CN109627749B - Platinum vulcanization mixing type polyurethane and preparation method thereof - Google Patents
Platinum vulcanization mixing type polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN109627749B CN109627749B CN201811611949.XA CN201811611949A CN109627749B CN 109627749 B CN109627749 B CN 109627749B CN 201811611949 A CN201811611949 A CN 201811611949A CN 109627749 B CN109627749 B CN 109627749B
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- hydrogen
- silicone oil
- parts
- containing silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention relates to platinum vulcanization mixing type polyurethane and a preparation method thereof. The polyurethane comprises the following raw materials in parts by weight: 100 parts of polyurethane, 10-50 parts of filler, 2-4 parts of hydrogen-containing silicone oil and 3-5 parts of vulcanizing agent. The preparation method comprises the following steps: the filler and the polyurethane are banburied uniformly in a banbury mixer, and then the banburied polyurethane is taken to be added with hydrogen-containing silicone oil and vulcanizing agent in turn in a small amount and multiple batches on an open rubber mixing mill. And finally, vulcanizing the mixed rubber on a flat rubber vulcanizing machine at the temperature of 150 ℃ and 190 ℃ for 5-15min to obtain the platinum vulcanization mixed polyurethane. The platinum vulcanization mixing type polyurethane has the characteristics of low hardness, good mechanical property, high safety and the like.
Description
Technical Field
The invention relates to platinum vulcanization mixing type polyurethane and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Among the mechanical properties of polyurethane rubber, the wear resistance and the tensile strength are not comparable with those of other rubbers, so that the polyurethane rubber is widely applied to industries such as mine mining and dressing, coal mines, chemical industry, metallurgy, machinery and the like. Polyurethane elastomers are classified into a Mixing Polyurethane (MPU), a Casting Polyurethane (CPU), and a Thermoplastic Polyurethane (TPU) according to the processing method. Thermoplastic polyurethanes have been widely used in the medical industry because of their good biocompatibility and their high mechanical properties. The mixed polyurethane elastomer (or polyurethane rubber) has 3 vulcanization systems such as sulfur vulcanization, peroxide vulcanization, isocyanate vulcanization and the like, wherein the sulfur vulcanization is the most common method, the mixed rubber vulcanized by the system has excellent tear resistance, the peroxide vulcanized rubber has the characteristics of good aging resistance and low compression deformation, and the isocyanate vulcanization system can be used for preparing high-hardness mixed rubber. Generally, the physical properties of the compounded polyurethane rubber are best within the range of Shore A hardness of 55-80 degrees.
The central vein catheterization through peripheral venipuncture is realized by utilizing a catheter to puncture from a vein of a peripheral arm, the catheter directly reaches a great vein close to a heart, the direct contact between chemotherapy drugs and the vein of the arm is avoided, and the blood flow speed of the great vein is high, so that the chemotherapy drugs can be quickly diluted, and the stimulation of the drugs to blood vessels is prevented. Among materials of a Peripherally Inserted Central Catheter (PICC), the PICC catheter made of a silicone rubber material is softer and has less damage to the inner wall of a blood vessel, but the mechanical property is poorer, the catheter wall is thicker, and the catheter flux of the same outer diameter is much smaller than that of a polyurethane PICC catheter. And polyurethane PICC pipe material is harder, causes the damage of blood vessel inner wall easily when putting the pipe, and its biocompatibility is relatively poor than silicon rubber PICC, causes phlebitis and thrombus etc. easily. But the mechanical property is better, the high pressure injection type PICC can be made into a high pressure injection type PICC for enhancing the high pressure injection contrast medium when in CT, and the central venous pressure can also be measured. And compared with silicon rubber PICC, the pipe is not easy to break. If a new material which has the advantages of good biocompatibility and soft texture of the silicone rubber catheter, and the advantages of good mechanical property of the polyurethane material and high pressure resistance and injectability can be developed, the PICC catheter made of the new material can greatly reduce the probability of complication occurrence and the occurrence of tube breakage rate, and reduce the pain of patients and the risk of body injury.
The mixing polyurethane has mechanical properties comparable to thermoplastic polyurethane, has soft texture, and is a potential for development into next generation PICC catheters. The vulcanization system of the mixing type polyurethane is divided into three types, which are respectively as follows: isocyanate vulcanization, peroxide vulcanization and sulfur vulcanization. However, the biocompatibility of MPU vulcanized by the three vulcanization systems is poor, and the requirements of implantable medical devices cannot be met. Therefore, how to achieve better biocompatibility of the mixing type polyurethane on the basis of keeping higher mechanical property and soft texture is a problem which needs to be solved urgently at present. At present, no report for solving the problem is found at home and abroad.
