binding ability with the bones, so that the bones are fixed by a mechanical method in which the bones grow. However, bone cement has begun to be used as an attempt to fix the implant to the surrounding bone tissue, which requires a long period of time of two to three months or longer before such bonding is achieved. Thus, it has been found that glass and crystallized glass containing CaO and SiO ₂ as the main components directly bind to the living bone, that is, bioactivity, and have been used as various artificial bone substitutes. However, in order to produce such a CaO-SiO ₂ -based bioactive glass and a crystallized glass, the CaO-SiO ₂ glass produced by the melting method must be melted at a high temperature of usually 1450 ° C. or more. When the content of SiO ₂ is 60 If the weight% is exceeded, the bioactivity is lost and it can not be directly bound to the living bone, so that it can not be used as a biomaterial.

Meanwhile, in order to solve the problems of conventional inorganic materials such as glass, crystallized glass and the like, a complex is prepared by using an organic polymer having no biodegradability such as high density polyethylene (HDPE) and the like, Studies have been made on the production of surface bioactive organic / inorganic composites which cause the glass and calcium phosphate compound fillers to exhibit bioactivity only on the surface of the organic / inorganic composite. Bonefield et al. Conducted a study to obtain a bioactive material similar to that of a living bone bone by simultaneously taking a mixture of HDPE and micrometer in a physiological saline-derived apatite ceramics powder.

However, despite these studies, there is a problem that separation of bioactive powder at the interface between them, problems of production techniques, and selectivity of composition and microstructure are small.

Prior art related to the present invention is Korean Patent No. 10-0890935 entitled "PIKE AND CALCIUM DIOXIDE-BIOACTIVE COMPOSITION FOR ARTIFICIAL BONES USING SILICON BONE AND METHOD FOR PRODUCING THE SAME, " ).

Accordingly, the present invention is to provide a method for producing a calcium / magnesium-based organic / inorganic composite having improved mechanical strength by mixing a calcium matrix-based calcium silicate compound with a polymer matrix.

The problems to be solved by the present invention are not limited to the above-mentioned problem (s), and another problem (s) not mentioned can be understood by those skilled in the art from the following description.

In order to solve the above-mentioned problems, the present invention provides a method for producing a calcium solution, comprising the steps of: stirring a limestone with a strong acid; Preparing a mixed solution by sequentially dissolving a dispersant, a calcium solution, a catalyst, and an organosilicon compound in a solvent; Gelling and aging the mixed solution to produce a wet gel; Drying the wet gel and subjecting it to a first heat treatment to produce amorphous calcium silicate; And mixing the prepared calcium amorphosilicate with a polymer matrix in an oil-based ball mill, followed by compression molding and a second heat treatment to prepare an organic-inorganic hybrid material.

At this time, the limestone is characterized in that the impurities are 0.4 to 0.8 wt% and the ignition loss is 42 to 44 wt% with respect to the total limestone weight.

The strong acid may be nitric acid, and the concentration of the strong acid is 1 to 10 M.

Further, the limestone is characterized by being contained in a mixing ratio (g / L) of 50 to 500 with respect to the total volume of strong acid.

The gelation and aging is performed at 30 to 80 ° C for 6 to 24 hours.

The first heat treatment is performed at 400 to 900 DEG C for 60 to 240 minutes.

The polymer matrix is characterized by being polyetheretherketone (PEEK).

The calcium silicate and the polymer matrix are mixed at a weight ratio of 10 to 40:90 to 60.

The press molding is performed at 90 to 110 kgf / cm < 2 >.

And the second heat treatment is performed at 310 to 360 ° C for 1 to 3 hours at a heating rate of 0.5 to 10 ° C / min.

The present invention also relates to a polyetheretherketone (PEEK) and an amorphous CaO-SiO ₂ , wherein the polyetheretherketone and amorphous CaO-SiO ₂ are in the range of 10-40: 90-60 Based complex containing a calcium solution.

According to the present invention, the first heat treatment temperature can be rapidly lowered by using the calcium solution formed from limestone, and the process cost can be saved because the first heat treatment temperature is lowered.

Also, since the amorphous calcium silicate is produced by adjusting the concentration of strong acid in the calcium solution prepared from limestone and strong acid, which has excellent mechanical strength of the organic-inorganic hybrid material including the polymer matrix, bioactivity can be greatly improved.

