CN112957524B

CN112957524B - Bone cement and preparation method and application thereof

Info

Publication number: CN112957524B
Application number: CN202110218587.3A
Authority: CN
Inventors: 聂洪涛; 张凯; 王璇; 张洪玮
Original assignee: Beijing Bonsci Technology Co ltd
Current assignee: Beijing Bonsci Technology Co ltd
Priority date: 2021-02-24
Filing date: 2021-02-24
Publication date: 2022-05-17
Anticipated expiration: 2041-02-24
Also published as: CN112957524A

Abstract

The invention provides bone cement and a preparation method and application thereof, and relates to the technical field of medical materials. The bone cement comprises powder and liquid, wherein the powder comprises polymethyl methacrylate, esterified starch, an initiator and a developer, and the liquid comprises a methyl methacrylate monomer, an accelerant and a polymerization inhibitor; the esterified starch is added into the powder, and when the powder and the liquid are mixed, the characteristic that the esterified starch can expand rapidly at a certain temperature is utilized, so that the solidification speed of the bone cement is accelerated, the solidification time is shortened, and the esterified starch has good mechanical properties and overcomes the defects of slow solidification speed and long solidification time of the existing bone cement. The invention also provides a preparation method and application of the bone cement, and the bone cement has good application in preparing materials for bone filling or bone repair in view of the advantages of the bone cement.

Description

Bone cement and preparation method and application thereof

Technical Field

The invention relates to the technical field of medical materials, in particular to bone cement and a preparation method and application thereof.

Background

Bone cement is a material mainly used for filling defects and fixing transplants in the orthopedic bone repair process. The bone cement may be of various types, for example, Polymethylmethacrylate (PMMA) bone cement, calcium phosphate bone cement, and the like. Because PMMA bone cement is easy to form and convenient to use, PMMA bone cement is one of the more commonly used bone cements at present.

However, in clinical use, PMMA bone cement is found to have a too long setting time, easily causing bone cement leakage, and to wait for a long time after filling with bone cement.

In view of the above, the present invention is particularly proposed to solve at least one of the above technical problems.

Disclosure of Invention

The first object of the present invention is to provide a bone cement which can be set rapidly, has a short setting time and has good mechanical properties.

The second object of the present invention is to provide a method for preparing the bone cement.

The third purpose of the invention is to provide the application of the bone cement.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the invention provides bone cement, which comprises the following raw materials: the mass volume ratio of the powder to the liquid is (2-2.2 g): 1 mL;

the powder comprises polymethyl methacrylate, esterified starch, an initiator and a developer; wherein the mass fraction of the esterified starch in the powder is 4-8%;

the liquid comprises methyl methacrylate monomer, an accelerator and a polymerization inhibitor.

Further, on the basis of the technical scheme of the invention, the powder comprises the following raw materials in percentage by mass, based on 100% of the weight of the powder:

77.5-87.5% of polymethyl methacrylate, 4-8% of esterified starch, 0.5-2.5% of initiator and 8-12% of developer.

Further, on the basis of the above technical scheme of the present invention, the preparation method of the esterified starch comprises the following steps:

mixing starch, a catalyst and a solvent, carrying out pre-catalysis treatment, then adding a modifier for esterification reaction, and separating the mixture obtained after modification to obtain the esterified starch.

Further, on the basis of the above technical solution of the present invention, the starch includes plant starch, preferably includes any one or a combination of at least two of cereal starch, bean starch or potato starch, and further preferably includes any one or a combination of at least two of corn starch, wheat starch, rice starch, sorghum starch, soybean starch, tapioca starch or potato starch;

preferably, the catalyst comprises any one or a combination of at least two of pyridine, triethylamine or 4-dimethylaminopyridine, preferably pyridine;

preferably, the solvent comprises any one of a mixture of lithium chloride and N, N-dimethylformamide, ethyl acetate or dimethyl sulfoxide, preferably comprises ethyl acetate;

