CN107513263B - Thermoplastic elastomer gasket material and production method thereof - Google Patents
Thermoplastic elastomer gasket material and production method thereof Download PDFInfo
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- CN107513263B CN107513263B CN201710973920.5A CN201710973920A CN107513263B CN 107513263 B CN107513263 B CN 107513263B CN 201710973920 A CN201710973920 A CN 201710973920A CN 107513263 B CN107513263 B CN 107513263B
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- thermoplastic elastomer
- gasket material
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- elastomer gasket
- coupling agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
A thermoplastic elastomer gasket material is produced by taking aliphatic polyketone resin (POK), Ethylene Propylene Diene Monomer (EPDM), hydrogenated styrene-butadiene-styrene copolymer (SEBS), filling oil, nano-filler, a silane coupling agent, an antioxidant and a lubricant as raw materials, and is technically characterized by comprising the following raw materials in percentage by weight: 35-75% of aliphatic polyketone resin (POK), 10-20% of hydrogenated styrene-butadiene-styrene copolymer (SEBS), 5-10% of Ethylene Propylene Diene Monomer (EPDM), 10-20% of filling oil, 2-15% of nano filler, 0.1-2% of silane coupling agent, 0.2-1.0% of antioxidant and 0.2-2% of lubricant. The thermoplastic elastomer gasket material has the characteristic of injection molding, reduces the complex steps of mixing, vulcanizing, edge removing, siliconizing and the like of the traditional rubber gasket rubber plug, realizes one-step molding, has low production cost, reduces the risk caused by the complex production process, has the characteristics of the rubber gasket rubber plug, and has better sealing property, rebound resilience and aging resistance.
Description
Technical Field
The invention relates to a thermoplastic elastomer gasket material capable of being injection molded, which is mainly used for oral liquid and nutrient solution gaskets in the medicine packaging material industry, gaskets in the pesticide packaging field and the like.
Background
With the development of medical health care, the requirements for oral liquid and infusion medical instruments are more and more refined, and the requirements are embodied in the aspects of safety, liquid medicine compatibility, transportation convenience, processing adaptability, convenient use and the like of an infusion container. The medicine packing material gasket and the rubber plug mainly use a butyl rubber material and a silicon rubber material at present, and the processing of the butyl rubber needs to be carried out by the processing steps of mixing, open milling, vulcanization, flash removal, silicification and the like. The formula of the butyl rubber plug is complex, and processing aids, anti-aging agents, vulcanizing agents and the like in the butyl rubber plug have the risk of separating out to pollute liquid medicine. The processing procedure of the butyl rubber plug is complex, the processing period of a single product is long, the labor and material resources are consumed, the rejection rate is high, and in view of the thermosetting characteristic of the butyl rubber, leftover materials and the like generated by the butyl rubber plug are difficult to recycle. The invention adopts the thermoplastic elastomer material to prepare the products such as the packing material gasket and the like, and has the characteristics of quick injection molding, simple processing, high production efficiency, simplified product formula components, no pollution to liquid medicine, low compression permanent deformation of the product, good sealing property and the like.
Disclosure of Invention
The invention aims to develop a thermoplastic elastomer gasket material meeting the injection molding requirement, so that the gasket material has the characteristics of quick injection molding, good sealing property, good liquid medicine compatibility and good lubricating property with a polypropylene syringe.
The thermoplastic elastomer gasket material is technically characterized by comprising the following raw materials in percentage by weight: 35-75% of aliphatic polyketone resin (POK), 10-20% of hydrogenated styrene-butadiene-styrene copolymer (SEBS), 5-10% of Ethylene Propylene Diene Monomer (EPDM), 10-20% of filling oil, 2-15% of nano filler, 0.1-2% of silane coupling agent, 0.2-1.0% of antioxidant and 0.2-2% of lubricant.
The raw materials of the invention have the preferable range of 40 to 70 weight percent of aliphatic polyketone resin (POK), 15 to 20 weight percent of hydrogenated styrene-butadiene-styrene copolymer (SEBS), 6 to 10 weight percent of Ethylene Propylene Diene Monomer (EPDM), 15 to 20 weight percent of filling oil, 3 to 13 weight percent of nano filler, 0.2 to 1.5 weight percent of silane coupling agent, 0.2 to 0.8 weight percent of antioxidant and 0.2 to 1.2 weight percent of lubricant.
The aliphatic polyketone resin (POK) is a copolymer of carbon monoxide, ethylene and propylene, and has a melt mass flow rate of 15-35g/10min at 240 ℃ under the condition of 2.16 kg.
The styrene content of the hydrogenated styrene-butadiene-styrene copolymer is 30-33%, and the molecular weight is more than or equal to 20 ten thousand.
The Ethylene Propylene Diene Monomer (EPDM) is granular, and the Mooney viscosity range is 51-61(M L125 ℃ 1+ 4).
The filling oil is naphthenic oil or paraffin oil or a mixture of the naphthenic oil and the paraffin oil in a ratio of 1: 2.
The nano filler is nano kaolin or nano silicon dioxide or a mixture of the nano kaolin and the nano silicon dioxide within the range of 1:1-1: 2.
A method of producing the foregoing thermoplastic elastomer gasket material is as follows:
material pretreatment: 1) adding SEBS into the filling oil, stirring at a high speed for 5 minutes, controlling the temperature to be 30-70 ℃, and standing for 48 hours; 2) adding a silane coupling agent diluted by glycerol into the nano filler, mixing at a low speed for 120 seconds, and drying for later use;
mixing materials: weighing materials according to the requirements, respectively adding POK resin, EPDM, oil-filled SEBS, nano filler treated by silane coupling agent, antioxidant and lubricant into a mixer, mixing at low speed for 120 seconds, mixing at high speed for 60 seconds, pouring into a hopper of an extruder, extruding, granulating and packaging by using a double-screw extruder, wherein the temperature of each section of the double screw is 85-105 ℃, 140-160 ℃, 160-200 ℃, 160-190 ℃ and the head temperature is 160-175 ℃.
The polyketone resin (POK), the Ethylene Propylene Diene Monomer (EPDM), the hydrogenated styrene-butadiene-styrene copolymer (SEBS), the filling oil, the silane coupling agent, the antioxidant, the nano filler, the lubricant and the like are matched and cooperated with each other in a proper proportion, so that the produced thermoplastic elastomer gasket material has the following excellent performances:
1) POK is used as a thermoplastic base material in the components, and on the basis of keeping the rubber characteristics of high resilience and low compression permanent deformation of ethylene propylene diene monomer, the molding plasticity required by granulation and injection molding is provided, so that the integral formula system has good rebound and pressure-variable characteristics and the characteristic of thermoplasticity processing;
2) the hardness and resilience in the oil-filled SEBS balance material; nanofillers balance hardness and strength in the material; lubricants are used to improve the processing and forming characteristics of the material; the antioxidant is used for improving the ageing resistance of the material.
Detailed Description
Material pretreatment: 1) adding SEBS into the filling oil, stirring at a high speed for 5 minutes, controlling the temperature to be 30-70 ℃, and standing for 48 hours; 2) adding a silane coupling agent diluted by glycerol into the nano filler, wherein the weight ratio of glycerol: and (3) mixing the silane coupling agent at a low speed for 120 seconds, and drying the mixture for later use.
Mixing materials: weighing the materials according to the requirements, respectively adding the POK resin, the EPDM, the oil-filled SEBS, the nano filler treated by the silane coupling agent, the antioxidant and the lubricant into a mixer, mixing at a low speed for 120 seconds, mixing at a high speed for 60 seconds, pouring into a hopper of an extruder, extruding by a double-screw extruder, granulating and packaging.
The temperature of each section of the twin-screw is 85-105 ℃, 140-160 ℃, 160-200 ℃, 160-190 ℃ and the head temperature is 160-175 ℃.
Example of the watch
Table two performance parameters of the examples:
the invention realizes the injection molding of the elastomer gasket material by the rubber-plastic blending of the multi-phase system of EPDM, POK resin, SEBS, filling oil and filler, simplifies the molding process of various gaskets for packaging and improves the drug safety of the gasket. And through the filler pretreatment, SEBS pre-oil charge and blending modification of a multiphase system, the rubber characteristic of the gasket is ensured on the basis of realizing injection molding, so that the gasket has the characteristics of required sealing property and resilience, is a thermoplastic elastomer gasket material with simplified processing and safe use, and becomes a new choice capable of replacing the traditional rubber material.
Claims (6)
1. A thermoplastic elastomer gasket material is produced by adopting aliphatic polyketone resin, ethylene propylene diene monomer, hydrogenated styrene-butadiene-styrene copolymer, filling oil, nano-filler, silane coupling agent, antioxidant and lubricant as raw materials, and is technically characterized by comprising the following raw materials in percentage by weight: 35-70% of aliphatic polyketone resin, 10-20% of hydrogenated styrene-butadiene-styrene copolymer, 5-10% of ethylene propylene diene monomer, 10-20% of filling oil, 2-15% of nano filler, 0.1-2% of silane coupling agent, 0.2-1.0% of antioxidant and 0.2-2% of lubricant;
the production method of the thermoplastic elastomer gasket material comprises the following steps:
material pretreatment: 1) adding hydrogenated styrene-butadiene-styrene copolymer into filling oil, stirring at high speed for 5 minutes, controlling the temperature to be 30-70 ℃, and standing for 48 hours; 2) adding a silane coupling agent diluted by glycerol into the nano filler, wherein the weight ratio of glycerol: mixing silane coupling agent 3:1 at low speed for 120 seconds, and drying for later use; mixing materials: weighing materials according to the requirements, respectively adding aliphatic polyketone resin, ethylene propylene diene monomer rubber, an oil-filled hydrogenated styrene-butadiene-styrene copolymer, a silane coupling agent treated nano filler, an antioxidant and a lubricant into a mixer, mixing at a low speed for 120 seconds, mixing at a high speed for 60 seconds, pouring into a hopper of an extruder, extruding and granulating by using a double-screw extruder, wherein the temperature of each section of the double screw is 85-105 ℃, 140-160 ℃, 160-200 ℃, 160-190 ℃ and the head temperature is 160-175 ℃.
2. A thermoplastic elastomer gasket material as claimed in claim 1, wherein said aliphatic polyketone resin is a copolymer of carbon monoxide, ethylene and propylene having a melt mass flow rate of from 15 to 35g/10min at 240 ℃ under 2.16 kg.
3. A thermoplastic elastomer gasket material as claimed in claim 1, wherein said hydrogenated styrene-butadiene-styrene copolymer has a styrene content of 30 to 33% and a molecular weight of 20 ten thousand or more.
4. The thermoplastic elastomer gasket material of claim 1, wherein said ethylene propylene diene monomer is in the form of particles and has a Mooney viscosity of 125 ℃ M L1 +4 value in the range of 51-61.
5. Thermoplastic elastomer gasket material according to claim 1, characterized in that the extender oil is naphthenic or paraffinic or a mixture of naphthenic and paraffinic oils in a ratio of 1: 2.
6. Thermoplastic elastomer gasket material according to claim 1, characterized in that the nanofiller is nano kaolin or nano silica or a mixture of nano kaolin and nano silica in the range of 1:1-1: 2.
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| CN201710973920.5A CN107513263B (en) | 2017-10-19 | 2017-10-19 | Thermoplastic elastomer gasket material and production method thereof |
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| CN201710973920.5A CN107513263B (en) | 2017-10-19 | 2017-10-19 | Thermoplastic elastomer gasket material and production method thereof |
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| CN107513263A CN107513263A (en) | 2017-12-26 |
| CN107513263B true CN107513263B (en) | 2020-08-04 |
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| US20220282078A1 (en) * | 2021-03-05 | 2022-09-08 | Parker-Hannifin Corporation | Thermoplastic Vulcanizates Comprising Aliphatic Polyketone and Ethylene-Propylene-Diene Monomer Rubber |
| CN116023736A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Styrene-butadiene rubber/polypropylene thermoplastic elastomer composition, vulcanized styrene-butadiene rubber/polypropylene thermoplastic elastomer, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998054261A2 (en) * | 1997-05-29 | 1998-12-03 | Bp Chemicals Limited | Toughened polyketone composition |
| CN1256289A (en) * | 1998-12-08 | 2000-06-14 | 罗姆和哈斯公司 | Impact resilience modifier composition and its prepn. |
| CN1322221A (en) * | 1998-10-07 | 2001-11-14 | 拜尔公司 | Body add-on parts based on thermoplastic polyketones |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USH302H (en) * | 1985-07-01 | 1987-07-07 | The United States Of America As Represented By The United States Department Of Energy | Ceramics containing dispersants for improved fracture toughness |
| CN100463942C (en) * | 2006-09-07 | 2009-02-25 | 浙江俊尔新材料有限公司 | Thermoplastic elastomer for injection adhering nylon material |
| CN101100593B (en) * | 2007-05-22 | 2010-05-26 | 深圳职业技术学院 | Environmental protection type SEBS thermoplastic elastic body sealing strip material and preparation method thereof |
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- 2017-10-19 CN CN201710973920.5A patent/CN107513263B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998054261A2 (en) * | 1997-05-29 | 1998-12-03 | Bp Chemicals Limited | Toughened polyketone composition |
| CN1322221A (en) * | 1998-10-07 | 2001-11-14 | 拜尔公司 | Body add-on parts based on thermoplastic polyketones |
| CN1256289A (en) * | 1998-12-08 | 2000-06-14 | 罗姆和哈斯公司 | Impact resilience modifier composition and its prepn. |
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