PRE-MIXED STRONTIUM SILICATE-BASED BIOLOGICAL HYDRAULIC CEMENTING PASTE COMPOSITION, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF

Abstract

A pre-mixed strontium silicate-based biological hydraulic cement paste composition and preparation method and use thereof are disclosed. The pre-mixed strontium silicate-based biological hydraulic cement paste of the disclosure uses strontium silicate as the main phase and at least one non-aqueous solvent that is miscible with water, and preferably, it may further include at least one calcium phosphate compound and at least one radiopaque material, to prepare a biological hydraulic cement paste with excellent injectability. The material remains as a fluid under a sealed condition, and hydrates, solidifies and hardens when it is placed in a physiological environment and contacts with a physiological body fluid. The strontium silicate-based material having excellent biocompatibility and biological activity is used to prepare a pre-mixed strontium silicate-based cement paste, which can be used for medical and dental applications including fields of pulp capping, root canal therapy, dental restorations and the like.

Claims

1. A pre-mixed strontium silicate-based cement paste composition, wherein, the pre-mixed strontium silicate-based cement paste composition includes: component (a): at least one strontium silicate compound; component (b): at least one substantially anhydrous liquid carrier mixed with the at least one strontium silicate compound.

2. The pre-mixed strontium silicate-based cement paste composition according to claim 1, wherein, in the pre-mixed strontium silicate-based cement paste composition, component (a) is a solid which accounts for 60%-92% of the total mass of the cement paste composition, and the liquid component (b) accounts for 8%-40% of the total mass of the cement paste composition.

3. The pre-mixed strontium silicate-based cement paste composition according to claim 1, wherein, the strontium silicate compound is selected from the group consisting of strontium silicate, tristrontium silicate, distrontium silicate, and mixtures thereof.

4. The pre-mixed strontium silicate-based cement paste composition according to claim 1, wherein, the substantially anhydrous liquid carrier is selected from the group consisting of ethylene glycol, propylene glycol, polyethylene glycol, liquid glycerin, ethanol, a silicone oil, clove oil, an animal oil, a vegetable oil, an organic acid, and mixtures thereof.

5. The pre-mixed strontium silicate-based cement paste composition according to claim 1, wherein, the strontium silicate-based cement paste composition further includes: component (c): at least one radiopaque material.

6. The pre-mixed strontium silicate-based cement paste composition according to claim 5, wherein, the radiopaque material is selected from at least one of zirconium oxide, bismuth oxide and tantalum oxide.

7. The pre-mixed strontium silicate-based cement paste composition according to claim 5, wherein, in the pre-mixed strontium silicate-based cement paste composition, components (a) and (c) are solid components which account for 60%-92% of the total mass of the cement paste composition, and the liquid component (b) accounts for 8%-40% of the total mass of the cement paste composition.

8. The pre-mixed strontium silicate-based cement paste composition according to claim 7, wherein, in the pre-mixed strontium silicate-based cement paste composition, the solid component (a) accounts for 20%-82% of the total mass of the cement paste composition, the solid component (c) accounts for 10%-40% of the total mass of the cement paste composition, and the liquid component (b) accounts for 8%-40% of the total mass of the cement paste composition.

9. The pre-mixed strontium silicate-based cement paste composition according to claim 1, wherein, the strontium silicate-based cement paste composition further includes: component (d): at least one calcium phosphate compound.

10. The pre-mixed strontium silicate-based cement paste composition according to claim 9, wherein, the calcium phosphate compound is selected from at least one of tricalcium phosphate, tetracalcium phosphate, calcium dihydrogen phosphate and hydroxyapatite.

11. The pre-mixed strontium silicate-based cement paste composition according to claim 9, wherein, in the pre-mixed strontium silicate-based cement paste composition, components (a) and (d) are solids which account for 60%-92% of the total mass of the cement paste composition, and the liquid component (b) accounts for 8%-40% of the total mass of the cement paste composition.

12. The pre-mixed strontium silicate-based cement paste composition according to claim 11, wherein, in the pre-mixed strontium silicate-based cement paste composition, the solid component (a) accounts for 10%-42% of the total mass of the cement paste composition, the solid component (d) accounts for 10%-40% of the total mass of the cement paste composition, and the liquid component (b) accounts for 8%-40% of the total mass of the cement paste composition.

13. The pre-mixed strontium silicate-based cement paste composition according to claim 5, wherein, the strontium silicate-based cement paste composition further includes: component (d): at least one calcium phosphate compound.

14. The pre-mixed strontium silicate-based cement paste composition according to claim 13, wherein, the calcium phosphate compound is selected from at least one of tricalcium phosphate, tetracalcium phosphate, calcium dihydrogen phosphate and hydroxyapatite.

15. The pre-mixed strontium silicate-based cement paste composition according to claim 13, wherein, in the pre-mixed strontium silicate-based cement paste composition, components (a), (c) and (d) are solids which account for 60%-92% of the total mass of the cement paste composition, and the liquid component (b) accounts for 8%-40% of the total mass of the cement paste composition.

16. The pre-mixed strontium silicate-based cement paste composition according to claim 15, wherein, in the pre-mixed strontium silicate-based cement paste composition, the solid component (a) accounts for 10%-42% of the total mass of the cement paste composition, the solid component (c) accounts for 10%-40% of the total mass of the cement paste composition, the solid component (d) accounts for 10%-40% of the total mass of the cement paste composition, and the liquid component (b) accounts for 8%-40% of the total mass of the cement paste composition.

17. (canceled)

18. A method of treating a tooth or bone of a subject, comprising the steps of: obtaining the pre-mixed strontium silicate-based cement paste composition of claim 1; and applying the pre-mixed strontium silicate-based cement paste composition to the tooth or bone of the subject.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0033] FIG. 1 shows the pre-mixed strontium silicate-based cement paste material obtained in Example 1;

[0034] FIG. 2 is a photograph of the strontium silicate-based cement paste obtained in Example 1 after hydraulic setting;

[0035] FIG. 3 is a micrograph of the material obtained in Example 1 after hydraulic setting; and

[0036] FIG. 4 is an XRD element analysis diagram of the material obtained in Example 1 after hydraulic setting.

DETAILED DESCRIPTION FOR THE INVENTION

[0037] The disclosure will be further described below in conjunction with specific examples, and the advantages and features of the disclosure will become clearer with the description. However, the examples are only exemplary and do not constitute any limitation to the scope of the disclosure. Those skilled in the art should understand that the details and forms of the technical solution of the disclosure can be modified or replaced without departing from the spirit and scope of the disclosure, but these modifications and replacements fall within the protection scope of the disclosure.

Test Method for Setting Time

1. Equipments

[0038] 1.1. Constant temperature and humidity chamber: an environment with a temperature of 37° C.±1° C. and a relative humidity of not less than 95% is maintained.

[0039] 1.2. Penetrometer: a flat end face indenter with a mass of 100 g±0.5 g and a diameter of 2 mm±0.1 mm; the tip of the indenter is a cylinder with a length of at least 5 mm, and the end face of the indenter should be a horizontal plane at right angles to the long axis.

[0040] 1.3 Mold: a stainless-steel ring mold; the mold cavity has an inner diameter d=10 mm and a height h=2 mm.

[0041] 1.4. Metal block: minimum size 8 mm×20 mm×10 mm, placed in the constant temperature and humidity chamber at 37° C.±1° C. for at least 1 h before use.

[0042] 1.5. Flat glass sheet: about 1 mm thick, for example, glass slide.

2. Sample Preparation

[0043] The stainless-steel mold was placed on the flat glass sheet and was filled with the blended root canal filling paste (i.e., the suspended stable pre-mixed strontium silicate-based cement paste prepared in the examples). The material was level with the upper end of the mold. After the completion of blending, the above components were placed on the metal block in the constant temperature and humidity chamber.

3. Steps

[0044] After curing for 8 h, the sample was taken out every 1 hour. The indenter of the penetrometer was gently and vertically placed on the horizontal surface of the root canal filling paste, raised and wiped clean. The above operations were repeated until no indentation can be seen with naked eyes. The period starting from the end of the blending, until the indentation no longer appears is recorded as the setting time.

4. Results

[0045] The setting time was recorded when there is no indentation.

Example 1 Preparation of a Suspended Stable Pre-Mixed Strontium Silicate-Based Cement Paste

[0046] (1) weighing the raw materials according to the following weight percentages:

[0047] component (a): 55% of tristrontium silicate;

[0048] component (b): 22% of polyethylene glycol; and

[0049] component (c): 23% of zirconium oxide;

[0050] (2) placing the components (a), (c) and (b) of step (1) into a glass container sequentially, mechanically mixing with a stainless-steel stirring rod, and thoroughly blending for 10 min;

[0051] (3) subsequently, transferring the mixed paste to a medical syringe equipped with an injection hose needle, to obtain the suspended stable pre-mixed strontium silicate-based cement paste.

[0052] The material remains as a fluid under sealed conditions. The sample is extruded and placed into a constant temperature and humidity chamber at 37° C. and a humidity of 95% or more (or filled into the teeth in contact with physiological body fluids) for hydration, solidification and hardening. Setting time: 13 hours.

[0053] FIG. 1 shows the pre-mixed strontium silicate-based cement paste material obtained in Example 1. FIG. 2 is a photograph of the strontium silicate-based cement paste obtained in Example 1 after hydraulic setting. FIG. 3 is a micrograph of the material obtained in Example 1 after hydraulic setting. FIG. 3 shows that the needle-like tissues on small pom-like structure of the strontium silicate hydration product Sr—S—H are fine and dense, interlaced, and crosslinked together to form a dense, high-strength microstructure, which is very similar to the hydroxyapatite pom-shaped structure and has good mechanical properties. FIG. 4 is an XRD element analysis diagram of the material obtained in Example 1 after hydraulic setting. FIG. 4 shows that the strontium silicate hydrate (Sr—S—H) is mainly composed of Sr, Si, and O elements (note: H element is not shown in XRD analysis of electron microscope). Strontium has a good effect on strengthening teeth and bones.

[0054] The pre-mixed strontium silicate-based cement paste material obtained in Example 1 was placed in a constant temperature and humidity chamber at 37° C. and a humidity of 95% for hydration test. The material was taken out at 0.5, 1, 2, 3, 5, 8, 12, 24, and 48 hours after being placed in, and measured with an infrared thermometer. The temperature was 37.0° C., 36.8° C., 37.1° C., 36.9° C., 37.0° C., 37.0° C., 36.6° C., 37.1° C., and 37.0° C., respectively. The temperature was substantially unchanged, indicating that the pre-mixed strontium silicate-based cement paste material prepared in Example 1 has an effect that the temperature rise during reaction is not significant.

Example 2 Preparation of a Suspended Stable Pre-Mixed Strontium Silicate-Based Cement Paste

[0055] (1) weighing the raw materials according to the following weight percentages:

[0056] component (a): 18% of tristrontium silicate;

[0057] component (b): 27% of polyethylene glycol;

[0058] component (c): 30% of tantalum oxide; and

[0059] component (d): 16% of anhydrous calcium dihydrogen phosphate and 9% of tetracalcium phosphate;

[0060] (2) placing the components (a), (c), (d) and (b) of step (1) into a glass container sequentially, mechanically mixing with a stainless-steel stirring rod, and thoroughly blending for 10 min;

[0061] (3) subsequently, transferring the mixed paste to a medical syringe equipped with an injection hose needle, to obtain the suspended stable pre-mixed strontium silicate-based cement paste 2.

[0062] The material remains as a fluid under sealed conditions. The sample is extruded and placed into a constant temperature and humidity chamber at 37° C. and a humidity of 95% or more (or filled into the teeth in contact with physiological body fluids) for hydration, solidification and hardening. Setting time: 13 hours.

[0063] The pre-mixed strontium silicate-based cement paste material obtained in Example 2 was placed in a constant temperature and humidity chamber at 37° C. and a humidity of 95% for hydration test. The material was taken out at 0.5, 1, 2, 3, 5, 8, 12, 24, and 48 hours after being placed in, and measured with an infrared thermometer. The temperature was substantially unchanged in the range of 36-38° C., indicating that the pre-mixed strontium silicate-based cement paste material prepared in Example 2 has an effect that the temperature rise during reaction is not significant.

Example 3 Preparation of a Suspended Stable Pre-Mixed Strontium Silicate-Based Cement Paste

[0064] (1) weighing the raw materials according to the following weight percentages:

[0065] component (a): 12% of tristrontium silicate and 7% of distrontium silicate;

[0066] component (b): 29% of glycerin;

[0067] component (c): 32% of bismuth trioxide; and

[0068] component (d): 20% of calcium dihydrogen phosphate;

[0069] (2) placing the components (a), (c), (d) and (b) of step (1) into a glass container sequentially, mechanically mixing with a stainless-steel stirring rod, and thoroughly blending for 10 min;

[0070] (3) subsequently, transferring the mixed paste to a medical syringe equipped with an injection hose needle, to obtain the suspended stable pre-mixed strontium silicate-based cement paste 3.

[0071] The material remains as a fluid under sealed conditions. The sample is extruded and placed into a constant temperature and humidity chamber at 37° C. and a humidity of 95% or more (or filled into the teeth in contact with physiological body fluids) for hydration, solidification and hardening. Setting time: 18 hours.

[0072] The pre-mixed strontium silicate-based cement paste material obtained in Example 3 was placed in a constant temperature and humidity chamber at 37° C. and a humidity of 95% for hydration test. The material was taken out at 0.5, 1, 2, 3, 5, 8, 12, 24, and 48 hours after being placed in, and measured with an infrared thermometer. The temperature was substantially unchanged in the range of 36-38° C., indicating that the pre-mixed strontium silicate-based cement paste material prepared in Example 3 has an effect that the temperature rise during reaction is not significant.

Example 4 Preparation of a Suspended Stable Pre-Mixed Strontium Silicate-Based Cement Paste

[0073] (1) weighing the raw materials according to the following weight percentages:

[0074] component (a): 65% of tristrontium silicate; and

[0075] component (b): 35% of polyethylene glycol;

[0076] (2) placing the components (a) and (b) of step (1) into a glass container sequentially, mechanically mixing with a stainless-steel stirring rod, and thoroughly blending for 10 min;

[0077] (3) subsequently, transferring the mixed paste to a medical syringe equipped with an injection hose needle, to obtain the suspended stable pre-mixed strontium silicate-based cement paste 4.

[0078] The material remains as a fluid under sealed conditions. The sample is extruded and placed into a constant temperature and humidity chamber at 37° C. and a humidity of 95% or more (or filled into the teeth in contact with physiological body fluids) for hydration, solidification and hardening. Setting time: 12 hours.

[0079] The pre-mixed strontium silicate-based cement paste material obtained in Example 4 was placed in a constant temperature and humidity chamber at 37° C. and a humidity of 95% for hydration test. The material was taken out at 0.5, 1, 2, 3, 5, 8, 12, 24, and 48 hours after being placed in, and measured with an infrared thermometer. The temperature was substantially unchanged around 37° C., indicating that the pre-mixed strontium silicate-based cement paste material prepared in Example 4 has an effect that the temperature rise during reaction is not significant.