preferably, the modifier comprises any one or a combination of at least two of acryloyl chloride, acetyl chloride, methacryloyl chloride, stearic acid acyl chloride, caprylic acid acyl chloride, dodecanoic acid acyl chloride or stearic acid acyl chloride, and preferably comprises methacryloyl chloride;

preferably, the mass ratio of the starch, the catalyst and the solvent is 1: (0.5-1): (0.5-1);

preferably, the mass of the modifier accounts for 4-6% of the mass of the starch;

preferably, the pre-catalysis temperature is 15-25 ℃, and the pre-catalysis time is 1-2 h;

preferably, the temperature of the esterification reaction is 20-50 ℃, preferably 25-30 ℃;

preferably, the esterification reaction time is from 0.5 to 6 hours, preferably from 1 to 4 hours.

Further, on the basis of the above technical solution of the present invention, the initiator includes any one or a combination of at least two of benzoyl peroxide, cyclohexanone peroxide or methyl ethyl ketone peroxide, and preferably includes benzoyl peroxide;

preferably, the developer comprises any one or a combination of at least two of barium sulfate, zirconium dioxide or tantalum powder, preferably barium sulfate and/or zirconium dioxide.

Further, on the basis of the technical scheme of the invention, the liquid comprises the following raw materials in percentage by mass, based on 100% of the weight of the liquid:

96.991-98.991% of methyl methacrylate monomer, 1.0-3.0% of accelerator and 0.009-0.011% of polymerization inhibitor.

Further, on the basis of the above technical solution of the present invention, the accelerator includes any one or a combination of at least two of N, N-dimethyl-p-toluidine, N-dimethylaniline, N-diethylaniline or thiol, preferably includes N, N-dimethyl-p-toluidine;

preferably, the polymerization inhibitor comprises any one or a combination of at least two of hydroquinone, 2, 4-dimethyl-6-tert-butylphenol or nitrosophenol, preferably comprises hydroquinone.

Further, on the basis of the technical scheme of the invention, the bone cement comprises powder and liquid, and the mass volume ratio of the powder to the liquid is 2-2.2 g: 1 mL;

the powder comprises the following raw materials in percentage by mass, based on 100% of the weight of the powder:

78-86.5% of polymethyl methacrylate, 4-8% of esterified corn starch, 0.5-2.5% of benzoyl peroxide and 8-12% of barium sulfate;

the liquid comprises the following raw materials in percentage by mass, calculated by taking the weight of the liquid as 100%:

96.991-98.991% of methyl methacrylate monomer, 1.0-3.0% of N, N-dimethyl-p-toluidine and 0.009-0.011% of hydroquinone.

The invention also provides a preparation method of the bone cement, which comprises the following steps:

mixing the powder and the liquid and then solidifying to obtain bone cement;

preferably, the setting time is 8.0-10.5 min.

The invention also provides application of the bone cement in preparing materials for bone filling or bone repair.

Compared with the prior art, the invention has the following technical effects:

(1) the invention provides bone cement, which comprises powder and liquid, wherein the powder comprises polymethyl methacrylate, esterified starch, an initiator and a developer, and the liquid comprises a methyl methacrylate monomer, an accelerator and a polymerization inhibitor; the esterified starch is added into the powder, and when the powder and the liquid are mixed, the characteristic that the esterified starch can expand rapidly at a certain temperature is utilized, so that the solidification speed of the bone cement is accelerated, the solidification time is shortened, and the esterified starch has good mechanical properties and overcomes the defects of slow solidification speed and long solidification time of the existing bone cement.

(2) The invention provides the preparation method of the bone cement, which is simple to operate and stable in process.

(3) The invention provides the application of the bone cement, and the bone cement has good application in preparing materials for bone filling or bone repair in view of the advantages of the bone cement.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the implementation, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.

According to a first aspect of the present invention, there is provided a bone cement comprising the following raw materials: powder and liquid, wherein the mass volume ratio of the powder to the liquid is 2-2.2 g: 1 mL;

the liquid comprises methyl methacrylate monomer, an accelerant and a polymerization inhibitor.

