CN109627749A - A kind of platinum vulcanization blending-type polyurethane and preparation method thereof - Google Patents
A kind of platinum vulcanization blending-type polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN109627749A CN109627749A CN201811611949.XA CN201811611949A CN109627749A CN 109627749 A CN109627749 A CN 109627749A CN 201811611949 A CN201811611949 A CN 201811611949A CN 109627749 A CN109627749 A CN 109627749A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- blending
- platinum
- type polyurethane
- vulcanization
- 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.)
- Granted
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 present invention relates to a kind of platinum vulcanization blending-type polyurethanes and preparation method thereof.The polyurethane includes the raw material of following parts by weight: 100 parts of polyurethane, 10-50 parts of filler, 2-4 parts of containing hydrogen silicone oil, 3-5 parts of vulcanizing agent.The preparation method comprises the following steps: mixing is uniform in mixer by filler and polyurethane, then take the polyurethane after mixing is a small amount of on opening rubber mixing machine multiple batches of to sequentially add containing hydrogen silicone oil and vulcanizing agent.Finally by rubber compound, 150-190 DEG C of vulcanization 5-15min obtains platinum vulcanization blending-type polyurethane on plate rubber vulcanizing machine.The platinum vulcanizes blending-type polyurethane, has the characteristics that low hardness, good mechanical property, highly-safe.
Description
Technical field
The present invention relates to a kind of platinum vulcanization blending-type polyurethanes and preparation method thereof, belong to high polymer material technology neck
Domain.
Background technique
In the mechanical performance of polyurethane rubber, wearability with tensile strength is that other rubber can not be compared, thus wide
It is general to be used for the industries such as mine selecting, coal mine, chemical industry, metallurgy, machinery.Polyurethane elastomer is divided into the poly- ammonia of mixed milling type by processing method
Ester (MPU), casting type polyurethane (CPU) and thermoplastic polyurethane (TPU).Thermoplastic polyurethane is because it is with good biofacies
Capacitive, and there is very high mechanical performance, it has been widely used in medical industry.Blending-type polyurethane elastomer (or it is poly-
Urethane rubber) there are 3 kinds of vulcanizing systems such as sulfur vulcanization, peroxide cure, isocyanates vulcanization, wherein sulfur vulcanization is most logical
The mixing rubber tearing-resistant performance of method, system vulcanization is excellent, and the rubber of peroxide cure has resistance to ag(e)ing
High rigidity mixed milling type glue can be made in the feature that energy is good, compressive deformation is low, isocyanates vulcanizing system.Usual blending-type polyurethane rubber
Glue physical property within the scope of shore a hardness 55-80 degree is best.
It is to be punctured using conduit from the vein of periphery arm, conduit is straight through periphery venipuncture central vein catheter
Up to the big vein close to heart, chemotherapeutics is avoided to contact with the direct of arm vein, in addition the blood flow velocity of big vein is quickly,
Dilute chemotherapeutics can be rushed rapidly, prevent stimulation of the drug to blood vessel.In the material of peripherally inserted central conduit (PICC),
The material is soft for the PICC conduit of silastic material, smaller to blood vessel damage, but its mechanical performance is poor, and tube wall is thicker, phase
It is more much smaller than the PICC conduit of polyurethane with diameter catheter circulation.And polyurethane PICC conduit material is harder, is setting Guan Shirong
Blood vessel is easily caused to damage, biocompatibility is poor compared with silicon rubber PICC, easily causes phlebitis and thrombus etc..But its machine
Tool better performances, high-pressure injection contrast agent when can be made into high pressure resistant injection-type PICC for enhanced CT, also can measure in it is calm
Pulse pressure.Easily broken pipe is not allowed also relative to silicon rubber PICC.If a kind of biocompatibility for both having possessed silicon catheter can be developed
Good, soft advantage, and have the advantages that the new material of polyurethane material good mechanical property, high pressure resistant injectable, it is this
PICC conduit made of new material will significantly mitigate complication occur probability and disconnected pipe rate generation, reduce patient pain and
Somatic damage risk.