In the experiment, the invention accidentally finds that the platinum and the hydrogen-containing silicone oil can vulcanize and form the mixed polyurethane at high temperature, and the principle of the invention is probably that the platinum is used for catalyzing the hydrogen-containing silicone oil to dehydrogenate to generate free radicals, so that the free radical addition reaction of double bonds in the mixed polyurethane can be initiated, and the mixed polyurethane is vulcanize and formed. The platinum is used for vulcanizing the mixed polyurethane, so that the mixed polyurethane vulcanized rubber has better biocompatibility on the basis of ensuring higher mechanical property and soft texture.
Disclosure of Invention
The invention aims to provide platinum vulcanization mixing type polyurethane and a preparation method thereof. Platinum is used as a vulcanizing agent, and hydrogen-containing silicone oil is dehydrogenated to form free radicals, so that the free radical crosslinking reaction of polyurethane double bonds is initiated, polyurethane is chemically crosslinked through carbon-carbon bonds to form a three-dimensional network structure, and the obtained vulcanized rubber has the advantages of high mechanical property, good biocompatibility and high safety. Can be widely applied to various fields, in particular to the medical field.
The invention provides platinum vulcanization mixing type polyurethane and a preparation method thereof, which are characterized in that: the platinum vulcanized mixed polyurethane consists of polyurethane, a filler, hydrogen-containing silicone oil and a vulcanizing agent, wherein the components of the platinum vulcanized mixed polyurethane in parts by weight are shown in the table below.
The polyurethane is mixed polyurethane containing double bonds.
The polyurethane is polyester polyurethane or polyether polyurethane.
The filler is as follows: one or more of carboxyl modified carbon nano tube, silane modified white carbon black, gas phase white carbon black, precipitation method white carbon black or active calcium carbonate, and the specific surface area of the carbon nano tube is 100-300m2/g。
The hydrogen-containing silicone oil is as follows: the side chain hydrogen-containing silicone oil has hydrogen content of 1-2% and viscosity of 50-300 mPa.
The vulcanizing agent is: platinum vulcanizing agent.
The invention also provides a preparation method of the platinum vulcanization mixing type polyurethane, which comprises the following specific steps: the white carbon black and the polyurethane are banburied evenly in a banbury mixer, and then the banburied polyurethane is taken to be added with hydrogen-containing silicone oil and a vulcanizing agent in a small amount and multiple batches in turn on an open type rubber mixing mill at the temperature of 40-60 ℃. And finally, vulcanizing the mixed rubber on a flat rubber vulcanizing machine at the temperature of 150 ℃ and 190 ℃ for 5-15min to obtain the platinum vulcanization mixed polyurethane.
The invention has the advantages that platinum is adopted as a vulcanizing agent, and the hydrogen-containing silicone oil is dehydrogenated to form free radicals, so that the free radical crosslinking reaction of polyurethane double bonds is initiated, the polyurethane is chemically crosslinked through carbon-carbon bonds to form a three-dimensional network structure, the tensile strength reaches 24MPa, and the mechanical property is excellent; the polyurethane has cytotoxicity of 1-2 grade and high biocompatibility, and can be used as an implant material.
The specific implementation mode is as follows:
the present invention is specifically described and further illustrated by the following examples, which should not be construed as limiting the scope of the invention. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
Test criteria used in the examples:
tensile strength: determination of tensile stress strain property of GBT 528-2009 vulcanized rubber or thermoplastic rubber
Tear strength: determination of the tear Strength of GBT 529-
Cytotoxicity test: GBT 16886.5-2017 in vitro cytotoxicity test
Delayed type hypersensitivity reaction: GBT 16886.10-2017 medical device biological evaluation part 10: irritation and skin sensitization test
Hemolysis test: GB T16886.4-2003 medical devices biological evaluation part 4 test selection for interaction with blood
The procedure for preparation of examples 1-7 and comparative examples 1-4 is as follows:
according to the raw material mass ratio shown in table 1, the filler and the polyurethane are banburying uniformly in a banbury mixer, and then the banburied polyurethane is taken out to be added with hydrogen-containing silicone oil and vulcanizing agent in turn in small quantities and multiple batches at 40-60 ℃ on an open rubber mixing mill. And finally, vulcanizing the mixed rubber on a flat rubber vulcanizing machine according to the vulcanization conditions shown in the table 1 to obtain the platinum vulcanization mixed polyurethane.
The mechanical properties of inventive examples 1-5 and comparative examples 1-4 are shown in Table 2.