Further, the organic-inorganic hybrid material according to the present invention can be used as an adhesive for fixing metals, polymers, ceramics and the like to bones and can be strongly bonded to bones in a short period of time. Therefore, implant fixation such as artificial joints, restoration of bones and teeth, It can be applied in a wide range of fields such as oral care, orthopedics, brain surgery, plastic surgery and oral surgery.

1 is a flowchart showing a method for producing a calcium-based organic-inorganic hybrid material according to a preferred embodiment of the present invention.
FIG. 2 is a photograph showing CaO-SiO ₂ according to concentration of calcium solution and drying time. FIG.
3 is a photograph showing the CaO-SiO ₂ compound before and after the heat treatment.
4 is a graph showing the weight loss rate of CaO-SiO ₂ before and after the heat treatment.
5 is a scanning electron microscope (SEM) photograph showing CaO-SiO ₂ in the manufacturing method according to the present invention.
6 is a scanning electron microscope (SEM) photograph of a polymer matrix PEEK.
7 is a scanning electron microscope (SEM) photograph (FIG. 7 (a)), energy dispersive spectroscopy (EDS) after mixing amorphous CaO-SiO ₂ and PEEK as a polymer matrix in a planetary ball mill in the manufacturing method according to the present invention, (Fig. 7 (b)) and the mapping result (Fig. 7 (c)).
8 is a schematic view showing a compression molding process of amorphous CaO-SiO ₂ and a polymer matrix PEEK in the manufacturing method according to the present invention, and a composite photograph before and after compression molding.
9 is a scanning electron microscope (SEM) photograph (FIG. 9A), an energy dispersive spectroscopy (EDS) result (FIG. 9B) and a mapping (FIG. 9B) of a composite after compression molding in the manufacturing method according to the present invention Mapping results (FIG. 9 (c)).
10 is a scanning electron microscope (SEM) photograph (FIG. 10A), an energy dispersive spectroscopy (EDS) result (FIG. 10B) and a mapping Mapping results (FIG. 10 (c)).

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.

The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

The present invention relates to a process for producing a calcium solution, comprising the steps of stirring a limestone with a strong acid and then filtering to prepare a calcium solution;

Preparing a mixed solution by sequentially dissolving a dispersant, a calcium solution, a catalyst, and an organosilicon compound in a solvent;

Gelling and aging the mixed solution to produce a wet gel;

Drying the wet gel and subjecting it to a first heat treatment to produce amorphous calcium silicate; And

And mixing the prepared calcium amorphosilicate with a polymer matrix in an oil-based ball mill, followed by compression molding and second heat treatment to prepare an organic-inorganic hybrid material.

The method for producing an organic-inorganic hybrid material according to the present invention can drastically lower the first heat treatment temperature by using the calcium solution formed from limestone, and can reduce the process cost due to the first heat treatment temperature being lowered. Also, the bioactivity of amorphous (amorphous, amorphous) calcium silicate compounds is greatly improved by controlling the concentration of strong acid in the calcium solution made of limestone and strong acid, which has excellent mechanical strength of the organic-inorganic hybrid material including the polymer matrix . Therefore, the organic / inorganic composite can be used as an adhesive for fixing metal, polymer, ceramic, etc. to the bone and can be strongly bonded to the bone in a short period of time. Therefore, it is possible to fix the implant such as artificial joint, restoration of bones and teeth, It can be applied in a wide range of fields such as surgery, brain surgery, plastic surgery, and oral surgery.

1 is a flowchart showing a method for producing a calcium-based organic-inorganic hybrid material according to the present invention. The present invention will be described in more detail with reference to Fig.

The method for producing a calcium-based organic-inorganic hybrid material according to the present invention includes a step (S10) of mixing a limestone with a strong acid and then filtering to prepare a calcium solution.

The limestone may have an impurity content of 0.4 to 0.8% by weight and a loss on ignition of 42 to 44% by weight based on the total weight of limestone. Specific examples of the limestone are shown in Table 1 of the following examples.

The limestone can be crushed and ground. The crushing may be performed with a jaw crusher and a cone crusher.