Blending-type polyurethane has the mechanical performance for the thermoplastic polyurethane that can match in excellence or beauty, and possesses soft quality, is one
Kind has exploitation at the potential quality of next-generation PICC conduit very much.The vulcanizing system of blending-type polyurethane is divided into three kinds, is respectively: isocyanide
Acid esters vulcanization, peroxide cure and sulfur cross-linking.But the MPU biocompatibility of these three vulcanizing systems vulcanization is poor, nothing
Method meets the requirement of Implantable Medical Device.Therefore blending-type polyurethane how to be made to keep higher mechanical performance and softness
Quality on the basis of, accomplish preferable biocompatibility, be current urgent problem.At present both at home and abroad there is not yet solving
The report of this problem.
The present invention is when testing, and blending-type polyurethane sulphur at high temperature can be made by chancing on platinum and containing hydrogen silicone oil
Chemical conversion type, pushing away its principle may be to be catalyzed containing hydrogen silicone oil dehydrogenation using platinum, generate free radicals, so as to cause the poly- ammonia of mixed milling type
The Radical Addition of double bond in ester, to make blending-type polyurethane sulfidization molding.Since the present invention is with platinum to mixing
Type polyurethane is vulcanized, to make blending-type polyurethane vulcanizate in the base for guaranteeing higher mechanical performance and soft quality
On plinth, there is preferable biocompatibility.
Summary of the invention
The object of the present invention is to provide a kind of platinum vulcanization blending-type polyurethanes and preparation method thereof.Use platinum as sulphur
Agent makes containing hydrogen silicone oil dehydrogenation form free radical, to cause the radical crosslinking reaction of polyurethane double bond, passes through polyurethane
Carbon-carbon bond chemical crosslinking, forms space network, and not only mechanical performance is strong for obtained vulcanizate, and good biocompatibility,
It is highly-safe.It can be widely applied to each Deng fields, especially medical field.
The present invention provides a kind of platinum vulcanization blending-type polyurethane and preparation method thereof, it is characterised in that: by polyurethane, fills out
The each group of material, containing hydrogen silicone oil, vulcanizing agent composition, a kind of platinum vulcanization blending-type polyurethane is grouped as mass fraction such as following table institute
Show.
The polyurethane is double bond containing blending-type polyurethane.
The polyurethane is polyester polyurethane or polyether polyurethane.
The filler are as follows: carboxy-modified carbon nanotube, silane-modified white carbon black, gas-phase silica, precipitated silica or
One of activated Calcium carbonate is a variety of, specific surface area 100-300m2/g。
The containing hydrogen silicone oil are as follows: side chain containing hydrogen silicone oil, hydrogen content 1-2%, viscosity 50-300mPas.
The vulcanizing agent are as follows: platinum vulcanizing agent.
The present invention also provides the preparation method of above-mentioned platinum vulcanization blending-type polyurethane, specific steps are as follows: by white carbon black
Mixing is uniform in mixer with polyurethane, then takes the polyurethane after mixing a small amount of at 40-60 DEG C on opening rubber mixing machine
Multiple batches of addition containing hydrogen silicone oil and vulcanizing agent successively.The finally 150-190 DEG C of vulcanization on plate rubber vulcanizing machine by rubber compound
5-15min obtains platinum vulcanization blending-type polyurethane.
The invention has the advantages that using platinum as vulcanizing agent, containing hydrogen silicone oil dehydrogenation is set to form free radical, to cause poly- ammonia
The radical crosslinking of ester double bond reacts, and is chemically crosslinked polyurethane by carbon-carbon bond, forms space network, and tensile strength reaches
To 24MPa, excellent in mechanical performance；The polyurethane cytotoxicity is 1-2 grades, and biocompatibility is high, can be used as implantation materials'use.
Specific embodiment:
The present invention is specifically described and is further illustrated below by embodiment, is not to be construed as limiting model of the invention
It encloses.The person skilled in the art in the field can make some non-intrinsically safe modifications and adaptations according to the content of aforementioned present invention.
