MEDICAL SILICON RUBBER HAVING HIGH MECHANICAL PROPERTY AND PREPARATION METHOD THEREOF

Abstract

The present disclosure relates to a medical silicon rubber having high mechanical property and a preparation method thereof. The medical silicon rubber comprises the following raw materials in parts by weight: 50˜90 parts of silicon rubber, 10˜50 parts of polyurethane, 10˜50 parts of fillers, 2˜6 parts of hydrogen-containing silicon oil and 2˜5 parts of a vulcanizing agent. The preparation method comprises: evenly mixing a part of fillers with silicon rubber in an internal mixer for later use, and evenly mixing the other part of fillers with polyurethane in the internal mixer; and mixing the mixed polyurethane on an open type rubber refining machine, then successively adding hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent into the open type rubber refining machine many times by small portions, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C.

Claims

1. A medical silicon rubber having high mechanical property, consisting of the following raw materials in parts by weight: 50˜90 parts of a silicon rubber, 10˜50 parts of a polyurethane, 10˜50 parts of a filler, 2˜6 parts of a hydrogen-containing silicon oil and 2˜5 parts of a vulcanizing agent.

2. The medical silicon rubber having high mechanical property according to claim 1, wherein the silicon rubber is one or two of a methylvinyl silicon rubber and a methylvinylphenyl silicon rubber.

3. The medical silicon rubber having high mechanical property according to claim 1, wherein the shore A hardness of the silicon rubber is 10-80 degrees.

4. The medical silicon rubber having high mechanical property according to claim 1, wherein the polyurethane is a polyester polyurethane or a polyether polyurethane containing a double bond.

5. The medical silicon rubber having high mechanical property according to claim 1, wherein the polyurethane is a mixing type polyurethane.

6. The medical silicon rubber having high mechanical property according to claim 1, wherein the filler is one or more of a carboxyl modified carbon nanotube, a silane modified silica, a fumed silica, a precipitated silica and an activated calcium carbonate.

7. The medical silicon rubber having high mechanical property according to claim 1, wherein the hydrogen-containing silicon oil is a hydrogen-containing silicon oil containing 1˜2 wt % of an activated hydrogen.

8. The medical silicon rubber having high mechanical property according to claim 1, wherein the vulcanizing agent is a platinum vulcanizing agent.

9. A preparation method of a medical silicon rubber having high mechanical property according to claim 1, comprising the following steps: step 1, evenly mixing a part of the filler with the silicon rubber in an internal mixer for later use, and evenly mixing the other part of the filler with the polyurethane in the internal mixer for later use; and step 2, mixing the mixed polyurethane on an open type rubber refining machine, then successively adding the hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent in the open type rubber refining machine many times by small portions, thinning three times after all the components are evenly mixed, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C. to obtain the medical silicon rubber having high mechanical property.

10. The preparation method according to claim 9, wherein the components are evenly mixed at 40˜60° C.

11. A preparation method of a medical silicon rubber having high mechanical property according to claim 2, comprising the following steps: step 1, evenly mixing a part of the filler with the silicon rubber in an internal mixer for later use, and evenly mixing the other part of the filler with the polyurethane in the internal mixer for later use; and step 2, mixing the mixed polyurethane on an open type rubber refining machine, then successively adding the hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent in the open type rubber refining machine many times by small portions, thinning three times after all the components are evenly mixed, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C. to obtain the medical silicon rubber having high mechanical property.

12. A preparation method of a medical silicon rubber having high mechanical property according to claim 3, comprising the following steps: step 1, evenly mixing a part of the filler with the silicon rubber in an internal mixer for later use, and evenly mixing the other part of the filler with the polyurethane in the internal mixer for later use; and step 2, mixing the mixed polyurethane on an open type rubber refining machine, then successively adding the hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent in the open type rubber refining machine many times by small portions, thinning three times after all the components are evenly mixed, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C. to obtain the medical silicon rubber having high mechanical property.