The crushed limestone is crushed, the crushed can be carried out with a pulverizer, and the crushed and crushed limestone can have a size of 3 mm or less. If the size of the crushed and ground limestone exceeds 3 mm, the limestone is dissolved in the strong acid, the reaction time is prolonged and the impurity mineral is not completely separated in addition to the limestone. Therefore, the solubility in strong acid is decreased, .

Crushed and pulverized limestone is stirred with strong acid, and nitric acid, hydrochloric acid, sulfuric acid and the like can be used as the strong acid, but nitric acid can greatly reduce the process cost and can maximally improve the dissolution rate of limestone.

The concentration of the strong acid may be 1 to 10M. If the concentration of the strong acid is less than 1M, the limestone can not be completely dissolved. If the concentration exceeds 10M, the concentration of the strong acid is high and the solid-liquid separation can not be performed after the limestone is dissolved.

In addition, the limestone may be contained at a mixing ratio (g / L) of 50 to 500 with respect to the total weight of strong acid. When the mixing ratio is less than 50 g / L in the concentration range of 1 M to 10 M of nitric acid and at the low concentration of 1 M, the amount of strong acid required to dissolve the limestone is excessively added to lower the economical efficiency. g / L, the amount of strong acid required to dissolve the limestone is insufficient, so that the limestone can not be completely dissolved. Also, since the water content is low in the mixture of limestone and strong acid, solid-liquid separation may be difficult. More specifically, when the amount of limestone added to nitric acid (volume) is 50 to 500 g, the amount of limestone that can be dissolved in nitric acid from the minimum to the maximum is set. That is, 50 g is the maximum amount that can be dissolved at the lowest concentration (1 M) of nitric acid, and therefore, in the case of less than 50 g, the acid necessary for dissolving the nitric acid limestone remains. In addition, 500 g is the maximum amount of nitric acid that can be dissolved at the highest concentration (10M), and when it exceeds 500 g, limestone remains because of insufficient melting acid. In case of melting more than 500 g, 10 M of strong acid is almost pure 60% of nitric acid, so there is almost no water. After the reaction with limestone, the viscosity (stickiness and fluidity) of the liquid becomes high and the filter (filtration) becomes impossible .

Stirring of the crushed and ground limestone and strong acid can be carried out for 5 to 15 minutes. When the agitation is performed for less than 5 minutes, the limestone and the strong acid are not sufficiently mixed to lower the dissolution rate of the limestone to the strong acid, so that the purification efficiency of the limestone may be lowered. In terms of process efficiency, 15 minutes or less is appropriate.

Next, a method for producing a calcium-based organic-inorganic hybrid material according to the present invention includes a step (S20) of sequentially dissolving a dispersant, a calcium solution, a catalyst and an organosilicon compound in a solvent to prepare a mixed solution.

When the dispersant, the calcium solution, the catalyst, and the organosilicon compound are sequentially added to a solvent and stirred, the respective materials are dissolved in the solvent, thereby preparing a mixed solution.

The solvent may include at least one selected from the group consisting of water, distilled water and deionized water.

The dispersant may include at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and polypropylene glycol glyceryl.

The catalyst may comprise nitric acid.

The organosilicon compound may include at least one selected from the group consisting of tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. .

The method for preparing a calcium-based organic-inorganic hybrid material according to the present invention includes a step (S30) of gelling and aging the mixed solution to prepare a wet gel.

The mixed solution is gelled with a wet gel at a temperature of 30 to 80 ° C, and the aging is also performed at 30 to 80 ° C. Specifically, the gelation and aging may be performed at 30 to 80 ° C for 6 to 24 hours. When the gelation and aging temperature is less than 30 ° C, the continuity of the element-binding network with Si is lowered in the case of a cation such as Ca, and when the temperature exceeds 80 ° C, the aging temperature is increased to cause dry cracking do.

In addition, the method for producing the organic-inorganic hybrid material according to the present invention includes a step (S40) of drying the wet gel and performing a first heat treatment.

