CN104163993A - Ethylene propylene diene monomer rubber and EPDM reclaimed rubber co-used rubber composition, and preparation method and application thereof - Google Patents
Ethylene propylene diene monomer rubber and EPDM reclaimed rubber co-used rubber composition, and preparation method and application thereof Download PDFInfo
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- CN104163993A CN104163993A CN201410279288.0A CN201410279288A CN104163993A CN 104163993 A CN104163993 A CN 104163993A CN 201410279288 A CN201410279288 A CN 201410279288A CN 104163993 A CN104163993 A CN 104163993A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K3/02—Elements
- C08K3/06—Sulfur
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/40—Thiurams, i.e. compounds containing groups
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- 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 ethylene propylene diene monomer rubber and EPDM reclaimed rubber co-used rubber composition, and a preparation method and application thereof. The ethylene propylene diene monomer rubber and EPDM reclaimed rubber co-used rubber composition comprises, by mass, 90-50 parts of ethylene propylene diene monomer rubber and 10-50 parts of R-EPDM. The ethylene propylene diene monomer rubber and EPDM reclaimed rubber co-used rubber composition may also comprise other components such as an accelerator or sulphur. By doping ethylene propylene diene monomer reclaimed rubber and other components in a raw rubber, an ethylene propylene diene monomer rubber and EPDM reclaimed rubber co-used rubber composition that has excellent physical properties, has greatly reduced cost and can be widely applied in automobile engineering materials is developed.
Description
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Technical field
The invention belongs to polymeric material field, especially relate to terpolymer EP rubber and EPDM reclaimed rubber and use glue composition and its preparation method and application.
Background technology
China is that rubber consumes big country, rubber resource scarcity big country especially, and finding rubber raw materials source and substitute material thereof becomes one of vital task that Chinese struggle on without cease.Therefore, reclaimed rubber causes the concern of relevant enterprise and a large amount of uses gradually, its on the one hand can replace rubber, has alleviated the serious scarcity of synthetic rubber, natural rubber; Make on the other hand waste old realize recycling, solved the problem of waste old contaminate environment.
Reclaimed rubber low price, kind is more, and wherein Ethylene Propylene Terpolymer reclaimed rubber (English: R-EPDM) is the larger a kind of rubber substitute material of usage quantity in recent years.It is shaped as black or colored block, powdery solid, and main component is the reductive agent of admixture in the terpolymer of ethene, propylene and non-conjugated diene hydrocarbon and regenerative process and softening oil, calcium carbonate etc.There are some researchs for Ethylene Propylene Terpolymer reclaimed rubber, such as research is known Ethylene Propylene Terpolymer reclaimed rubber and is had the level and smooth feature such as bright of the dielectric properties such as good anti-aging, resistance to oxidation, anti-ozone and erosion-resistant ability and high-low temperature resistant, high insulation and powerful high, good springiness, product surface, therefore relevant enterprise replaces part second the third rubber with it, or with rubber use, play the effect reducing production costs.
But people are still abundant not to the understanding of Ethylene Propylene Terpolymer reclaimed rubber, how to apply better Ethylene Propylene Terpolymer reclaimed rubber, respectively use producer still constantly groping.Visit according to investigations, relevant enterprise, using Ethylene Propylene Terpolymer reclaimed rubber ubiquity only by rule of thumb, is ignored it and is mixed ratio, singly asks the requirement of client to some performance, carries out mixing use.Be mainly used in roof single ply waterproofing coiled material etc.; Electric wire aspect, is mainly used in civilian and input line, building wire, mine cable, used in nuclear power station electric wire, automobile ignition wire, control and signal cable etc. commercial building; Automotive industry aspect, is mainly used in automobile, truck and bus tyre and non-tyre element, comprises the water tank of automobile and parts, wiper bar, base plate and the endless tube etc. on heating hose, sealed strip, string rubber, vehicle body and chassis.Yet there are no the ratio of the mixing research report for automobile rubber pipe, sealed strip etc.
Summary of the invention
One of object of the present invention is by filling a prescription and mix Ethylene Propylene Terpolymer reclaimed rubber and other components by a certain percentage in rubber, exploration show that a kind of physicals is good, can be widely used in terpolymer EP rubber and the EPDM reclaimed rubber on automobile engineering material and use glue composition.
Another object of the present invention is to explore a kind of preparation method that can be widely used in terpolymer EP rubber and the EPDM reclaimed rubber on automobile engineering material and use glue.
Terpolymer EP rubber of the present invention and EPDM reclaimed rubber also comprise mass fraction with glue composition:
Ethylene-propylene diene copolymer 90-50 part
R-EPDM 10-50 part.