13. A preparation method of a medical silicon rubber having high mechanical property according to claim 4, comprising the following steps: step 1, evenly mixing a part of the filler with the silicon rubber in an internal mixer for later use, and evenly mixing the other part of the filler with the polyurethane in the internal mixer for later use; and step 2, mixing the mixed polyurethane on an open type rubber refining machine, then successively adding the hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent in the open type rubber refining machine many times by small portions, thinning three times after all the components are evenly mixed, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C. to obtain the medical silicon rubber having high mechanical property.

14. A preparation method of a medical silicon rubber having high mechanical property according to claim 5, comprising the following steps: step 1, evenly mixing a part of the filler with the silicon rubber in an internal mixer for later use, and evenly mixing the other part of the filler with the polyurethane in the internal mixer for later use; and step 2, mixing the mixed polyurethane on an open type rubber refining machine, then successively adding the hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent in the open type rubber refining machine many times by small portions, thinning three times after all the components are evenly mixed, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C. to obtain the medical silicon rubber having high mechanical property.

15. A preparation method of a medical silicon rubber having high mechanical property according to claim 6, comprising the following steps: step 1, evenly mixing a part of the filler with the silicon rubber in an internal mixer for later use, and evenly mixing the other part of the filler with the polyurethane in the internal mixer for later use; and step 2, mixing the mixed polyurethane on an open type rubber refining machine, then successively adding the hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent in the open type rubber refining machine many times by small portions, thinning three times after all the components are evenly mixed, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C. to obtain the medical silicon rubber having high mechanical property.

16. A preparation method of a medical silicon rubber having high mechanical property according to claim 7, comprising the following steps: step 1, evenly mixing a part of the filler with the silicon rubber in an internal mixer for later use, and evenly mixing the other part of the filler with the polyurethane in the internal mixer for later use; and step 2, mixing the mixed polyurethane on an open type rubber refining machine, then successively adding the hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent in the open type rubber refining machine many times by small portions, thinning three times after all the components are evenly mixed, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C. to obtain the medical silicon rubber having high mechanical property.

17. A preparation method of a medical silicon rubber having high mechanical property according to claim 8, comprising the following steps: step 1, evenly mixing a part of the filler with the silicon rubber in an internal mixer for later use, and evenly mixing the other part of the filler with the polyurethane in the internal mixer for later use; and step 2, mixing the mixed polyurethane on an open type rubber refining machine, then successively adding the hydrogen-containing silicon oil, the evenly mixed silicon rubber and the vulcanizing agent in the open type rubber refining machine many times by small portions, thinning three times after all the components are evenly mixed, and finally vulcanizing the mixed rubber on a plate rubber vulcanizing machine for 5˜15 min at 150˜190° C. to obtain the medical silicon rubber having high mechanical property.

18. The preparation method according to claim 11, wherein the components are evenly mixed at 40˜60° C.

19. The preparation method according to claim 12, wherein the components are evenly mixed at 40˜60° C.

20. The preparation method according to claim 13, wherein the components are evenly mixed at 40˜60° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIG. 1 shows a medical silicon rubber test piece having high mechanical property and a thickness of 2 mm according to the present disclosure.

DESCRIPTION OF THE EMBODIMENTS

[0020] Next, the present disclosure will be specially described and further explained through examples, and cannot be understood as limiting the scope of the present disclosure. Those skilled in the art make some non-nature improvements and regulations according to the above content of the present disclosure.