The drying may be carried out at 30 to 80 ° C for 5 to 7 days. When the drying temperature is less than 30 ° C, unnecessary energy is consumed by the delay of the drying time in drying the wetting gel (white, wet gel after gelation and aging). When the drying temperature exceeds 80 ° C, The shape of the plate shape is a problem that the moisture in the wet gel is rapidly evaporated so that the center portion of the wet gel is bent toward the back surface with respect to the quadrangular surface, resulting in deterioration of the formability and cracking of the shape of the square plate due to dry crack.

Also, the first heat treatment may be performed at 400 to 900 ° C. for 60 to 240 minutes. When the temperature of the heat treatment is less than 400 ° C, there is a problem that spherical particles can not be aggregated in the porous structure having continuous pores. When the temperature exceeds 900 ° C, the crystalline product of quartz and cristobalite Is formed.

The method for producing a calcium-based organic-inorganic hybrid material according to the present invention includes a step (S50) of mixing the prepared calcium silicate and a polymer matrix with an oil-based ball mill, followed by compression molding and a second heat treatment to prepare an inorganic hybrid material.

As the polymer matrix, polyether ether ketone (PEEK) or the like may be used.

The calcium silicate and the polymer matrix of Apolpose may be mixed at a weight ratio of 10-40: 90-60. When the weight ratio is out of the above range, there is a problem in the strength of the obtained organic / inorganic hybrid material.

In addition, the press molding can be performed at 90 to 110 kgf / cm < 2 >. When the pressure molding is performed at less than 90 kgf / cm 2, there is a problem with the strength of the obtained organic / inorganic hybrid material. When the pressure molding exceeds 110 kgf / cm 2, more than necessary pressure is used, which is inefficient in terms of energy efficiency.

The second heat treatment may be performed at 310 to 360 ° C for 1 to 3 hours at a heating rate of 0.5 to 10 ° C / min. When the second heat treatment temperature is less than 310 ° C, the polyether ether ketone (PEEK) as a polymer is not completely dissolved and the strength of the organic-inorganic hybrid material deteriorates. When the second heat treatment temperature is higher than 360 ° C, (PEEK) is completely dissolved.

The present invention also relates to a polyetheretherketone (PEEK) and amorphous CaO-SiO ₂ , wherein the polyetheretherketone and amorphous CaO-SiO ₂ are present in a weight ratio of 10-40: 90-60 Based complex having a calcium-based solution.

The organic-inorganic hybrid material derived from the calcium solution can be prepared by the above-described production method, and has excellent mechanical strength including a polymer matrix and excellent amorphous CaO-SiO ₂ -containing bioactivity, so that it can be used as an artificial bone composite have.

Example 1: Preparation of organic-inorganic hybrid material (CaO-SiO ₂ / PEEK) 1

Stirring the limestone with a strong acid and then filtering to prepare a calcium solution (S10):

The limestone of Table 1 below was crushed using a jaw crusher and a cone crusher. The crushed limestone was pulverized using a pulverizer. Crushed and pulverized limestone had a size distribution of less than 3 mm. 100 g of the crushed and ground limestone and 1000 mL of nitric acid were mixed by stirring for 10 minutes. At this time, the concentration of nitric acid was 1M. The mixture of limestone and strong acid was filtered to prepare a calcium solution.

Table 1 shows the results of analysis of the components and contents of limestone by X-ray fluorescence (XRF).

ingredient SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO Weight loss content(%) 0.13 0.03 0.11 55.70 0.59 43.34

(S20) of preparing a mixed solution by sequentially dissolving a dispersant, a calcium solution, a catalyst and an organosilicon compound in a solvent,

First, the CaO-SiO ₂ gel was prepared by hydrolysis of tetraethoxysilane (TEOS: Si (C ₂ H ₅ O ₄ )) in an aqueous solution and then polycondensation.

Specifically, a solution of 4.9 g of polyethylene glycol, 10 g of the above calcium solution (concentration: 1M, 2M, 3M, 4M and 5M respectively) and 5.6 g of nitric acid (62 wt%) were added sequentially to 60 g of distilled water , And 41.66 g of tetraethoxysilane (TEOS: Si (C ₂ H ₅ O ₄ )) was added while vigorously stirring, and the solution was stirred until the solution became transparent to prepare a solution solution.

Step S30 of gelling and aging the mixed solution:

The mixed solution was transferred into a plastic container. The lid was sealed with a tape and placed in a volume of 40 DEG C to form a wet gel, followed by aging in an oven at 40 DEG C for 18 hours.

Drying and heat-treating step S40:

The wet gel prepared above was taken out of the plastic container, dried continuously in an oven at 40 ° C for 6 days, and then dried. Then, heat treatment was performed in a furnace using a siliconite heating element. The heat treatment was performed at a heating rate of 800 ° C for 8 hours and then maintained for 2 hours. After 2 hours, the furnace was slowly cooled in the furnace to produce amorphous CaO-SiO ₂ .

Mixing the calcium silicate and the polymer matrix with a planetary ball mill, compression molding and performing a second heat treatment (S50);

16 g of the amorphous CaO-SiO ₂ prepared above and ₂₄ g of PEEK (main component: carbon, average particle size of 50 탆) were placed in a planetary ball mill equipped with 10 mm zirconia balls (100) and then mixed at 300 rpm for 60 minutes Respectively. 0.25 g of a mixture of amorphous CaO-SiO ₂ and PEEK was compression molded at 100 kgf / cm 2 (9.8 MPa) for 2 minutes and then heated in an electric furnace at a heating rate of 5 ° C / min for 2 hours at 320 ° C cooled after step ruling prepare a CaO-SiO ₂ / PEEK organic-inorganic composite.

Example 2: Preparation of an organic-inorganic hybrid material (CaO-SiO ₂ / PEEK) 2

Except that 20 g of calcium solution (concentration: 1M, 2M, 3M, 4M and 5M respectively) were dissolved in distilled water during the preparation of the mixed solution, and the CaO-SiO ₂ / PEEK organic solvent Complex.

Example 3: Preparation of organic-inorganic hybrid material (CaO-SiO ₂ / PEEK) 3

Except that 30 g of calcium solution (concentration: 1M, 2M, 3M, 4M, and 5M respectively) were dissolved in distilled water during the preparation of the mixed solution, except that CaO-SiO ₂ / PEEK organic Complex.

FIG. 2 is a photograph showing the CaO-SiO ₂ compound according to the concentration of the calcium solution and the drying time.

FIG. 3 is a photograph showing the CaO-SiO ₂ compound before and after the first heat treatment, FIG. 3 (a) is CaO-SiO ₂ before the heat treatment, and FIG. 3 (b) is the CaO-SiO ₂ compound after the heat treatment. As shown in FIG. 3, it can be seen that the amorphous CaO-SiO ₂ compound is reduced in weight and reduced in volume before the heat treatment by performing the heat treatment.

Table 2 After the dried gel of CaO-SiO ₂ by weight and the heat treatment after measuring the weight of the amorphous CaO-SiO ₂ compound shows the rate of weight decrease.

Yes Calcium solution Mass of dried CaO-SiO ₂
(g) Mass of CaO-SiO ₂ after heat treatment
(g) Weight reduction rate
(%) Example 1 1M 20.12 12.22 60.74 2M 20.90 13.14 62.87 3M 20.66 12.58 60.89 4M 20.46 13.02 63.64 5M 20.47 12.45 60.82 Example 2 1M 20.90 12.57 60.14 2M 21.91 13.19 60.20 3M 22.30 13.26 59.46 4M 21.99 12.82 58.30 5M 22.12 12.97 58.63 Example 3 1M 21.45 12.43 57.95 2M 24.32 12.32 50.66 3M 24.63 12.78 51.89 4M 24.50 13.39 54.65 5M 24.72 13.38 54.13

4 is a graph showing a weight reduction rate of CaO-SiO ₂ before and after the first heat treatment based on the results of Table 2 above.

FIG. 5 is a scanning electron microscope (SEM) photograph of CaO-SiO ₂ in the manufacturing method according to the present invention, and FIG. 6 is a scanning electron microscope (SEM) photograph of a polymer matrix PEEK. As shown in FIG. 5, it can be seen that the amorphous CaO-SiO ₂ has a spherical shape of about 3 micrometers. Further, as shown in FIG. 6, it can be seen that PEEK is a polymer having an average particle size of 50 micrometers, and its main component is carbon.