Further, also comprise: promotor 0.5-3 part.
Further, described promotor is two kinds and use in promotor TT and captax.
Further, also comprise: sulphur 1-2 part.
Further, also comprise: also comprise carbon black 25-45 part.
Further, also comprise: zinc oxide, or stearic acid, or one or several in paraffin oil; Wherein zinc oxide is 3-5 part, and stearic acid is 1-2 part, and paraffin oil is 5-10 part.
Further, described ethylene-propylene diene copolymer is 50 parts; Described R-EPDM is 50 parts.
The preparation method who prepares terpolymer EP rubber and EPDM reclaimed rubber and use glue of the present invention, comprises step:
A) raw material is equipped with and samples:
B) mixing: mixing order of addition(of ingredients) is: sheet under the glue → stearic acid of reborning, zinc oxide → Valelinum Liquidum → carbon black → promotor → sulphur → evenly rear thin-pass;
C) back mixing: step B) described rubber unvulcanizate after 22～24h parks, carries out back mixing by rubber unvulcanizate and by 3.5 ± 0.5mm thickness slice 23 ± 2 DEG C of room temperatures;
D) sulfuration;
E) test and data analysis.
The present invention is by carrying out reasonably optimizing to rubber, Ethylene Propylene Terpolymer reclaimed rubber and other components, Science Explorations, determine rational component and massfraction proportioning thereof, developed terpolymer EP rubber and the EPDM reclaimed rubber that can be widely used on automobile engineering material and used glue composition.In addition, the present invention has also explored one and can be applied to industrial terpolymer EP rubber and EPDM reclaimed rubber and use glue preparation technology, ensureing, under the prerequisite of product mechanical property, significantly to reduce raw materials cost, is with a wide range of applications.
Brief description of the drawings
Fig. 1 is different and uses the tensile strength of ratio reclaimed rubber to change comparison diagram;
Fig. 2 is different and uses the elongation change comparison diagram of ratio reclaimed rubber;
Fig. 3 is that 200% tensile modulus changes comparison diagram.
Embodiment
For the present invention being had to further understanding, below in conjunction with specific embodiment, the present invention is done to further explanation fully.
experimental installation used and measurer
Balance 0877 type Shanghai Medicine Laser Instrument Plant
Vulcanization forming machine YX-630A open form Zhejiang Yuyao Machinery Plant of Light Industry
Jiangdu, tension testing machine WQB-2500B type Nanjing test machines factory
Shuan Leng Test Devices Inc. of heat aging test chamber 40B type landlord city
Open type plastic purificating set SK-160 type Shanghai rubber machinery plant
Vulcanization of rubber instrument MDR-200DE type Wuxi City Li Garden E-factory instrument factory
Durometer Shao Er Shi LX-A type Jiangdu test machines factory
experiment material
Terpolymer EP rubber Qingdao Ai Lite Chemical Co., Ltd.
Ethylene Propylene Terpolymer reclaimed rubber Zhejiang Hang Yuan specialty elastomer company limited
The good milli of sulphur zunyi, guizhou sulphur plant
Promotor TT Tianjin La Bo auxiliary agent company limited
Promote M Tianjin La Bo auxiliary agent company limited
Zinc oxide Liuzhou Xin Pin limited-liability company
Stearic acid Zibo Ke Hong grease company limited
Paraffin oil Cangzhou Yu Dong Chemical trade company limited
Carbon black N774 Shanghai Yi Chuan Chemical Co., Ltd.
experiment process
Determine → raw material of formula is equipped with and sample → mixing → back mixing → sulfuration → test and data analysis.
The component (mass fraction) of table 1 specific embodiment
Note: promotor TT chemistry is by name: tetramethyl-thiuram disulfide, captax chemistry is by name: 2-thiol benzothiazole.
Starting material are equipped with and weigh
Get the required variety of raw material of formula from robber materials storehouse and weigh by formula requirement.Wherein sulphur, promotor weighing are accurate to 0.02 gram; Stearic acid, zinc oxide weigh and are accurate to 0.1 gram; It is ± 10% that other component weighs tolerance range.
Mixing
Mixing order of addition(of ingredients) is: sheet under the glue → stearic acid of reborning, zinc oxide → Valelinum Liquidum → carbon black → promotor → sulphur → evenly rear thin-pass.
Device roller, apart from being adjusted into the distance of 1.7mm, is dropped into rubber or the reclaimed rubber of plasticating, after sizing material bag roller smooth surface and gum deposit form and stir continuously, add other Synergist S-421 95 to carry out mixing; And roll spacing to be adjusted to 0.5mm with glue, mixing by carrying out after its thin-pass 4 times.
After rubber heat refining is good, add successively stearic acid, zinc oxide → Valelinum Liquidum → carbon black → promotor → sulphur by reinforced requirement, sneak into completely after rubber until each Synergist S-421 95, cutting turns refining and broaching tool descends sheet 3 times afterwards.
Roll spacing is adjusted to only 0.5mm, allows rubber unvulcanizate lower roll 3 times (wherein secondary is for playing triangle bag, once for not wrapping roller rule) again roll spacing is adjusted into the distance of 1.7mm, allow rubber unvulcanizate bag roller cutting turn refining, sizing material without bubble after under sheet stand-by.
Back mixing
Rubber unvulcanizate after 22～24h parks, carries out back mixing by rubber unvulcanizate and by 3.5 ± 0.5mm thickness slice 23 ± 2 DEG C of room temperatures.
Cut and quite size of test piece mould by rolling direction, weight is the sample of 26 grams.
Sulfuration
Test piece mould is placed in vulcanizer flat board to preheating 30 minutes.Plate temperature is 160 ± 1 DEG C.
After mould temperature is stable, flat board is fallen, open mould and put into each two of 1#, 2# sample.
Rise dull and stereotyped, apply the pressure of 12MPa to mould, and pressurize 20 minutes (equipment self-clocking).
After curing time completes, flat board is opened automatically, and test piece is opened and taken out to pull-out mould, on request, put on the contents such as formula number, date, curing temperature and curing time to test piece.Successively remaining 3#, 4#, 5#, 6#, 7# are pressed.
Test piece is placed on after having vulcanized parks 16h and hands over examination chamber to test under 23 ± 2 DEG C of conditions.
Test and data analysis
Table 2 is also used sizing material physical and mechanical properties index
The data that draw from embodiment, the mechanical and physical performance aspect of 100% Ethylene Propylene Terpolymer rubber (1#), the hardness of reclaimed rubber is greater than rubber, in the data of tensile strength at yield, elongation, tensile modulus three aspects: reflection rubber strength quality, rubber will be apparently higher than 100% reclaimed rubber (2#).
Draw according to above data and Fig. 1-3: from 3# to 7#, fill a prescription, along with continuing to increase of reclaimed rubber ratio from 10% to 50%, sizing material tensile strength at yield, elongation, 200% tensile modulus present continuous downtrending.Reach 50%(7# when mixing reclaimed rubber) time, the tensile strength at yield of sizing material is 7.2Mpa, elongation is 360%, 200% surely to stretch for 3.5Mpa, the product standard QC/T 639-2004 automobile rubber weather strip performance requriements providing according to main engine plants.When reclaimed rubber is mixed ratio and reached 50%, its mechanical property still can reach product requirement.
cost analysis:
The up-to-date purchase price analysis providing by enterprise: Ethylene Propylene Terpolymer rubber price: 25.2 yuan/kg
Ethylene Propylene Terpolymer reclaimed rubber price: 6.5 yuan/kg
Add various starting material auxiliary agents, as calculated: the full rubber formula of Ethylene Propylene Terpolymer (1#): 18.16 yuan/kg
Ethylene Propylene Terpolymer is mixed 13.78 yuan/kg of 50% regenerated rubber formula (7#)
Every kg saves: 18.16-13.78=4.38 unit
Saving rate: 4.38 ÷ 18.16=0.25 saving rates are 25%
Save 4.38 yuan by every kilogram, 4380 yuan of saving per ton, through preliminary investigation Liuzhou City sized Auto Fittings Enterprises use the amount of ethylene-propylene diene copolymer every year 1000 tons of left and right, estimate by this amount, cost-saved is over a year 4,380,000 yuan, economic benefit is fairly obvious.
Table 3 raw materials cost table look-up
Claims (10)
1. terpolymer EP rubber and EPDM reclaimed rubber, also with a glue composition, comprise mass fraction:
Ethylene-propylene diene copolymer 90-50 part
R-EPDM 10-50 part.
2. terpolymer EP rubber as claimed in claim 1 and EPDM reclaimed rubber, also with glue composition, is characterized in that, also comprise: promotor 0.5-3 part.
3. terpolymer EP rubber as claimed in claim 2 and EPDM reclaimed rubber, also with glue composition, is characterized in that, described promotor is promotor TT and captax and uses.
4. terpolymer EP rubber as claimed in claim 1 and EPDM reclaimed rubber, also with glue composition, is characterized in that, also comprise: sulphur 1.3-1.38 part.
5. terpolymer EP rubber as claimed in claim 1 and EPDM reclaimed rubber, also with glue composition, is characterized in that, also comprise: also comprise carbon black 25-45 part.
6. terpolymer EP rubber as claimed in claim 1 and EPDM reclaimed rubber with glue composition, is characterized in that, also comprises: zinc oxide, or stearic acid, or one or several in paraffin oil; Wherein zinc oxide is 3-5 part, and stearic acid is 1-2 part, and paraffin oil is 5-10 part.
7. the terpolymer EP rubber as described in claim 1-6 any one and EPDM reclaimed rubber, also with glue composition, is characterized in that, described ethylene-propylene diene copolymer is 50 parts; Described R-EPDM is 50 parts.
8. prepare terpolymer EP rubber and EPDM reclaimed rubber the preparation method with glue, comprise step:
A) raw material is equipped with and samples:
B) mixing: mixing order of addition(of ingredients) is: sheet under the glue → stearic acid of reborning, zinc oxide → Valelinum Liquidum → carbon black → promotor → sulphur → evenly rear thin-pass;
C) back mixing: step B) described rubber unvulcanizate after 22～24h parks, carries out back mixing by rubber unvulcanizate and by 3.5 ± 0.5mm thickness slice 23 ± 2 DEG C of room temperatures;
D) sulfuration;
E) test and data analysis.
9. terpolymer EP rubber and EPDM reclaimed rubber the application on automobile engineering material with glue composition described in claim 1-7 any one.
10. described in claim 8, method is prepared and next terpolymer EP rubber and EPDM reclaimed rubber the application on automobile engineering material with glue.
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| CN201410279288.0A CN104163993A (en) | 2014-06-20 | 2014-06-20 | Ethylene propylene diene monomer rubber and EPDM reclaimed rubber co-used rubber composition, and preparation method and application thereof |
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| CN201410279288.0A CN104163993A (en) | 2014-06-20 | 2014-06-20 | Ethylene propylene diene monomer rubber and EPDM reclaimed rubber co-used rubber composition, and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496816A (en) * | 2016-11-17 | 2017-03-15 | 华晨汽车集团控股有限公司 | A kind of rubber composition for connecting flexible pipe for auto sunroof water drain pipe bottom |
| CN106566094A (en) * | 2016-11-17 | 2017-04-19 | 华晨汽车集团控股有限公司 | Rubber composition for automobile skylight drain pipe sheath |
| CN108774363A (en) * | 2018-06-12 | 2018-11-09 | 柳州市大新实业有限公司 | A kind of EPDM rubber formula and preparation method containing rubber powder |
| CN110885504A (en) * | 2019-12-23 | 2020-03-17 | 南京博丞橡塑有限公司 | Sealing strip suitable for glass curtain wall frame and production process thereof |
| CN117511235A (en) * | 2023-11-28 | 2024-02-06 | 苏州风载材料科技有限公司 | Heat-insulating composite waterproof coiled material and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| CN101289557A (en) * | 2008-06-13 | 2008-10-22 | 中国船舶重工集团公司第七二五研究所 | Method for preparing mildewproof rubber by using regenerated rubber as basal body |
-
2014
- 2014-06-20 CN CN201410279288.0A patent/CN104163993A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289557A (en) * | 2008-06-13 | 2008-10-22 | 中国船舶重工集团公司第七二五研究所 | Method for preparing mildewproof rubber by using regenerated rubber as basal body |
Non-Patent Citations (1)
| Title |
|---|
| 林新志等: "三元乙丙橡胶/EPDM再生胶并用胶压缩永久变形性能的研究", 《"三元乙丙橡胶/EPDM再生胶并用胶压缩永久变形性能的研究》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496816A (en) * | 2016-11-17 | 2017-03-15 | 华晨汽车集团控股有限公司 | A kind of rubber composition for connecting flexible pipe for auto sunroof water drain pipe bottom |
| CN106566094A (en) * | 2016-11-17 | 2017-04-19 | 华晨汽车集团控股有限公司 | Rubber composition for automobile skylight drain pipe sheath |
| CN108774363A (en) * | 2018-06-12 | 2018-11-09 | 柳州市大新实业有限公司 | A kind of EPDM rubber formula and preparation method containing rubber powder |
| CN110885504A (en) * | 2019-12-23 | 2020-03-17 | 南京博丞橡塑有限公司 | Sealing strip suitable for glass curtain wall frame and production process thereof |
| CN117511235A (en) * | 2023-11-28 | 2024-02-06 | 苏州风载材料科技有限公司 | Heat-insulating composite waterproof coiled material and preparation method thereof |
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