As shown in Table 1, the tear strength and the tensile strength of examples 1 to 5 and comparative example 4 were 55 KN/m or more and 19MPa or more, respectively, and they had high mechanical strength. Compared with the examples 1-5, the filler in the comparative example 1 is only added by 5 parts, and the filler has a reinforcing effect on the mixing polyurethane and plays a role in physical winding and crosslinking, so that the tensile strength and the tear strength of the polyurethane are lower; in comparative example 2, only 1 part of hydrogen-containing silicone oil and 2 parts of vulcanizing agent are added, and vulcanization molding is not carried out during vulcanization, which shows that the hydrogen-containing silicone oil and the vulcanizing agent need to reach certain amounts to ensure that the mixed polyurethane can achieve the purpose of vulcanization. In comparative example 3, vulcanization conditions of 140 ℃ and 4min were adopted, and the vulcanizate obtained was inferior in properties because the vulcanizate was not completely vulcanized in the rubber compound under the vulcanization conditions.
The safety tests of examples 1 to 5 of the present invention and comparative examples 1 to 4 are shown in Table 3.
As can be seen from Table 3, the cytotoxicity test, delayed type hypersensitivity and hemolysis test of examples 1 to 5 and comparative examples 1 to 3 were all passed, indicating that the platinum vulcanization kneading type polyurethane of the present invention has a better biocompatibility. The reason why the cytotoxicity test, the delayed type hypersensitivity reaction and the hemolysis test of comparative example 4 were not satisfied is that the peroxide (bis-dipentamethylenediamine) added as the vulcanizing agent of the millable polyurethane in comparative example 4 had a large amount of residual substances of the peroxide vulcanizing agent after vulcanization and had a certain influence on the biocompatibility.
In conclusion, the platinum vulcanization mixing type polyurethane prepared by the invention not only has good mechanical property, but also has the characteristics of no toxicity, no stimulation and high safety to organisms.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the description as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (3)
1. A platinum vulcanization mixing type polyurethane is characterized in that: the polyurethane rubber is prepared from 100 parts by mass of polyurethane, 10-50 parts by mass of filler, 2-4 parts by mass of hydrogen-containing silicone oil and 3-5 parts by mass of vulcanizing agent; wherein the polyurethane is double-bond-containing mixing polyurethane; the hydrogen-containing silicone oil is side chain hydrogen-containing silicone oil, the hydrogen content of the side chain hydrogen-containing silicone oil is 1-2%, and the viscosity of the side chain hydrogen-containing silicone oil is 50-300mPa & s; the vulcanizing agent is a platinum vulcanizing agent;
the preparation method comprises the following specific steps: the filler and polyurethane are banburied evenly in a banbury mixer, the banburied polyurethane is taken to be added with hydrogen-containing silicone oil and a vulcanizing agent in a small amount and multiple batches in turn at 40-60 ℃ on an open rubber mixing mill, and finally the mixed rubber is vulcanized for 5-15min at the temperature of 150-190 ℃ on a flat rubber vulcanizing machine to obtain the platinum vulcanization mixed polyurethane.
2. The platinum vulcanization mixing type polyurethane according to claim 1, characterized in that: the polyurethane is polyester polyurethane or polyether polyurethane.
3. The platinum vulcanization mixing type polyurethane according to claim 1, characterized in that: the filler is as follows: one or more of carboxyl modified carbon nano tube, silane modified white carbon black, gas phase white carbon black, precipitation method white carbon black or active calcium carbonate, and the specific surface area of the carbon nano tube is 100-300m2/g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811611949.XA CN109627749B (en) | 2018-12-27 | 2018-12-27 | Platinum vulcanization mixing type polyurethane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811611949.XA CN109627749B (en) | 2018-12-27 | 2018-12-27 | Platinum vulcanization mixing type polyurethane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109627749A CN109627749A (en) | 2019-04-16 |
| CN109627749B true CN109627749B (en) | 2020-12-18 |
Family
ID=66078343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811611949.XA Active CN109627749B (en) | 2018-12-27 | 2018-12-27 | Platinum vulcanization mixing type polyurethane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109627749B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3325016B2 (en) * | 2000-12-27 | 2002-09-17 | 東洋ゴム工業株式会社 | Method of manufacturing polyurethane polishing pad for semiconductor polishing |
| CN102016728A (en) * | 2008-05-01 | 2011-04-13 | 株式会社普利司通 | Conductive endless belt |