7 is a scanning electron microscope (SEM) photograph (FIG. 7 (a)), energy dispersive spectroscopy (EDS) after mixing amorphous CaO-SiO ₂ and PEEK as a polymer matrix in a planetary ball mill in the manufacturing method according to the present invention, (Fig. 7 (b)) and the mapping result (Fig. 7 (c)). As shown in FIG. 7, it can be seen that amorphous CaO-SiO ₂ is embedded on the surface of the PEEK matrix, and both materials are synthesized in the result of EDS and mapping, so that amorphous CaO-SiO ₂ aggregates on the entire PEEK Dispersed, and mixed effectively.

8 is a schematic view showing a compression molding process of calcium amorphosilicate and a polymer matrix PEEK in a manufacturing method according to the present invention, and a composite photograph before and after compression molding.

9 is a scanning electron microscope (SEM) photograph (FIG. 9A), an energy dispersive spectroscopy (EDS) result (FIG. 9B) and a mapping (FIG. 9B) of a composite after compression molding in the manufacturing method according to the present invention Mapping results (FIG. 9 (c)). As shown in FIG. 9, in the scanning electron microscope photographs magnified 1,000 times, it can be seen that amorphous CaO-SiO ₂ is distributed in the PEEK matrix. As a result of EDS component analysis, the carbon of PEEK is detected, and amorphous CaO- ₂ , Ca, Si, and O components are present together. Also, in the mapping photograph, it can be seen that amorphous CaO-SiO ₂ is uniformly distributed in the PEEK matrix.

10 is a scanning electron microscope (SEM) photograph (FIG. 10A), an energy dispersive spectroscopy (EDS) result (FIG. 10B) and a mapping Mapping results (FIG. 10 (c)). As shown in FIG. 10, when the compression-molded composite was subjected to the second heat treatment, the matrix PEEK began to be melted and the integrity with CaO-SiO ₂ was effectively achieved. On the surface, amorphous CaO-SiO ₂ was drawn on the surface, but it was confirmed that the two materials were made into a single composite because the melted PEEK grabbed amorphous CaO-SiO ₂ . The results of the EDS mapping show that PEEK and amorphous CaO-SiO ₂ are evenly dispersed after the second heat treatment.

Although the present invention has been described with respect to specific embodiments of the method for producing a calcium-based organic-inorganic hybrid material according to the present invention, it is apparent that various modifications can be made without departing from the scope of the present invention.

Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.

It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.

Claims

Stirring the limestone with a strong acid and then filtering to prepare a calcium solution;
Preparing a mixed solution by sequentially dissolving a dispersant, a calcium solution, a catalyst, and an organosilicon compound in a solvent;
Gelling and aging the mixed solution to produce a wet gel;
Drying the wet gel and subjecting it to a first heat treatment to produce amorphous calcium silicate; And
And mixing the prepared calcium silicate with the polymer matrix in an oil-based ball mill, followed by compression molding and second heat treatment to produce an organic-inorganic hybrid material.

The method according to claim 1,
Wherein the limestone has an impurity content of 0.4 to 0.8% by weight and a loss on ignition of 42 to 44% by weight based on the total weight of the limestone.

The method according to claim 1,
Wherein the strong acid is nitric acid.

The method according to claim 1,
Wherein the concentration of the strong acid is 1 to 10M.

The method according to claim 1,
Wherein the limestone is contained in a mixing ratio (g / L) of 50 to 500 with respect to the total volume of strong acid.

The method according to claim 1,
Wherein the gelation and aging are carried out at 30 to 80 캜 for 6 to 24 hours.

The method according to claim 1,
Wherein the first heat treatment is performed at 400 to 900 DEG C for 60 to 240 minutes.

The method according to claim 1,
Wherein the polymer matrix is polyether ether ketone (PEEK).

The method according to claim 1,
Wherein the calcium silicate and the polymer matrix are mixed at a weight ratio of 10-40: 90-60.

The method according to claim 1,
Wherein the press molding is performed at 90 to 110 kgf / cm < 2 >.

The method according to claim 1,
Wherein the second heat treatment is performed at 310 to 360 ° C for 1 to 3 hours at a temperature raising rate of 0.5 to 10 ° C / min.

(PEEK) and amorphous CaO-SiO ₂ , and the polyether ether ketone and amorphous CaO-SiO ₂ are present in a weight ratio of 10 to 40:60 to 90 Complexes.