[0021] Various properties of products obtained from examples and comparative examples are tested using the following standard:

[0022] Tensile strength: GBT 528-2009 determination of tensile stress-strain property of vulcanized rubber or thermoplastic rubber

[0023] Tearing strength: GBT 529-2008 determination of a tearing strength of vulcanized rubber or thermoplastic rubber (trouser, right angle and crescent simples)

[0024] Cytotoxicity test: GBT 16886.5-2017 in vitro cytotoxicity test

[0025] Delayed type hypersensitivity and intracutaneous irritation test: GBT 16886.10-2017 Part 10 of biological assessment of medical apparatus and instruments: irritation and skin sensitization test

[0026] Preparation of Medical Silicon Rubber Having High Mechanical Property

[0027] Raw materials and mass parts of medical silicon rubbers in examples 1˜7 and comparative examples 1˜4 are shown in Table 1, in which the silicon rubber is methylvinyl silicon rubber which has a Shore A hardness of 75 degrees, the polyurethane is polyurethane mixing type polyurethane containing a double bond, the filler is fumed silica, the hydrogen-containing silicon oil is hydrogen-containing silicon oil containing 1.5 wt % of activated hydrogen, and the vulcanizing agent is a platinum vulcanizing agent. The preparation method is as follows. As shown in Table 1, raw materials were weighed, a part of the filler and silicon rubber were evenly mixed in an internal mixer for later use, and the remaining filler and polyurethane were evenly mixed in the internal mixer for later use. Then, the mixed polyurethane was mixed on an open type rubber refining machine at the mixing temperature of 40-60° C. The hydrogen-containing silicon oil, the silicon rubber and the vulcanizing agent were successively added many times by small portions. Thinning was performed for three times after all the components were evenly mixed, and finally the mixed rubber was vulcanized on a plate rubber vulcanizing machine according to the vulcanizing temperature and time shown in Table 1 to obtain the medical silicon rubber having high mechanical property.

TABLE-US-00001 TABLE 1 Preparation conditions of medical silicon rubbers having high mechanical property in examples 1~7 and comparative examples 1~4 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Comparative Comparative Comparative Comparative ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 example 1 example 2 example 3 example 4 Components Mass parts Silicon rubber 70 50 90 70 70 70 70 30 70 70 70 Polyurethane 30 50 10 30 30 30 30 70 30 30 30 Filler 30 30 30 10 50 30 30 30 5 30 30 Hydrogen- 4 4 4 6 2 4 4 4 4 1 4 containing silicon oil Vulcanizing 3.5 3.5 3.5 2 4 3.5 3.5 3.5 3.5 1 3.5 agent Vulcanizing 170 170 170 170 170 150 190 170 170 170 140 temperature (° C.) Vulcanizing 10 10 10 10 10 15 5 10 10 10 4 time (min)
The mechanical properties of products obtained in examples 1˜7 and comparative examples 1˜4 are tested, and results are shown in Table 2.

TABLE-US-00002 TABLE 2 Comparison of products obtained in examples and comparative examples in the present disclosure Tearing strength Tensile strength (KN/m) (MPa) Example 1 61.2 17.6 Example 2 56.0 19.8 Example 3 60.2 15.1 Example 4 60.1 16.7 Example 5 56.2 16.5 Example 6 59.6 17.1 Example 7 59.4 17.3 Comparative example 1 54.0 21.4 Comparative example 2 27.0 10.2 Comparative example 3 No vulcanization No vulcanization and formation and formation Comparative example 4 18    8.7
As described in Table 2, all the products obtained in examples 1˜7 have a tearing strength of 55 KN/m or more and a tensile strength of 15 MPa or more, and have a high mechanical strength. By comparing comparative examples 1˜4 with examples 1˜7, only 5 parts of filler are added in comparative example 2, and the filler has a reinforcement effect on the mixed type polyurethane and silicon rubber and plays a role in physically twining and cross linking, and thus its tensile strength and tearing strength are low; only 1 part of hydrogen-containing silicon oil and 1 part of vulcanizing agent are added in comparative example 3, when in vulcanization, vulcanization and formation does not occur, indicating that co-vulcanization of the silicon rubber and the mixed type polyurethane is achieved only when the hydrogen-containing silicon oil and the vulcanizing agent reach certain amounts. In comparative example 4, the vulcanization condition of 140° C. and 4 min is adopted, so the property of the obtained vulcanized rubber is poor, which is caused by incomplete vulcanization of the mixed rubber under the vulcanization conditions.

[0028] The safety of products in examples 1˜7 and comparative examples 1˜4 is tested, and results are shown in Table 3 and Table 4.

TABLE-US-00003 TABLE 3 Safety test results of safety of products in examples 1~6 of the present disclosure Cytotoxicity test Delayed type hypersensitivity Intradermic irritation test Detection Detection Examination results Conclusion results Conclusion results Conclusion Example 1 Cell response No Delayed type No delayed Difference No score = 0 cytotoxicity hypersensitivity type between intradermic grade = 0 hypersensitivity average scores irritation of a test sample and solvent control = 0.54 Example 2 Cell response No Delayed type No delayed Difference No score = 0 cytotoxicity hypersensitivity type between intradermic grade = 0 hypersensitivity average scores irritation of a test sample and solvent control = 0.63 Example 3 Cell response No Delayed type No delayed Difference No score = 0 cytotoxicity hypersensitivity type between intradermic grade = 0 hypersensitivity average scores irritation of a test sample and solvent control = 0.42 Example 4 Cell response No Delayed type No delayed Difference No score = 0 cytotoxicity hypersensitivity type between intradermic grade = 0 hypersensitivity average scores irritation of a test sample and solvent control = 0.79 Example 5 Cell response No Delayed type No delayed Difference No score = 0 cytotoxicity hypersensitivity type between intradermic grade = 0 hypersensitivity average scores irritation of a test sample and solvent control = 0.66 Example 6 Cell response No Delayed type No delayed Difference No score = 0 cytotoxicity hypersensitivity type between intradermic grade = 0 hypersensitivity average scores irritation of a test sample and solvent control = 0.39

TABLE-US-00004 TABLE 4 Safety test results of products in example 7 and comparative examples 1~4 of the present disclosure Example 7 Cell No Delayed type No delayed Difference No response = 0 cytotoxicity hypersensitivity type between intradermic grade = 0 hypersensitivity average scores irritation of a test sample and solvent control = 0.56 Comparative Cell No Delayed type No delayed Difference Intradermic example 1 response = 0 cytotoxicity hypersensitivity type between irritation grade = 0 hypersensitivity average scores of a test sample and solvent control = 1.21 Comparative Cell No Delayed type No delayed Difference No example 2 response = 0 cytotoxicity hypersensitivity type between intradermic grade = 0 hypersensitivity average scores irritation of a test sample and solvent control = 0.68 Comparative Cell No Delayed type No delayed Difference Intradermic example 3 response = 0 cytotoxicity hypersensitivity type between irritation grade = 0 hypersensitivity average scores of a test sample and solvent control = 1.66 Comparative Cell No Delayed type No delayed Difference Intradermic example 4 response = 0 cytotoxicity hypersensitivity type between irritation grade = 0 hypersensitivity average scores of a test sample and solvent control = 1.33
It can be seen from Table 3 and Table 4 that cytotoxicity tests, delayed type hypersensitivity tests and intradermic irritation tests of products in examples 1˜7 are qualified, indicating that the medical silicon rubber having high mechanical property of the present disclosure has good biocompatibility. Intradermic irritations of comparative example 1, comparative example 3 and comparative example 4 are all unqualified, which is because excessive mixing type polyurethane is added in comparative example 1. Complete vulcanization in comparative example 3 and comparative example 4 is not accomplished.

[0029] In summary, the medical silicon rubber having high mechanical property prepared in the present disclosure has good mechanical property and also has the characteristics of no toxicity, no irritation and high organism safety.

[0030] Various technical features in the above examples can be arbitrarily combined. For concisely description, all possible combinations of various technical features in the above examples are not described, however, all the combinations of these technical features should be deemed to be included within the scope of the present disclosure only if the combinations of these technical features are not in conflict.

[0031] The above examples only express several embodiments of the present disclosure, and the description is more specific and detailed, but it can not be understood as a limitation on the patent scope of the present disclosure. It should be noted that for persons of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present disclosure, which belong to the protection scope of the present disclosure. Therefore, the scope of protection of the invention patent shall be subjected to the attached claims.