Testing standard used by embodiment:
Tensile strength: the measurement of GBT 528-2009 vulcanized rubber or thermoplastic elastomer tensile stress-strain performance
Tearing strength: measurement (the trousers shape, square and new of GBT 529-2008 vulcanized rubber or thermoplastic elastomer tearing strength
Month shape sample)
Cell toxicity test: GBT 16886.5-2017 vitro cytotoxicity test
Delayed allergy: the 10th part of GBT 16886.10-2017 BiologicalEvaluationofMedicalDevice: stimulation is caused with skin
Quick test
Hemolytic test: the 4th part of GB T 16886.4-2003 BiologicalEvaluationofMedicalDevice and blood interaction test choosing
It selects
Embodiment 1-7 and comparative example 1-4 step preparation method are as follows:
By the ratio of material quality shown in table 1, by filler and polyurethane, mixing is uniform in mixer, then the polyurethane after mixing is taken to exist
It is a small amount of at 40-60 DEG C on opening rubber mixing machine multiple batches of to sequentially add containing hydrogen silicone oil and vulcanizing agent.Finally rubber compound is existed
Vulcanized on plate rubber vulcanizing machine by conditions of vulcanization shown in table 1, obtains platinum vulcanization blending-type polyurethane.
The mechanical performance of 1-5 of the embodiment of the present invention and comparative example 1-4 are listed in table 2.
As shown in above-mentioned table 1, the tearing strength of embodiment 1-5 and comparative example 4 has all reached 55 KN/m or more, stretches strong
Degree has all reached 19MPa or more, mechanical strength with higher.And comparative example 1-3 is compared with embodiment 1-5,1 filler of comparative example
Only add 5 parts, and filler has reinforcing effect to blending-type polyurethane, plays the role of physical entanglement crosslinking, so it is stretched
Intensity and tearing strength are lower；Comparative example 2 have added 1 part of containing hydrogen silicone oil and 2 parts of vulcanizing agents, when vulcanization, without sulfidization molding,
Illustrate that containing hydrogen silicone oil and vulcanizing agent need to achieve the purpose that a certain amount of can just blending-type polyurethane be made to reach vulcanization.Comparative example 3 is adopted
With 140 DEG C, the conditions of vulcanization of 4min, gained cured properties is poor, this is because under this conditions of vulcanization, rubber compound vulcanization
Not exclusively.
The safety testing of 1-5 of the embodiment of the present invention and comparative example 1-4 are listed in table 3.
By table 3 it is found that embodiment 1-5 and comparative example 1-3 cell toxicity test, delayed allergy and hemolytic test are all closed
Lattice illustrate that platinum vulcanization blending-type polyurethane of the present invention has preferable biocompatibility.And the cytotoxicity examination of comparative example 4
Test, delayed allergy and hemolytic test it is all unqualified, this is because joined peroxide (double two or five sulphur in comparative example 4
Agent) vulcanizing agent as blending-type polyurethane, peroxide vulcanizing agent residuals are more after curing, to biocompatibility
It has a certain impact.
Platinum vulcanization blending-type polyurethane prepared by the present invention not only has good mechanical performance in summary, but also
Have the characteristics that nontoxic, non-stimulated, highly-safe to organism.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of specification record.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (7)
1. a kind of platinum vulcanizes blending-type polyurethane, it is characterised in that: it is made of polyurethane, filler, containing hydrogen silicone oil, vulcanizing agent,
It is as shown in the table that a kind of each group of the platinum vulcanization blending-type polyurethane is grouped as mass fraction.
2. a kind of platinum according to claim 1 vulcanizes blending-type polyurethane, it is characterised in that: the polyurethane is containing double
The blending-type polyurethane of key.
3. a kind of platinum according to claim 1 vulcanizes blending-type polyurethane, it is characterised in that: the polyurethane is polyester
Type polyurethane or polyether polyurethane.