| CN102977612A (en) * | 2012-11-05 | 2013-03-20 | 安徽金桥电缆有限公司 | Flame-retardant and environmentally-friendly acrylate rubber cable material and its preparation method |
| CN103376651A (en) * | 2012-04-27 | 2013-10-30 | 富士胶片株式会社 | Resin composition for laser engraving, relief printing plate precursor, relief printing plate, and process for making the relief printing plate precursor and the relief printing plate |
| CN105482125A (en) * | 2016-01-13 | 2016-04-13 | 上海应用技术学院 | Resin for UV-curing LED packaging adhesive and preparation method |
| CN106433548A (en) * | 2016-10-12 | 2017-02-22 | 武汉鼎丰设备备件材料有限公司 | Special instantaneous self-healing seal |
| CN108587123A (en) * | 2018-05-10 | 2018-09-28 | 成都思立可科技有限公司 | A kind of dynamic-vulcanization thermoplastic Polyurethane/Polysiloxane elastomer and preparation method thereof |
| CN109021583A (en) * | 2018-08-15 | 2018-12-18 | 山东百多安医疗器械有限公司 | Three component tear-proof silicon rubber of one kind and preparation method |
-
2018
- 2018-12-27 CN CN201811611949.XA patent/CN109627749B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3325016B2 (en) * | 2000-12-27 | 2002-09-17 | 東洋ゴム工業株式会社 | Method of manufacturing polyurethane polishing pad for semiconductor polishing |
| CN102016728A (en) * | 2008-05-01 | 2011-04-13 | 株式会社普利司通 | Conductive endless belt |
| CN103376651A (en) * | 2012-04-27 | 2013-10-30 | 富士胶片株式会社 | Resin composition for laser engraving, relief printing plate precursor, relief printing plate, and process for making the relief printing plate precursor and the relief printing plate |
| CN102977612A (en) * | 2012-11-05 | 2013-03-20 | 安徽金桥电缆有限公司 | Flame-retardant and environmentally-friendly acrylate rubber cable material and its preparation method |
| CN105482125A (en) * | 2016-01-13 | 2016-04-13 | 上海应用技术学院 | Resin for UV-curing LED packaging adhesive and preparation method |
| CN106433548A (en) * | 2016-10-12 | 2017-02-22 | 武汉鼎丰设备备件材料有限公司 | Special instantaneous self-healing seal |
| CN108587123A (en) * | 2018-05-10 | 2018-09-28 | 成都思立可科技有限公司 | A kind of dynamic-vulcanization thermoplastic Polyurethane/Polysiloxane elastomer and preparation method thereof |
| CN109021583A (en) * | 2018-08-15 | 2018-12-18 | 山东百多安医疗器械有限公司 | Three component tear-proof silicon rubber of one kind and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 聚氨酯/硅橡胶动态硫化热塑性弹性体的制备及性能研究;李善良;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20111015(第10期);B016-65 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109627749A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6730989B2 (en) | Nano composite elastomer | |
| US9931440B2 (en) | Biocompatible self-lubricating polymer compositions and their use in medical and surgical devices | |
| CN109651822B (en) | Medical silicone rubber with high mechanical property and preparation method thereof | |
| US5516857A (en) | Thermoplastic urethane elastomeric alloys | |
| EP3581603A1 (en) | Thermoplastic organosilicone-polyurethane elastomer and preparation method therefor | |
| CN1299382A (en) | Polysiloxane-contg. polyurethane elastomeric compositions | |
| ES2073528T3 (en) | PROCEDURE FOR PREPARING ELASTOMER POLYMERS OF POLYURETHANE AND POLYURETHANE-UREA, AS WELL AS PREPARED POLYURETHANES. | |
| CN109627749B (en) | Platinum vulcanization mixing type polyurethane and preparation method thereof | |
| CN104177836A (en) | Medical silicon rubber formula and preparation method thereof | |
| DE212013000299U1 (en) | Latex Sponge | |
| CN106867260A (en) | A kind of rubber composition for X-ray protection and preparation method thereof | |
| KR100271832B1 (en) | How to incorporate chitosan reinforced tires and chitosan into elastomers | |
| CN111303618A (en) | Organic silicon modified TPU medical catheter and preparation method thereof | |
| CN113773462A (en) | Invisible orthodontic polyurethane film, preparation method and application | |
| CN107189246A (en) | A kind of formula of brombutyl/silicon rubber and preparation method thereof | |
| Ghatge et al. | Elastomers from castor oil | |
| US20150203651A1 (en) | High wear resistance shoe sole material and manufacturing method thereof | |
| CN109796700A (en) | The medical PVC plastics of high transparency | |
| CN116217884A (en) | Self-repairing polyurethane elastomer material and preparation method thereof | |
| McMilin | An Assessment of Elastomers Biomedical Applications | |
| CN106928726A (en) | A kind of rubber composition and preparation method thereof | |
| CN102898689A (en) | Ultra-soft rubber for sole and preparation method thereof | |
| JPS5825338A (en) | Rubber composition | |
| CN111134783B (en) | Rubber ring for haemorrhoids ligation | |
| CN109054305B (en) | Material for three-cavity two-capsule tube and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 251100 Dezhou Qihe Economic Development Zone, Shandong Applicant after: Shandong baiduoan Medical Equipment Co.,Ltd. Address before: 251100 Dezhou Qihe Economic Development Zone, Shandong Applicant before: Shandong Branden Medical Device Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |