CN112898650A - Environment-friendly self-lubricating rubber hose mandrel rubber material and preparation method thereof - Google Patents
Environment-friendly self-lubricating rubber hose mandrel rubber material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
The invention discloses an environment-friendly self-lubricating rubber hose mandrel rubber material which comprises the following raw materials in parts by weight: 100 parts of NBR/PVC alloy and 110-2 parts of silica gel composite material, 15-35 parts of reinforcing agent, 35-70 parts of semi-reinforcing carbon black, 1-3 parts of coupling agent, 5-15 parts of environment-friendly plasticizer, 2-3 parts of antioxidant, 2-3 parts of processing aid, 5-15 parts of heat-resistant aid, 0.5-2.5 parts of vulcanizing agent and 2-5 parts of crosslinking aid; wherein, the composite material of the NBR/PVC alloy and the silica gel 110-2 is a mixture of the NBR/PVC alloy and the silica gel 110-2. Meanwhile, the invention also provides a preparation method of the rubber material. The rubber tube prepared from the mandrel rubber material obtained by the invention meets the national environmental protection upgrade and European Union ROSH standard, and has low DEHP content; in the production of the rubber tube, the core pulling operation efficiency is high, and the scratch rate of the inner layer of the rubber tube is low.
Description
Technical Field
The invention belongs to the technical field of rubber composite materials, and particularly relates to an environment-friendly self-lubricating rubber hose mandrel rubber material and a preparation method thereof.
Background
In recent years, the demand for rubber parts for automobiles has increased dramatically due to the increasing production of automobiles. If the rubber tube is used by 10 meters averagely per vehicle, the minimum requirement of the automobile rubber tube for the maintenance of new vehicles and old vehicles reaches hundreds of millions of meters by 2019 years, so that only one automobile rubber tube part needs thousands of tons of rubber materials of various rubber tubes, and millions of tons of rubber materials of rubber tube mandrels are needed.
At present, the rubber material of the automobile rubber hose mandrel in China is mainly nitrile rubber. Although the nitrile rubber has better oil resistance and excellent physical properties, when the nitrile rubber is used as a rubber tube mandrel material, most of the formulations use plasticizers such as DOP (dope) as plasticizers, and the mandrel material is used as a processing accessory in the production of rubber tubes. In addition, because the surface lubricity of the existing common mandrel material is poor, the core pulling efficiency is low and the inner layer of the rubber tube is easily scratched in the core pulling process.
Therefore, the development of the environment-friendly self-lubricating rubber tube mandrel rubber material is imperative and necessary, and great economic benefits and social benefits are certainly generated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the environment-friendly self-lubricating rubber tube mandrel rubber material and the preparation method thereof.
An environment-friendly self-lubricating rubber hose mandrel rubber material comprises the following raw materials in parts by weight:
100 parts of NBR/PVC alloy and 110-2 parts of silica gel composite material, 15-35 parts of reinforcing agent, 35-70 parts of semi-reinforcing carbon black, 1-3 parts of coupling agent, 5-15 parts of environment-friendly plasticizer, 2-3 parts of antioxidant, 2-3 parts of processing aid, 5-15 parts of heat-resistant aid, 0.5-2.5 parts of vulcanizing agent and 2-5 parts of crosslinking aid;
wherein the composite material of the NBR/PVC alloy and the silica gel 110-2 is prepared from the following components in percentage by mass (92-98): (2-8) NBR/PVC alloy and silica gel 110-2 mixture;
the NBR/PVC alloy is prepared by an emulsion polymerization method; the silica gel 110-2 is a paste fluid.
Preferably, the reinforcing agent is nano white carbon black.
Preferably, the coupling agent is a silane coupling agent or a titanate coupling agent.
Preferably, the environment-friendly plasticizer is at least one of environment-friendly oil or environment-friendly silicone oil.
Preferably, the antioxidant is a mixture of antioxidant NBC and any one of antioxidant 445 or antioxidant D, and the antioxidant NBC accounts for 75-95% of the weight of the antioxidant.
Preferably, the processing aid is at least one of dispersant L-24 and waxy polyethylene.
Preferably, the heat-resistant auxiliary agent is prepared from the following components in a mass ratio of 1: (1-3) a mixture of EVM and cerium oxide.
Preferably, the crosslinking assistant is any one or two of active zinc oxide, a promoter BZ, a promoter CZ, a promoter TE and a promoter DTDM.
The preparation method of the environment-friendly self-lubricating rubber hose mandrel rubber material comprises the following steps:
(1) plasticating: mixing NBR/PVC alloy and silica gel 110-2, mixing and thinly passing the mixture in an open mill to 100 ℃ Mooney viscosity ML1+440-60 to obtain the master batch;
(2) mixing: transferring the master batch into an internal mixer, adding a reinforcing agent, semi-reinforcing carbon black and a coupling agent, mixing for 3min at the rotation speed of 50-120rpm at the temperature of 130 ℃ of 120-; thinly passing through an open mill for 3-4 times, taking out the sheet, hanging and airing, standing for 12 hours, adding a vulcanizing agent and a crosslinking assistant into the open mill, selecting DCP/S/HVA-2/DTDM as a vulcanizing system, controlling the roller temperature to be not more than 60 ℃, thinly passing through for 4-5 times, taking out the sheet and cooling;
(3) and (3) vulcanization: remilling the rubber compound obtained in the step (2), and vulcanizing for 10-15min at the temperature of 160-180 ℃ and under the pressure of 10-15 MPa.
The invention can be realized by adopting the NBR/PVC alloy prepared by emulsion polymerization in the prior art.
The invention has the advantages that:
(1) the rubber tube prepared from the mandrel rubber material obtained by the invention meets the national environmental protection upgrade and European Union ROSH standard, and has low DEHP content;
(2) the material obtained by the invention has self-lubricating property, the core pulling operation efficiency is high in the production of the rubber tube, and the scratch rate of the inner layer of the rubber tube is low.
Detailed Description
Example 1
An environment-friendly self-lubricating rubber hose mandrel rubber material comprises the following raw materials in parts by weight:
100 parts of composite material of NBR/PVC alloy and silica gel 110-2, 15 parts of reinforcing agent, 70 parts of semi-reinforcing carbon black, 1 part of coupling agent, 15 parts of environment-friendly plasticizer, 3 parts of antioxidant, 2 parts of processing aid, 5 parts of heat-resistant aid, 0.5 part of vulcanizing agent and 2 parts of crosslinking aid;
wherein the composite material of the NBR/PVC alloy and the silica gel 110-2 is a mixture of the NBR/PVC alloy and the silica gel 110-2 with the mass ratio of 98: 2;
the reinforcing agent is nano white carbon black;
the coupling agent is a silane coupling agent KH 550;
the environment-friendly plasticizer is environment-friendly oil;
the antioxidant is a mixture of an antioxidant NBC and an antioxidant 445, and the antioxidant NBC accounts for 95% of the weight of the antioxidant.
The processing aid is a mixture of a dispersing agent L-24 and waxy polyethylene in a mass ratio of 1: 1;
the heat-resistant auxiliary agent is a mixture of EVM and cerium oxide in a mass ratio of 1: 1;
the crosslinking assistant is active zinc oxide;
the preparation method of the environment-friendly self-lubricating rubber hose mandrel rubber material comprises the following steps:
(1) plasticating: mixing NBR/PVC alloy and silica gel 110-2, mixing and thinly passing the mixture in an open mill to 100 ℃ Mooney viscosity ML1+440-60 to obtain the master batch;
(2) mixing: transferring the master batch into an internal mixer, adding a reinforcing agent, semi-reinforcing carbon black and a coupling agent, mixing at the rotation speed of 120 ℃ and 50rpm for 3min, adding an environment-friendly plasticizer, an antioxidant, a processing aid and a heat-resistant aid, mixing for 5min, adjusting the temperature to 100 ℃ and discharging; thinly passing through an open mill for 3 times, taking out the slices, hanging and airing, standing for 12 hours, adding a vulcanizing agent and a crosslinking assistant into the open mill, selecting DCP/S/HVA-2/DTDM as a vulcanizing system, controlling the roll temperature to be not more than 60 ℃, thinly passing for 4 times, taking out the slices and cooling;
(3) and (3) vulcanization: and (3) remilling the mixed rubber obtained in the step (2), and vulcanizing for 15min at the temperature of 170 ℃ and under the pressure of 10 MPa.
Example 2
The composite material of the NBR/PVC alloy and the silica gel 110-2 is a mixture of the NBR/PVC alloy and the silica gel 110-2 with the mass ratio of 95:5, and the rest is the same as the embodiment 1.
Example 3
The composite material of the NBR/PVC alloy and the silica gel 110-2 is a mixture of the NBR/PVC alloy and the silica gel 110-2 with the mass ratio of 92:8, and the rest is the same as the embodiment 1.
Example 4
An environment-friendly self-lubricating rubber hose mandrel rubber material comprises the following raw materials in parts by weight:
100 parts of composite material of NBR/PVC alloy and silica gel 110-2, 35 parts of reinforcing agent, 35 parts of semi-reinforcing carbon black, 3 parts of coupling agent, 5 parts of environment-friendly plasticizer, 2 parts of antioxidant, 3 parts of processing aid, 15 parts of heat-resistant aid, 2.5 parts of vulcanizing agent and 5 parts of crosslinking aid;
wherein the composite material of the NBR/PVC alloy and the silica gel 110-2 is a mixture of the NBR/PVC alloy and the silica gel 110-2 with the mass ratio of 98: 2;
the reinforcing agent is nano white carbon black;
the coupling agent is a titanate coupling agent;
the environment-friendly plasticizer is environment-friendly silicone oil;
the antioxidant is a mixture of an antioxidant NBC and an antioxidant D, and the antioxidant NBC accounts for 75% of the weight of the antioxidant.
The processing aid is a dispersant L-24;
the heat-resistant auxiliary agent is a mixture of EVM and cerium oxide in a mass ratio of 1: 3;
the crosslinking auxiliary agent is an accelerant BZ and an accelerant CZ with equal mass;
the preparation method of the environment-friendly self-lubricating rubber hose mandrel rubber material comprises the following steps:
(1) plasticating: mixing NBR/PVC alloy and silica gel 110-2, mixing and thinly passing the mixture in an open mill to 100 ℃ Mooney viscosity ML1+440-60 to obtain the master batch;
(2) mixing: transferring the master batch into an internal mixer, adding a reinforcing agent, semi-reinforcing carbon black and a coupling agent, mixing at the rotating speed of 130 ℃ and 120rpm for 3min, adding an environment-friendly plasticizer, an antioxidant, a processing aid and a heat-resistant aid, mixing for 10min, adjusting the temperature to 105 ℃ and discharging; thinly passing the mixture on an open mill for 4 times, taking out the sheet, hanging and airing the sheet, standing the sheet for 12 hours, adding a vulcanizing agent and a crosslinking assistant into the open mill, selecting DCP/S/HVA-2/DTDM as a vulcanizing system, controlling the roller temperature to be not more than 60 ℃, thinly passing the sheet for 5 times, taking out the sheet and cooling the sheet;
(3) and (3) vulcanization: and (3) remilling the mixed rubber obtained in the step (2), and vulcanizing for 10min at the temperature of 160 ℃ and under the pressure of 15 MPa.
Example 5
An environment-friendly self-lubricating rubber hose mandrel rubber material comprises the following raw materials in parts by weight:
100 parts of composite material of NBR/PVC alloy and silica gel 110-2, 20 parts of reinforcing agent, 50 parts of semi-reinforcing carbon black, 2 parts of coupling agent, 10 parts of environment-friendly plasticizer, 2 parts of antioxidant, 3 parts of processing aid, 10 parts of heat-resistant aid, 1 part of vulcanizing agent and 3 parts of crosslinking aid;
wherein the composite material of the NBR/PVC alloy and the silica gel 110-2 is a mixture of the NBR/PVC alloy and the silica gel 110-2 with the mass ratio of 98: 2;
the reinforcing agent is nano white carbon black;
the coupling agent is a titanate coupling agent;
the environment-friendly plasticizer is environment-friendly silicone oil and environment-friendly oil with equal mass;
the antioxidant is a mixture of an antioxidant NBC and an antioxidant D, and the antioxidant NBC accounts for 90% of the weight of the antioxidant.
The processing aid is waxy polyethylene;
the heat-resistant auxiliary agent is a mixture of EVM and cerium oxide in a mass ratio of 1: 2;
the crosslinking auxiliary agent is an accelerant TE and an accelerant DTDM with equal mass;
the preparation method of the environment-friendly self-lubricating rubber hose mandrel rubber material comprises the following steps:
(1) plasticating: mixing NBR/PVC alloy and silica gel 110-2, mixing and thinly passing the mixture in an open mill to 100 ℃ Mooney viscosity ML1+440-60 to obtain the master batch;
(2) mixing: transferring the master batch into an internal mixer, adding a reinforcing agent, semi-reinforcing carbon black and a coupling agent, mixing at the rotating speed of 120 ℃ and 80rpm for 3min, adding an environment-friendly plasticizer, an antioxidant, a processing aid and a heat-resistant aid, mixing for 5min, adjusting the temperature to 100 ℃ and discharging; thinly passing through an open mill for 3 times, taking out the slices, hanging and airing, standing for 12 hours, adding a vulcanizing agent and a crosslinking assistant into the open mill, selecting DCP/S/HVA-2/DTDM as a vulcanizing system, controlling the roll temperature to be not more than 60 ℃, thinly passing for 4 times, taking out the slices and cooling;
(3) and (3) vulcanization: and (3) remilling the mixed rubber obtained in the step (2), and vulcanizing for 10min at the temperature of 180 ℃ and under the pressure of 15 MPa.
Example 6
The coupling agent is KH570 or A151, and the other steps are the same as those in example 1.
Performance detection
The basic properties of the rubber materials provided in examples 1 to 3 were examined under the same examination conditions among the different examples, and the results are shown in Table 1.
TABLE 1 test results
As shown in the detection results in Table 1, with the increase of the silica gel 110-2, the core-pulling rate is obviously increased, the scratch rate of the product is reduced, and the DEHP detected by ROSH reaches the standard.
Claims (9)
1. The utility model provides an environment-friendly self-lubricating rubber tube dabber rubber material which characterized in that: the feed comprises the following raw materials in parts by weight:
100 parts of NBR/PVC alloy and 110-2 parts of silica gel composite material, 15-35 parts of reinforcing agent, 35-70 parts of semi-reinforcing carbon black, 1-3 parts of coupling agent, 5-15 parts of environment-friendly plasticizer, 2-3 parts of antioxidant, 2-3 parts of processing aid, 5-15 parts of heat-resistant aid, 0.5-2.5 parts of vulcanizing agent and 2-5 parts of crosslinking aid;
wherein the composite material of the NBR/PVC alloy and the silica gel 110-2 is prepared from the following components in percentage by mass (92-98): (2-8) NBR/PVC alloy and silica gel 110-2 mixture;
the NBR/PVC alloy is prepared by an emulsion polymerization method; the silica gel 110-2 is a paste fluid.
2. The environment-friendly self-lubricating rubber hose mandrel rubber material as claimed in claim 1, wherein: the reinforcing agent is nano white carbon black.
3. The environment-friendly self-lubricating rubber hose mandrel rubber material as claimed in claim 1, wherein: the coupling agent is a silane coupling agent or a titanate coupling agent.
4. The environment-friendly self-lubricating rubber hose mandrel rubber material as claimed in claim 1, wherein: the environment-friendly plasticizer is at least one of environment-friendly oil or environment-friendly silicone oil.
5. The environment-friendly self-lubricating rubber hose mandrel rubber material as claimed in claim 1, wherein: the antioxidant is a mixture of an antioxidant NBC and any one of an antioxidant 445 or an antioxidant D, and the antioxidant NBC accounts for 75-95% of the weight of the antioxidant.
6. The environment-friendly self-lubricating rubber hose mandrel rubber material as claimed in claim 1, wherein: the processing aid is at least one of dispersing agent L-24 and waxy polyethylene.
7. The environment-friendly self-lubricating rubber hose mandrel rubber material as claimed in claim 1, wherein: the heat-resistant auxiliary agent is prepared from the following components in a mass ratio of 1: (1-3) a mixture of EVM and cerium oxide.
8. The environment-friendly self-lubricating rubber hose mandrel rubber material as claimed in claim 1, wherein: the crosslinking assistant is one or two of active zinc oxide, a promoter BZ, a promoter CZ, a promoter TE and a promoter DTDM.
9. The preparation method of the environment-friendly self-lubricating rubber hose mandrel rubber material as claimed in any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:
(1) plasticating: mixing NBR/PVC alloy and silica gel 110-2, mixing and thinly passing the mixture in an open mill to 100 ℃ Mooney viscosity ML1+440-60 to obtain the master batch;
(2) mixing: transferring the master batch into an internal mixer, adding a reinforcing agent, semi-reinforcing carbon black and a coupling agent, mixing for 3min at the rotation speed of 50-120rpm at the temperature of 130 ℃ of 120-; thinly passing through an open mill for 3-4 times, taking out the sheet, hanging and airing, standing for 12 hours, adding a vulcanizing agent and a crosslinking assistant into the open mill, selecting DCP/S/HVA-2/DTDM as a vulcanizing system, controlling the roller temperature to be not more than 60 ℃, thinly passing through for 4-5 times, taking out the sheet and cooling;
(3) and (3) vulcanization: remilling the rubber compound obtained in the step (2), and vulcanizing for 10-15min at the temperature of 160-180 ℃ and under the pressure of 10-15 MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115058061A (en) * | 2022-05-19 | 2022-09-16 | 青岛昂记橡塑科技有限公司 | Rubber additive for improving aging resistance of rubber, and preparation method and application thereof |
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| CN106397882A (en) * | 2016-10-18 | 2017-02-15 | 南京利德东方橡塑科技有限公司 | Highly thermal-aging-resistant and ozone-aging-resistant butyronitrile/polyvinyl chloride rubber composition |
| CN107033409A (en) * | 2017-04-11 | 2017-08-11 | 山东美晨先进高分子材料科技有限公司 | A kind of NBR, PVC rubber compounding composition of high osmotic-pressure-tolerant |
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| CN103804732A (en) * | 2014-02-21 | 2014-05-21 | 河北春风银星胶辊有限公司 | Coating rubber sizing material of dual-purpose printing rubber roller for UV (ultraviolet) ink and common ink |
| CN106397882A (en) * | 2016-10-18 | 2017-02-15 | 南京利德东方橡塑科技有限公司 | Highly thermal-aging-resistant and ozone-aging-resistant butyronitrile/polyvinyl chloride rubber composition |
| CN107033409A (en) * | 2017-04-11 | 2017-08-11 | 山东美晨先进高分子材料科技有限公司 | A kind of NBR, PVC rubber compounding composition of high osmotic-pressure-tolerant |
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Cited By (2)
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| CN115058061A (en) * | 2022-05-19 | 2022-09-16 | 青岛昂记橡塑科技有限公司 | Rubber additive for improving aging resistance of rubber, and preparation method and application thereof |
| CN115058061B (en) * | 2022-05-19 | 2024-02-09 | 青岛昂记橡塑科技有限公司 | Rubber additive for improving ageing resistance of rubber, preparation method and application |
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