The bone cement provided by the invention comprises powder and liquid, wherein the powder comprises polymethyl methacrylate, esterified starch, an initiator and a developer, and the liquid comprises a methyl methacrylate monomer, an accelerator and a polymerization inhibitor; the esterified starch is added into the powder, and when the powder and the liquid are mixed, the characteristic that the esterified starch can expand rapidly at a certain temperature is utilized, so that the solidification speed of the bone cement is accelerated, the solidification time is shortened, and the defects of slow solidification speed and long solidification time of the conventional bone cement are overcome.

In particular, bone cement is also called bone cement, which is a medical material used for orthopedic surgery. The bone cement of the invention takes polymethyl methacrylate as a main body and mainly consists of two phases of powder and liquid. The typical but non-limiting mass to volume ratio of powder to liquid is 2 g: 1mL, 2.1 g: 1mL or 2.2 g: 1 mL.

Besides polymethyl methacrylate, the powder also comprises an initiator and a developer. The main function of the initiator is to initiate the polymerization reaction of methyl methacrylate monomer in the liquid when the powder is mixed with the liquid. The main function of the developer is to develop sufficiently to facilitate surgical observation.

The accelerator in the liquid mainly serves as an activator and a coinitiator of free radical polymerization to promote the polymerization of the monomer; the polymerization inhibitor mainly acts to stabilize the monomer and prevent the monomer from polymerizing prematurely.

Different from the conventional bone cement, the esterified starch is added into the powder of the bone cement provided by the invention. The esterified starch in the present invention refers to a product obtained by subjecting starch to esterification modification. It was found in the present invention that, when the temperature exceeds 45 ℃, the aqueous solution of esterified starch loses its stability and its viscosity rises rapidly with increasing temperature. The main reason is that when the temperature is increased to a certain value in the heating process, the esterified starch particles begin to absorb water and expand, even gelatinize, and molecular chains stretch, so that the viscosity of the whole system is rapidly increased. In view of the above characteristics of the esterified starch, the esterified starch can be added into bone cement to promote the rapid setting of the bone cement and shorten the setting time.

The esterified starch typically, but not by way of limitation, comprises 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 6.5% or 8% by mass of the powder.

The term "comprising" as used herein means that it may include, in addition to the raw materials, other raw materials acceptable in the bone cement art, which may impart different properties to the bone cement. In addition, the term "comprising" as used herein may be replaced by "being" or "made from … …" as closed.

In a preferred embodiment of the present invention, the powder comprises the following raw materials in percentage by mass, based on 100% by weight of the powder:

In particular, the polymethyl methacrylate is typically, but not limited to, 77.5%, 78%, 79%, 80%, 82%, 84%, 85%, 86%, 86.5%, 87% or 87.5% by mass. The esterified starch typically, but not exclusively, has a mass fraction of 4%, 5%, 6%, 7% or 8%. Typical but not limiting mass fractions of initiator are 0.5%, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.3% or 2.5%. The developer is typically, but not limited to, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, or 12% by mass.

The use performance and the mechanical property of the bone cement can reach more excellent and stable levels by further limiting the use amount of each raw material in the powder.

As a preferred embodiment of the present invention, the method for preparing esterified starch comprises the steps of:

The starch is pre-catalyzed by adopting a catalyst, and then a modifier is added for esterification reaction, so that the catalyst and the modifier can form an active complex, and the reaction activity is improved. After esterification reaction, hydroxyl on the surface of the starch is changed into ester group, so that hydrophobicity is enhanced, gelatinization temperature is reduced, retrogradation is weakened, stability to acid and heat is improved, viscosity of the gelatinized starch is increased, and biodegradation speed is reduced.

As a preferred embodiment of the present invention, the starch comprises a plant starch, preferably comprises any one or a combination of at least two of cereal starch, bean starch or potato starch, further preferably comprises any one or a combination of at least two of corn starch, wheat starch, rice starch, sorghum starch, soybean starch, tapioca starch or potato starch.

As a preferred embodiment of the present invention, the catalyst comprises any one of pyridine, triethylamine or 4-dimethylaminopyridine, or a combination of at least two thereof, preferably pyridine.

As a preferred embodiment of the present invention, the solvent includes any one of a mixture of lithium chloride and N, N-dimethylformamide, ethyl acetate or dimethyl sulfoxide, and preferably includes ethyl acetate.

As a preferred embodiment of the present invention, the modifier includes any one or a combination of at least two of acryloyl chloride, acetyl chloride, methacryloyl chloride, stearic acid chloride, octanoic acid chloride, dodecanoic acid chloride, or octadecanoic acid chloride, and preferably includes methacryloyl chloride.

In a preferred embodiment of the present invention, the mass ratio of the starch, the catalyst and the solvent is 1: (0.5-1): (0.5-1).

Starch, catalyst and solvent typically, but not by way of limitation, in a mass ratio of 1: 0.5: 0.5, 1: 0.5: 0.6, 1: 0.5: 0.8, 1: 0.5: 1. 1: 0.6: 0.5, 1: 0.8: 0.5, 1: 1: 0.5, 1: 0.5: 0.6, 1: 0.6: 0.6, 1: 0.7: 0.7, 1: 0.8: 0.8, 1: 0.9: 0.9 or 1: 1: 1.

in a preferred embodiment of the invention, the mass of the modifier is 4-6% of the mass of the starch.

The mass of modifier as a percentage of the mass of starch is typically, but not limited to, 4%, 4.2%, 4.4%, 4.5%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.5%, 5.6%, 5.8% or 6%.

As a preferred embodiment of the invention, the pre-catalysis temperature is 15-25 ℃ and the pre-catalysis time is 1-2 h.

Typical but non-limiting temperatures for pre-catalysis are 15 ℃, 18 ℃, 20 ℃, 22 ℃, 24 ℃ or 25 ℃. Typical but non-limiting times for pre-catalysis are 1h, 1.5h or 2 h.

As a preferred embodiment of the present invention, the temperature of the esterification reaction is 20 to 50 ℃, preferably 25 to 30 ℃; typical but non-limiting temperatures are 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, or 50 ℃.

Preferably, the esterification reaction time is from 0.5 to 6 hours, preferably from 1 to 4 hours. Typical but non-limiting temperatures are 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6 h.

By further limiting each reaction raw material and reaction conditions in the preparation process of the esterified starch, the starch esterification efficiency is improved, the prepared esterified starch has stronger hydrophobicity, and the thermal stability and the mechanical property are obviously improved.

As a preferred embodiment of the present invention, the initiator comprises any one or a combination of at least two of benzoyl peroxide, cyclohexanone peroxide or methyl ethyl ketone peroxide, preferably benzoyl peroxide;

In a preferred embodiment of the present invention, the liquid comprises the following raw materials in mass fraction, based on 100% of the weight of the liquid:

Specifically, typical but non-limiting mass fractions of methyl methacrylate monomer are 96.991%, 97.0%, 97.2%, 97.4%, 97.5%, 97.6%, 97.8%, 98.0%, 98.2%, 98.4%, 98.5%, 98.6%, 98.8%, or 98.991%. Typical but not limiting mass fractions of accelerators are 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.2%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3.0%. Typical but not limiting mass fractions of polymerization inhibitors are 0.009%, 0.0095%, 0.01% or 0.011%.

The use performance and the mechanical property of the bone cement can reach more excellent and stable level by further limiting the use amount of each raw material in the liquid.

As a preferred embodiment of the present invention, the accelerator comprises any one or a combination of at least two of N, N-dimethyl-p-toluidine, N-dimethylaniline, N-diethylaniline or a thiol, preferably comprising N, N-dimethyl-p-toluidine;

as a preferred embodiment of the present invention, the polymerization inhibitor comprises any one or a combination of at least two of hydroquinone, 2, 4-dimethyl-6-tert-butylphenol or nitrosophenol, preferably hydroquinone.

In a preferred embodiment of the present invention, the bone cement comprises powder and liquid, wherein the mass volume ratio of the powder to the liquid is 2-2.2 g: 1 mL;

the liquid comprises the following raw materials in percentage by mass, based on 100% of the weight of the liquid:

By further limiting the types and the use amounts of the raw materials in the bone cement, the service performance and the mechanical property of the bone cement reach more excellent and stable levels.

According to a second aspect of the present invention, there is also provided a method for preparing the above bone cement, comprising the steps of:

and mixing the powder and the liquid, and solidifying to obtain the bone cement.

The preparation method is simple to operate and stable in process.

As a preferred embodiment of the present invention, the setting time is 8.5 to 10 min. Typical but non-limiting setting times are 8.5min, 9.0min, 9.5min or 10 min.

According to a third aspect of the present invention, there is also provided the use of the above bone cement in the preparation of a material for bone filling or bone repair.

In view of the advantages of the bone cement, the bone cement has good application in preparing materials for bone filling or bone repair.

The present invention will be further described with reference to specific examples and comparative examples.

Example 1

The embodiment provides a bone cement, which comprises powder and liquid, wherein the mass-volume ratio of the powder to the liquid is 2 g: 1 mL;

78% of polymethyl methacrylate, 8% of esterified starch, 2.0% of benzoyl peroxide and 12% of barium sulfate;

98.99 percent of methyl methacrylate monomer, 1.0 percent of N, N-dimethyl-p-toluidine and 0.01 percent of hydroquinone.

The preparation method of the esterified starch in the embodiment comprises the following steps:

drying starch in a 60 ℃ oven for 24 hours, mixing the dried starch with a catalyst and a solvent for pre-catalysis treatment at the pre-catalysis temperature of 15 ℃ for 2 hours, then adding a modifier for esterification reaction at the esterification reaction temperature of 25 ℃ for 1 hour, and washing and centrifuging the modified mixture after the reaction is finished to obtain the esterified starch.

Wherein, the starch is corn starch, the corresponding esterified starch is esterified corn starch, the catalyst is pyridine, the solvent is ethyl acetate, the modifier is methacryloyl chloride, and the mass ratio of the starch to the catalyst to the solvent is 1: 0.5: 0.5; the mass of the modifier accounts for 4 percent of the mass of the starch.

Example 2

This example provides a bone cement, in which the types, amounts and preparation methods of the raw materials are the same as those of example 1, except that corn starch is replaced by wheat starch, and the corresponding esterified corn starch is replaced by esterified wheat starch.

Example 3

This example provides a bone cement, which is prepared by replacing corn starch with soybean starch, and replacing the corresponding esterified corn starch with esterified soybean starch, and which has the same types of raw materials, amounts, and preparation methods as example 1.

Example 4

This example provides a bone cement, which is prepared by replacing corn starch with tapioca starch, and replacing esterified corn starch with esterified tapioca starch, and the types, amounts and preparation methods of the other raw materials are the same as those of example 1.

Example 5

This example provides a bone cement, and the types, amounts and preparation methods of the raw materials were the same as those of example 1, except that the amounts of the raw materials in the powder were changed.

The powder in the embodiment comprises the following raw materials in percentage by mass, based on 100% of the weight of the powder:

82% of polymethyl methacrylate, 4% of esterified starch, 2.0% of benzoyl peroxide and 12% of barium sulfate.

Example 6

86.5 percent of polymethyl methacrylate, 4 percent of esterified starch, 1.5 percent of benzoyl peroxide and 8 percent of barium sulfate.

Example 7

This example provides a bone cement, except that the mass of the modifier in the preparation method of the esterified starch is 8% of the mass of the starch, and the types, the amounts and the preparation methods of the other raw materials are the same as those in example 1.

Example 8

This example provides a bone cement, which is the same as example 1 except that the mass of the modifier is 3% of the mass of the starch in the preparation method of the esterified starch, and the kinds, amounts and preparation methods of the other raw materials are the same.

Example 9

This example provides a bone cement, except that the mass of the modifier in the preparation method of the esterified starch is 6% of the mass of the starch, and the types, the amounts and the preparation methods of the other raw materials are the same as those in example 1.

Example 10

The embodiment provides bone cement, which comprises powder and liquid, wherein the mass-volume ratio of the powder to the liquid is 2.2 g: 1 mL;

82.2 percent of polymethyl methacrylate, 6 percent of esterified starch, 1.8 percent of benzoyl peroxide and 10 percent of barium sulfate;

98% of methyl methacrylate monomer, 1.991% of N, N-dimethyl-p-toluidine and 0.009% of hydroquinone.

The preparation method of the esterified starch comprises the following steps:

drying starch in a 60 ℃ oven for 24 hours, mixing the dried starch with a catalyst and a solvent for pre-catalysis treatment at the pre-catalysis temperature of 15 ℃ for 2 hours, then adding a modifier for esterification reaction at the esterification reaction temperature of 25 ℃ for 2 hours, and washing and centrifuging the modified mixture after the reaction is finished to obtain the esterified starch.

Wherein, the starch is corn starch, the corresponding esterified starch is esterified corn starch, the catalyst is pyridine, the solvent is ethyl acetate, the modifier is triethylamine, and the mass ratio of the starch, the catalyst and the solvent is 1: 1: 1; the mass of the modifier accounts for 5 percent of the mass of the starch.

Example 11

The embodiment provides bone cement, which comprises powder and liquid, wherein the mass-volume ratio of the powder to the liquid is 2.1 g: 1 mL;

84% of polymethyl methacrylate, 4.4% of esterified starch, 1.6% of cyclohexanone peroxide and 10% of zirconium dioxide;

98.5% of methyl methacrylate monomer, 1.49% of N, N-diethylaniline and 0.01% of 2, 4-dimethyl-6-tert-butylphenol.

The preparation method of the esterified starch comprises the following steps:

drying starch in a 60 ℃ oven for 24 hours, mixing the dried starch with a catalyst and a solvent for pre-catalysis treatment at the temperature of 20 ℃ for 1.5 hours, adding a modifier for esterification reaction at the temperature of 25 ℃ for 3 hours, and washing and centrifuging the modified mixture after the reaction is finished to obtain the esterified starch.

Wherein the starch is sorghum starch, the corresponding esterified starch is esterified sorghum starch, the catalyst is pyridine, the solvent is ethyl acetate, the modifier is 4-dimethylamino pyridine, and the mass ratio of the starch to the catalyst to the solvent is 1: 0.8: 0.8; the mass of the modifier accounts for 4.5% of the mass of the starch.

Examples 1-11 provide a method of preparing a bone cement comprising the steps of:

Comparative example 1

This comparative example provides a bone cement, the kind, amount and preparation method of the raw materials were the same as those of example 1, except that the esterified starch (esterified corn starch) in the powder was replaced with starch (corn starch), i.e., starch was not subjected to esterification reaction.

Comparative example 2

This comparative example provides a bone cement, the kind, amount and preparation method of which were the same as those of example 1 except that the amount of each raw material in the powder was changed.

The powder in the comparative example comprises the following raw materials in percentage by mass, based on 100% of the weight of the powder:

83% of polymethyl methacrylate, 3% of esterified starch, 2% of benzoyl peroxide and 12% of barium sulfate.

Comparative example 3

76% of polymethyl methacrylate, 10% of esterified starch, 2% of benzoyl peroxide and 12% of barium sulfate.

Comparative example 4

This comparative example provides a bone cement, except that esterified starch was not added to the powder (i.e., the mass fraction of esterified starch was 0%), and the mass fraction of polymethylmethacrylate was 86%, the kinds, amounts, and preparation methods of the remaining raw materials were the same as those of example 1.

Comparative example 5

This comparative example provides a bone cement, except that esterified starch was not added to the powder (i.e., the mass fraction of esterified starch was 0%), and the mass fraction of polymethylmethacrylate was 88.2%, the kinds, amounts, and preparation methods of the remaining raw materials were the same as those of example 10.

Comparative example 6

This comparative example provides a bone cement, except that esterified starch was not added to the powder (i.e., the mass fraction of esterified starch was 0%), and the mass fraction of polymethylmethacrylate was 88.4%, the kinds, amounts, and preparation methods of the remaining raw materials were the same as those of example 11.

Comparative examples 1 to 6 provide bone cements prepared in the same manner as examples 1 to 11.

To verify the technical effects of the respective examples and comparative examples, the following experiments were conducted.

Experimental example 1

The working time, setting time, compressive strength and bending strength of the bone cements provided in examples 1 to 11 and comparative examples 1 to 6 were measured, and the results are shown in table 1.

Wherein, the detection method of the working time and the setting time refers to the method of appendix B and C in YY0459-2003, in particular, the powder and the liquid of the bone cement are placed in a constant temperature box with the ambient temperature of 23 +/-1 ℃ and the humidity of 100 percent, a testing mold, a temperature testing device (thermocouple) and a stopwatch are prepared, then mixing and stirring the bone cement powder and the liquid, pressing a stopwatch to start recording time, recording the time when the bone cement reaches a dough period, meanwhile, about 25g of bone cement is placed into the female die, the male die is used for compacting the bone cement to a certain volume, so that the temperature sensing device is deep into the bone cement, and then removing the male die to enable the bone cement to be fully exposed in the environment and contact moisture, and finally recording and calculating the working time and the setting time of the bone cement, wherein the working time is the difference between the setting time and the dough time.

The test methods for the compression resistance and the compression and bending strength were carried out according to the methods of appendices E and F of standard YY 0459-2003.

TABLE 1

As can be seen from the data in Table 1, the bone cement provided by the embodiments of the present invention has a short setting time and good mechanical properties.

Specifically, example 5, comparative example 2 and comparative example 3 are control experiments of example 1. As can be seen from the data in the table, within a certain numerical range, the working time and the setting time of the bone cement are gradually reduced along with the increase of the content of the esterified starch, and the mechanical properties have no obvious difference, which may be because the gelatinization speed of the starch with more addition is faster and the distribution is more uniform along with the increase of the system temperature in the curing process of the bone cement, so the working time and the setting time are reduced, and the mechanical properties have no obvious change, which may be because the distribution of the esterified starch is more uniform and the content is lower, so the mechanical properties have no obvious influence. Too low esterified starch content (comparative example 2) will not contribute to a significant decrease in setting time, while too high esterified starch content (comparative example 3) will reduce setting time, but will cause a significant decrease in mechanical properties of bone cement due to too much addition, which affects clinical use of bone cement.

Examples 7-9 are control experiments of example 1, with the difference that the mass fraction of modifier to starch is different. As can be seen from the data in the table, the higher the content of the modifier in a certain range during the esterification of the starch, the higher the degree of substitution of the starch, and the more uniform the distribution of the starch in the powder under the same addition amount, therefore, the shorter the solidification time. If the content of the modifier is increased beyond a specific range, the degree of substitution of the starch is not significantly affected, and thus the setting time is not further shortened.

Comparative example 1 is also a control experiment for example 1. Although the addition of the same amount of starch content in comparative example 1 also serves to shorten the setting time, compared to the esterified starch added in example 1, starch may be easily unevenly distributed during the mixing and stirring process and thus the mechanical properties of the resulting cement may be poor. Therefore, the addition of a certain amount of esterified starch in the bone cement powder can not only reduce the setting time of the bone cement, but also ensure the mechanical strength of the bone cement, and is beneficial to the clinical application of the bone cement.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. The bone cement is characterized by comprising the following raw materials: the mass volume ratio of the powder to the liquid is (2-2.2 g): 1 mL;

2. The bone cement of claim 1, wherein the powder comprises the following raw materials by mass percent, based on 100% by weight of the powder:

3. The bone cement of claim 2, wherein the preparation method of the esterified starch comprises the steps of:

4. The bone cement of claim 3, wherein the starch comprises a vegetable starch.

5. Bone cement according to claim 4, characterized in that the starch comprises any one of cereal starch, legume starch or potato starch or a combination of at least two thereof.

6. The bone cement of claim 4, wherein the starch comprises any one of or a combination of at least two of corn starch, wheat starch, rice starch, sorghum starch, soybean starch, tapioca starch, or potato starch.

7. The bone cement of claim 4, wherein the catalyst comprises any one of pyridine, triethylamine, or 4-dimethylaminopyridine, or a combination of at least two thereof.

8. The bone cement of claim 7, wherein the catalyst comprises pyridine.

9. The bone cement of claim 4, wherein the solvent comprises any one of a mixture of lithium chloride and N, N-dimethylformamide, ethyl acetate, or dimethyl sulfoxide.

10. The bone cement of claim 9, wherein the solvent comprises ethyl acetate.

11. The bone cement of claim 4, wherein the modifier comprises any one of acryloyl chloride, acetyl chloride, methacryloyl chloride, stearoyl chloride, octanoyl chloride, dodecanoyl chloride, or octadecanoyl chloride, or a combination of at least two thereof.

12. The bone cement of claim 11, wherein the modifying agent comprises methacryloyl chloride.

13. The bone cement of claim 4, wherein the mass ratio of the starch, the catalyst and the solvent is 1: (0.5-1): (0.5-1).

14. Bone cement according to claim 4, characterized in that the mass of the modifier is between 4 and 6% of the mass of the starch.

15. Bone cement according to claim 4, characterized in that the pre-catalysis temperature is 15-25 ℃ and the pre-catalysis time is 1-2 h.

16. A bone cement according to claim 4, characterized in that the temperature of the esterification reaction is 20-50 ℃.

17. The bone cement of claim 16, wherein the temperature of the esterification reaction is 25-30 ℃.

18. The bone cement of claim 4, wherein the esterification reaction time is 0.5 to 6 hours.

19. The bone cement of claim 18, wherein the esterification reaction time is 1 to 4 hours.

20. The bone cement of claim 2, wherein the initiator comprises any one of or a combination of at least two of benzoyl peroxide, cyclohexanone peroxide, or methyl ethyl ketone peroxide.

21. The bone cement of claim 20, wherein the initiator comprises benzoyl peroxide.

22. The bone cement of claim 20, wherein the imaging agent comprises any one of barium sulfate, zirconium dioxide, or tantalum powder, or a combination of at least two thereof.

23. The bone cement of claim 22, wherein the imaging agent comprises barium sulfate and/or zirconium dioxide.

24. Bone cement according to any of claims 1 to 23, characterized in that the liquid comprises the following raw materials in mass fraction, based on 100% by weight of liquid:

25. The bone cement of claim 24, wherein the accelerator comprises any one or a combination of at least two of N, N-dimethyl-p-toluidine, N-dimethylaniline, N-diethylaniline, or a thiol.

26. The bone cement of claim 25, wherein the accelerator comprises N, N-dimethyl-p-toluidine.

27. The bone cement of claim 25, wherein the polymerization inhibitor comprises any one or a combination of at least two of hydroquinone, 2, 4-dimethyl-6-tert-butylphenol, or nitrosophenol.

28. The bone cement of claim 27, wherein the polymerization inhibitor comprises hydroquinone.

29. The bone cement according to any one of claims 1-23, comprising a powder and a liquid, wherein the mass volume ratio of the powder to the liquid is 2-2.2 g: 1 mL;

30. A method of preparing a bone cement according to any one of claims 1 to 29, comprising the steps of:

31. The method of claim 30, wherein the setting time is 8.0-10.5 min.

32. Use of a bone cement according to any one of claims 1 to 29 or prepared by the method of claim 30 or 31 in the preparation of a material for bone filling or bone repair.