CN110101905A - A kind of iron content polyacrylate bone cement and preparation method - Google Patents

Abstract

The present invention relates to a kind of iron content polyacrylate bone cement and preparation methods.Iron content polyacrylate, barium sulfate and benzoyl peroxide are weighed according to the mass percentage of powder, is uniformly mixed to get bone cement powder；According to powder liquid 1~3:1 of mass ratio, powder is added in liquid and is uniformly mixed, solidification obtains iron content polyacrylate bone cement, and bone cement injection time is 5~12min；Ferroso-ferric oxide is introduced in the preparation process of polyacrylate powder, the particle size distribution of the iron content polyacrylate powder of preparation is 0.2~100 μm, improves the syringeability of bone cement.The mechanical property of bone cement is improved, and compression strength is up to 80.82MPa.Due to the addition of ferroso-ferric oxide, reduce the sharply release of energy in bone cement polymerization process, reduces bone cement polymerization to the thermal damage of tissue, there is good biocompatibility and osteoinductive, can be used for the fixation of a variety of fracture, the filling of bone defect.

Description

A kind of iron-containing polyacrylate bone cement and preparation method thereof

technical field

The invention relates to an iron-containing polyacrylate bone cement and a preparation method, and belongs to the field of orthopedic materials.

Background technique

Polyacrylate (PMMA) bone cement is currently the most widely used bone cement in clinical practice. It consists of powder and liquid. The main component of powder is polymethyl methacrylate, and the main component of liquid is methyl methacrylate monomer. Bone cement can be injection molded and made into any shape. It has the advantages of good mechanical strength and stable performance. It is currently a widely used vertebroplasty material. At present, there are at least 40 kinds of PMMA bone cement on the domestic market, which are widely used in orthopedic filling materials and fixation materials, especially in the treatment of vertebral compression fractures by vertebroplasty, which can quickly stabilize the injured vertebral body and relieve the symptoms of patients. . However, there are still some limitations of bone cement, such as slightly poor mechanical properties and poor fusion with surrounding tissues. Therefore, the research on modified PMMA bone cement is particularly important. Through the improvement of performance, its physical and chemical properties and biological properties can be improved.

Among the magnetic substances, the most studied is iron tetroxide, commonly known as iron oxide black, magnets, etc. It is a black crystal with magnetic properties, so it is also called magnetic iron oxide. As a multifunctional magnetic material, it has been widely used in tumor treatment, microwave absorption material, catalyst carrier, cell separation, magnetic recording material, magnetic fluid, medicine and other fields. Magnetic bone cement is about introducing a magnetic substance into the bone cement, giving the bone cement good magnetic properties and improving the mechanical properties of the bone cement. However, there are few reports on the bone cement containing magnetic iron oxide.

Therefore, a kind of iron-containing polyacrylate bone cement is designed in the present invention. In the process of preparing PMMA powder, ferric tetroxide is introduced to give PMMA certain magnetic properties, and the ratio of the reaction is controlled to prepare iron-containing PMMA, and it is mixed with Bone cement is prepared by compounding polyacrylate, barium sulfate, etc. Through the introduction of magnetic ferric oxide, the bone cement can be heated by magnetic hysteresis to achieve the effect of magnetic therapy and sterilization, and at the same time improve the injectability and mechanical strength of bone cement , to improve the biocompatibility and osteoinductivity of bone cement. There is no report on the research on the relevant content of the present invention.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide an iron-containing polyacrylate bone cement and a preparation method. In the process of preparing the polyacrylate powder, adding ferric tetroxide can improve the particle size distribution range of the polyacrylate powder and improve the availability of the bone cement. Injectable, and improve the mechanical properties of bone cement, its compressive strength is as high as 80.82MPa. Secondly, the introduction of ferric tetroxide imparts magnetic properties to the bone cement, which can be heated by the hysteresis loss phenomenon in the bone cement to achieve the effect of magnetic therapy sterilization, and at the same time endow the bone cement with good biocompatibility and osteoinductivity.

The technical scheme of the present invention is as follows:

An iron-containing polyacrylate bone cement, the bone cement composition and mass percentage are:

Powder:

Iron-containing polyacrylate 65% to 89%;

Barium sulfate 10% to 30%;

Benzoyl peroxide 1% to 5%;

liquid:

N,N-dimethyl-p-toluidine 0.5%～5%;

Hydroquinone 0.05%～2%;

Methyl methacrylate 93-99.45%;

The mass ratio of powder to liquid is 1 to 3:1.

The preparation method of the iron-containing polyacrylate bone cement of the present invention comprises the following steps:

1) Weigh iron-containing polyacrylate, barium sulfate and benzoyl peroxide according to the mass percentage of the powder, and uniformly mix to obtain the bone cement powder;

2) According to the mass ratio of powder to liquid of 1～3:1, add the powder into the liquid and mix evenly, solidify to obtain iron-containing polyacrylate bone cement, and the injection time of the bone cement is 5～12min;

Wherein: the preparation method of iron-containing polyacrylate powder is as follows:

(1) According to the ferric oxide: cetyl trimethyl ammonium bromide: methyl methacrylate molar ratio of 0.1 ~ 0.5: 0.2: 1, ferric tetroxide, cetyl trimethyl bromide Ammonium is added to methyl methacrylate, ultrasonically dispersed, and then mechanically stirred to obtain a suspension liquid of ferric oxide;

(2) Prepare a suspension containing 0.2-3% dibenzoyl peroxide (BPO), the solution temperature is 90-135°C, and then add 0.001%-0.002% dodecyl mercaptan to the BPO suspension And continue to stir to obtain the BPO suspension containing dodecyl mercaptan;

(3) the suspension liquid of ferric tetroxide prepared in step (1) is heated to 60～80 ℃ and then added to the BPO suspension liquid in the stirring process, uniformly mixed and continuously stirred for reaction, washed with water, dried and filtered to obtain iron-containing liquid Polyacrylate powder.

The ultrasonic dispersion condition in the step (1) is 5KHz ultrasonic dispersion for 10-30 minutes.

In the step (1), mechanical stirring is performed for 10-30 min, and the stirring rate is 600-1200 rpm.

In the step (2), the stirring time is 4-8 h, and the stirring speed is 600-1200 rpm.

In the step (3), the mass ratio of the ferric oxide suspension to the BPO suspension is 1:1, the stirring reaction is performed for 12-36 hours, and the stirring rate is 600-1200 rpm.

The particle size distribution range of the iron-containing polyacrylate is 0.2-100 μm.

The advantages of the present invention lie in that ferric tetroxide is introduced in the preparation process of the polyacrylate powder, the particle size distribution range of the prepared iron-containing polyacrylate powder is 0.2-100 μm, and the injectability of the bone cement is improved. Secondly, the mechanical properties of bone cement were improved, and its compressive strength was as high as 80.82MPa. In addition, the introduction of iron-containing polyacrylate imparts certain magnetic properties to the polyacrylate powder. When the bone cement is implanted in the defect, the bone cement can be heated by magnetic hysteresis through the change of the magnetic field strength, which has the function of bactericidal and bacteriostatic. On the other hand, due to the addition of ferric oxide, the rapid release of energy in the process of bone cement polymerization is reduced, and the thermal damage to the tissue caused by bone cement polymerization is reduced. , to achieve the effect of bactericidal and bacteriostatic, with good biocompatibility and osteoinductivity, and can be used for the fixation of various fractures and the filling of bone defects.

Description of drawings

Figure 1: Compressive strength graph of iron-containing bone cement.

Detailed ways

The content of the present invention will be further described in detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.

The preparation method of iron-containing polyacrylate bone cement is as follows:

(1) According to the ferric oxide: cetyl trimethyl ammonium bromide: methyl methacrylate molar ratio of 0.1 ~ 0.5: 0.2: 1, ferric tetroxide, cetyl trimethyl bromide Ammonium is added to methyl methacrylate, 5KHz ultrasonic dispersion is performed for 10-30 minutes, and mechanical stirring is performed for 10-30 minutes to obtain a suspension liquid of ferric oxide, and the stirring speed is 600-1200 rpm.

(2) Prepare a BPO suspension containing 0.2-3%, the solution temperature is 90-135°C, then add 0.001%-0.002% dodecyl mercaptan to the BPO suspension and continue stirring for 4-8h, stirring The speed is 600～1200rpm;

(3) the suspension liquid of ferric tetroxide prepared in step (1) is heated to 60～80° C. in the stirring process, and added to the BPO suspension liquid of step (2), the suspension liquid of ferric oxide The mass ratio to the BPO suspension is 1:1, the reaction is continuously stirred for 12 to 36 hours, the stirring speed is 600 to 1200 rpm, and the iron-containing polyacrylate powder can be obtained by washing with water, drying and filtering;

(4) weighing iron-containing polyacrylate, barium sulfate and benzoyl peroxide according to the mass percentage of the powder, and uniformly mixing to obtain bone cement powder;

(5) According to the mass ratio of powder to liquid of 1 to 3:1, the powder is added to the liquid and mixed evenly, and solidified to obtain iron-containing polyacrylate bone cement, and the injection time of the bone cement is 5 to 12 minutes.

The particle size distribution range of the iron-containing polyacrylate is 0.2-100 μm.

Example 1

Bone cement is powder containing 89g iron-containing polyacrylate, 10g barium sulfate, 1g benzoyl peroxide; liquid contains 5g N,N dimethyl-p-toluidine, 2g hydroquinone, 93g methyl alcohol Methyl acrylate.

The iron-containing polyacrylate bone cement and its preparation method are as follows:

(1) 23.154 g of ferric oxide, hexadecyl trimethyl bromide, 23.154 g of ferric tetroxide, hexadecyl trimethyl bromide were 0.1:0.2:1 according to the molar ratio of ferric oxide: cetyl trimethyl ammonium bromide: methyl methacrylate 72.89g of ammonium was added to 100.1g of methyl methacrylate, 5KHz ultrasonic dispersion was carried out for 30min, and then mechanical stirring was performed for 10min to obtain a suspension liquid of ferric oxide, and the stirring speed was 600rpm;

(2) 3g of BPO was added to 97g of deionized water to obtain a BPO suspension containing 3%, the solution temperature was 135°C, and 0.002g of dodecyl mercaptan was added, and the stirring was continued for 4h at a stirring speed of 600rpm;

(3) 100g of the suspension liquid of ferric tetroxide was heated to 80°C during the stirring process, added to 100g of BPO suspension liquid, continued to stir and react for 12h, the stirring speed was 600rpm, washed with water, dried and filtered to obtain the iron-containing liquid. Polyacrylate powder, the particle size distribution range of iron-containing polyacrylate is 0.2～100μm;

(4) take by weighing the iron-containing polyacrylate of 89g, the barium sulfate of 10g, the benzoyl peroxide of 1g according to the mass percentage content of the powder, and uniformly mix to obtain the bone cement powder;

(5) According to the mass ratio of powder to liquid of 2:1, take 100 g of powder and 50 g of liquid, add the powder to the liquid and mix evenly, solidify to obtain iron-containing polyacrylate bone cement, and the injection time of bone cement is 10 minutes.

The iron-containing polyacrylate bone cement was injected into the sample preparation mold, and after curing, a sample with a diameter of 6.0 mm and a length of 12 mm was obtained. The compressive strength test was carried out on a universal mechanical testing machine. As shown in Figure 1-A, the compressive strength of the prepared sample was 79.45 MPa.

Example 2

The powder contains 65g of iron-containing polyacrylate, 30g of barium sulfate, and 5g of benzoyl peroxide; the liquid contains 0.5g of N,N-dimethyl-p-toluidine, 0.05g of hydroquinone, and 99.45g of methylbenzene. Methyl acrylate.

The iron-containing polyacrylate bone cement and its preparation method are as follows:

(1) 115.77g of ferric oxide, hexadecyl trimethyl bromide, 115.77 g of ferric tetroxide, hexadecyl trimethyl bromide according to the molar ratio of ferric oxide: cetyl trimethyl ammonium bromide: methyl methacrylate 0.5: 0.2: 1 72.89g of ammonium was added to 100.1g of methyl methacrylate, ultrasonically dispersed at 5KHz for 10min, and then mechanically stirred for 30min to obtain a suspension liquid of ferric oxide, and the stirring speed was 1000rpm;

(2) 0.2g of BPO was added to 99.8g of deionized water to obtain a BPO suspension containing 0.2%, the solution temperature was 135°C, 0.001g of dodecyl mercaptan was added, and the stirring was continued for 6h at a stirring speed of 1000rpm. ;

(3) 100g of the suspension liquid of ferric tetroxide was heated to 60°C during stirring, added to 100g of BPO suspension, continuously stirred and reacted for 36h, the stirring speed was 1000rpm, washed with water, dried and filtered to obtain iron-containing liquid. Polyacrylate powder, the particle size distribution range of iron-containing polyacrylate is 0.2 to 100 μm;

(4) take by weighing the iron-containing polyacrylate of 65g, the barium sulfate of 30g, the benzoyl peroxide of 5g according to the mass percentage content of the powder, and uniformly mix to obtain the bone cement powder;

(5) According to the mass ratio of powder to liquid of 3:1, add 60 g of powder to 20 g of liquid and mix evenly, solidify to obtain iron-containing polyacrylate bone cement, and the injection time of bone cement is 5 minutes.

The iron-containing polyacrylate bone cement was injected into the sample preparation mold, and after curing, a sample with a diameter of 6.0 mm and a length of 12 mm was obtained. The compressive strength test was carried out on a universal mechanical testing machine. As shown in Figure 1-B, the compressive strength of the prepared sample was 80.82 MPa.

Example 3

The powder contains 70g of iron-containing polyacrylate, 27g of barium sulfate, and 3g of benzoyl peroxide; the liquid contains 2g of N,N-dimethyl-p-toluidine, 1g of hydroquinone, and 97g of methyl methacrylate. ester.

The iron-containing polyacrylate bone cement and its preparation method are as follows:

(1) According to the ferric oxide: cetyl trimethyl ammonium bromide: methyl methacrylate molar ratio of 0.3: 0.2: 1, ferric oxide 69.462g, cetyl trimethyl bromide 72.89g of ammonium was added to 100.1g of methyl methacrylate, 5KHz ultrasonic dispersion was performed for 20min, and then mechanical stirring was performed for 20min to obtain a suspension liquid of ferric oxide, and the stirring speed was 1200rpm;

(2) 2g of BPO was added to 98g of deionized water to obtain a BPO suspension containing 2%, the solution temperature was 110°C, and the solution was continuously stirred for 4h, and 0.0016g of dodecyl mercaptan was added, and the stirring rate was 1200rpm;

(3) 100g of the suspension liquid of ferric oxide was heated to 70°C during stirring, added to 100g of BPO suspension, continuously stirred for 24h, the stirring rate was 1200rpm, washed with water, dried and filtered to obtain the iron-containing polymer Acrylic powder;

(4) take by weighing the iron-containing polyacrylate of 70g, the barium sulfate of 27g, the benzoyl peroxide of 3g according to the mass percentage content of the powder, and uniformly mix to obtain the bone cement powder;

(5) According to the mass ratio of powder to liquid of 1:1, add 50 g of powder to 50 g of liquid and mix evenly, solidify to obtain iron-containing polyacrylate bone cement, and the injection time of bone cement is 12 minutes.

The bone cement was injected into the sample preparation mold, and after curing, a sample with a diameter of 6.0 mm and a length of 12 mm was obtained. The compressive strength test was carried out on a universal mechanical testing machine. As shown in Figure 1-C, the compressive strength of the prepared sample was 75.11 MPa.

The iron-containing polyacrylate bone cement disclosed and proposed in the present invention and its preparation method can be realized by those skilled in the art by referring to the content of this article and appropriately changing the conditions and routes, although the method and preparation technology of the present invention have been implemented through better implementation. The examples are described, and those skilled in the art can obviously modify or recombine the methods and technical routes described herein without departing from the content, spirit and scope of the present invention to realize the final preparation technology. It should be particularly pointed out that all similar substitutions and modifications apparent to those skilled in the art are deemed to be included in the spirit, scope and content of the present invention.

Claims (7)

1. an iron-containing polyacrylate bone cement is characterized in that the bone cement composition and mass percentage are: Powder: Iron-containing polyacrylate 65% to 89%; Barium sulfate 10～30%; Benzoyl peroxide 1% to 5%; liquid: N,N dimethyl-p-toluidine 0.5%～5%; Hydroquinone 0.05%～2%; Methyl methacrylate 93-99.45%; The mass ratio of powder to liquid is 1 to 3:1. 2. the preparation method of the iron-containing polyacrylate bone cement of claim 1, is characterized in that comprising the steps: 1) Weigh iron-containing polyacrylate, barium sulfate and benzoyl peroxide according to the mass percentage of the powder, and uniformly mix to obtain the bone cement powder; 2) According to the mass ratio of powder to liquid of 1～3:1, add the powder into the liquid and mix evenly, solidify to obtain iron-containing polyacrylate bone cement, and the injection time of the bone cement is 5～12min; Wherein: the preparation method of iron-containing polyacrylate powder is as follows: (1) According to the ferric oxide: cetyl trimethyl ammonium bromide: methyl methacrylate molar ratio of 0.1 ~ 0.5: 0.2: 1, ferric tetroxide, cetyl trimethyl bromide Ammonium is added to methyl methacrylate, ultrasonically dispersed, and then mechanically stirred to obtain a suspension liquid of ferric oxide; (2) Prepare a suspension containing 0.2-3% dibenzoyl peroxide (BPO), the solution temperature is 90-135°C, and then add 0.001%-0.002% dodecyl mercaptan to the BPO suspension And continue to stir to obtain the BPO suspension containing dodecyl mercaptan; (3) the suspension liquid of ferric oxide prepared in step (1) is heated to 60～80 ℃ and then added to the BPO suspension liquid in the stirring process, and the suspension liquid of ferric oxide and the BPO suspension liquid are added to the BPO suspension liquid. The mass ratio of the powder is 1:1, the mixture is evenly mixed and the reaction is continued for 12-36 hours, washed with water, dried and filtered to obtain the iron-containing polyacrylate powder. 3. The method of claim 2, wherein the ultrasonic dispersion condition in the step (1) is 5KHz ultrasonic dispersion for 10-30 min. 4. The method according to claim 2, characterized in that in the step (1), mechanical stirring is performed for 10-30 min, and the rotating speed is 600-1200 rpm. 5. The method according to claim 2, characterized in that in the step (2), the stirring time is 4-8h, and the rotating speed is 600-1200rpm. 6. The method of claim 2, characterized in that in the step (3), the reaction is stirred for 12 to 36 h, and the rotating speed is 600 to 1200 rpm. 7. The method of claim 2, wherein the particle size distribution range of the iron-containing polyacrylate is 0.2-100 μm.