4. a kind of platinum according to claim 1 vulcanizes blending-type polyurethane, it is characterised in that: the filler are as follows: carboxyl
One of modified carbon nano-tube, silane-modified white carbon black, gas-phase silica, precipitated silica or activated Calcium carbonate are more
Kind, specific surface area 100-300m2/g。
5. a kind of platinum according to claim 1 vulcanizes blending-type polyurethane, it is characterised in that: the containing hydrogen silicone oil are as follows:
Side chain containing hydrogen silicone oil, hydrogen content 1-2%, viscosity 50-300mPas.
6. a kind of platinum according to claim 1 vulcanizes blending-type polyurethane, it is characterised in that: the vulcanizing agent are as follows: platinum
Golden vulcanizing agent.
7. the preparation method of claim 1 to 6 any platinum vulcanization blending-type polyurethane, specific steps are as follows: will be white
Carbon black and polyurethane mixing in mixer are uniform, then take the polyurethane after mixing on opening rubber mixing machine at 40-60 DEG C
A small amount of multiple batches of addition containing hydrogen silicone oil and vulcanizing agent successively.Finally by rubber compound 150-190 DEG C on plate rubber vulcanizing machine
Vulcanization 5-15min obtains platinum vulcanization blending-type polyurethane.
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 true CN109627749A (en) | 2019-04-16 |
| CN109627749B 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 |
|---|
| 李善良: "聚氨酯/硅橡胶动态硫化热塑性弹性体的制备及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109627749B (en) | 2020-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nurhamiyah et al. | Wholly biobased, highly stretchable, hydrophobic, and self-healing thermoplastic elastomer | |
| JP6730989B2 (en) | Nano composite elastomer | |
| Hernández Santana et al. | Routes to make natural rubber heal: A review | |
| CN106317530B (en) | A kind of heat resistant hydro-expansive rubber and preparation method thereof | |
| CN109651822B (en) | Medical silicone rubber with high mechanical property and preparation method thereof | |
| Yew et al. | Emerging crosslinking techniques for glove manufacturers with improved nitrile glove properties and reduced allergic risks | |
| Maji et al. | Styrenic Block copolymer‐based thermoplastic elastomers in smart applications: Advances in synthesis, microstructure, and structure–property relationships—a review | |
| AT501393A1 (en) | NETWORKABLE AND LUBRICATED PLASTIC CLOSURE PLASTIC | |
| ES2073528T3 (en) | PROCEDURE FOR PREPARING ELASTOMER POLYMERS OF POLYURETHANE AND POLYURETHANE-UREA, AS WELL AS PREPARED POLYURETHANES. | |
| CN108192162B (en) | A kind of Sports shoe sole abrasive rubber and preparation method thereof | |
| CN102086287A (en) | Thermoplastic elastomer material and plastic plug made of same | |
| CN101343346A (en) | Chitosan polyurethane material and preparation thereof | |
| Rao et al. | Mechanical properties of thermoplastic elastomeric blends of chitosan and natural rubber latex | |
| CN107722281A (en) | A kind of silicon rubber based on POSS reinforcement and crosslinking and preparation method thereof | |
| KR20200038300A (en) | Ziegler-Natta catalyzed polyisoprene articles | |
| Wei et al. | Asymmetric “Janus” Biogel for Human‐Machine Interfaces | |
| CN109627749A (en) | A kind of platinum vulcanization blending-type polyurethane and preparation method thereof | |
| CN106366470A (en) | High-purity rubber plug formula | |
| Wypych | Handbook of Curatives and Crosslinkers | |
| CN104788753B (en) | Pre-vulcanized natural rubber latex/chitosan/poly butyric ester blend material and preparation method | |
| CN109796700A (en) | The medical PVC plastics of high transparency | |
| Low et al. | Self-healing synthetic rubber composites: review of recent progress and future directions towards sustainability | |
| CN105837970B (en) | A kind of preparation method of trachea cannula pvc material | |
| CN104744948A (en) | Gelatin-based elastomer raw rubber, gelatin-based elastomer nano composite material and preparation method of two | |
| CN112538271A (en) | Hydrophilic silicone rubber capable of being used as medical catheter and preparation method and application 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 |
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. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |