CN108610562A - A kind of low pressure becomes high temperature resistant EP rubbers material and preparation method thereof - Google Patents
A kind of low pressure becomes high temperature resistant EP rubbers material and preparation method thereof Download PDFInfo
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- CN108610562A CN108610562A CN201810401695.2A CN201810401695A CN108610562A CN 108610562 A CN108610562 A CN 108610562A CN 201810401695 A CN201810401695 A CN 201810401695A CN 108610562 A CN108610562 A CN 108610562A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 103
- 239000005060 rubber Substances 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- 238000004132 cross linking Methods 0.000 claims abstract description 31
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000005864 Sulphur Substances 0.000 claims description 17
- 238000004073 vulcanization Methods 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000012824 chemical production Methods 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000007906 compression Methods 0.000 abstract description 35
- 230000006835 compression Effects 0.000 abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 18
- 239000004014 plasticizer Substances 0.000 abstract description 13
- 230000032683 aging Effects 0.000 abstract description 9
- 239000011787 zinc oxide Substances 0.000 abstract description 9
- 235000021355 Stearic acid Nutrition 0.000 abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000008117 stearic acid Substances 0.000 abstract description 8
- 239000006229 carbon black Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000003483 aging Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
-
- 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
- C08K3/04—Carbon
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
-
- 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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of low pressure to become high temperature resistant EP rubbers material and preparation method thereof, belongs to field of rubber technology.The rubber material of the present invention includes the component of following parts by weight：100 parts of EP rubbers raw rubber, 5 parts of zinc oxide, 1.2 parts of stearic acid, 445 2 parts of anti-aging agent, 45~55 parts of 4~8 parts of Ative CHO, fast extrude in carbon black N550, soften 45 6.0~8.0 parts of 5~10 parts of plasticizer S2550,1.5~2.0 parts of crosslinking coagent N308E and vulcanizing agent GF.The rubber material of the present invention has excellent high temperature resistance, there can be good physical property after 175 DEG C of agings, the remarkable advantage simultaneously with low compression set, reaches performance requirement of germany volkswagen PV3330 and the PV3307 standard to compression set.
Description
Technical field
The invention belongs to field of rubber technology, more specifically to a kind of low pressure become high temperature resistant EP rubbers material and
Preparation method.
Background technology
EP rubbers sealing element is higher and higher to EP rubbers material high temperature resistant, the requirement of low compression set performance.
The quality of its performance directly affects the sealing performance of rubber seal.High temperature resistant EP rubbers often applies the cooling in automobile
In system, low compression set is one of the technical indicator of rubber seal most critical.
Examination criteria generally for EP rubbers sealing element is national standard buckling (GB/T7759) and international buckling
(ISO815), GB/T7759 and ISO815 test methods require sample after high-temperature cabinet takes out cooling, and compression clamper is unclamped,
Measure the compression set of sample after allowing sample to restore 30 minutes again, and detection of the germany volkswagen company to EP rubbers material
Using PV3330 and PV3307 standards, the test method requirement of this two kinds of examination criterias is harsher.Wherein, germany volkswagen
PV3330 is in sample after high-temperature cabinet taking-up is cooled to room temperature, and release compression clamper completes experiment in 20 seconds, and requires
PV3330 compression sets ＜ 40% after 150 DEG C × hot air aging for 24 hours；It is more for this viscoelastic material of rubber
Number sample had little time to restore in 20 seconds at all, therefore to the performance requirement higher of EP rubbers material；And germany volkswagen
PV3307 be sample after 150 DEG C × aging for 24 hours after high-temperature cabinet taking-up is cooled to room temperature, unclamp complete in compression clamper 5 seconds
At experiment test, it is desirable that PV3307 compression sets ＜ 60%, it is more harsher than the requirement of PV3330 experimental method, to the third rubber of second
The performance requirement of glue material then higher, and the requirement quilt of the PV3307 compression sets of EP rubbers material of the present invention
Client rises to ＜ 42%, and complexity is self-evident.
Chinese Patent Application No. 201710492764.0, publication number CN107090133A disclose a kind of automobile radiator systems
Sealing element EP rubbers material and its production method, rubber material include the component of following parts by weight：EP rubbers raw rubber 100
Part, 5 parts of zinc oxide, 0.5~1.5 part of stearic acid, 3~6 parts of anti-aging agent, 20~30 parts of fast extrude in carbon black N550, semi-reinforcing hydrocarbon black
5~8.5 parts of 10~20 parts of N774,3.5~7 parts of crosslinking coagent Ricon 153D and vulcanizing agent Perkadox 14-40B-GR.
The rubber material has excellent high temperature resistance, can be used for a long time under conditions of -50 DEG C~150 DEG C, while having resistance to
The remarkable advantage of low temperature, low compression set.But the rubber material is compressed using germany volkswagen PV3307 standards
The performance that is permanently deformed test, after 150 DEG C × hot air aging for 24 hours, PV3307 compression sets are 42.6%~45.6%, because
This is difficult to meet using EP rubbers seal prepared by the component and this method in the present invention permanent to PV3307 compressions
Deform the rigors of ＜ 42%.Softening plasticizer, institute is not used in this application in order to obtain low compression set performance
EP rubbers material obtained is difficult to obtain preferable process flowability.
Chinese Patent Application No. 201210038982.4, publication number CN103254511A disclose a kind of ethylene-propylene-diene monomer
Glue, the rubber are containing ethylene propylene diene rubber sizing material, vulcanizing agent, vulcanizing activator system, accelerating agent, reinforcing agent and softening plasticising
The composition of agent be kneaded and vulcanize and the product that is formed, wherein the vulcanizing agent is insoluble sulfuy and/or pre-dispersed Sulfur,
The vulcanizing activator system contains component A and stearic acid, and the component A is selected from activated zinc oxide and/or pre-dispersed zinc oxide,
In the composition, relative to 100 parts by weight ethylene propylene diene rubber sizing materials, the content of the vulcanizing agent is 0.5-4.5 weight
Part, the content of the vulcanizing activator system be 4-13 parts by weight, the content of the accelerating agent is 3-10 parts by weight, the enhancing
The content of agent be 40-90 parts by weight, it is described softening plasticizer content be 5-60 parts by weight, the component A with it is stearic heavy
Amount is than being 1-10: 1.Preferred ethylene propylene diene rubber no blooming that the invention provides does not generate nitrosamine and mechanical property is good.But
It is to have used 45~55 parts of softening plasticizer and common sulfur cross-linking system in this application, can all makes compression set performance
It is deteriorated, it is also difficult to be resistant to 175 DEG C of high temperature, therefore simultaneously difficult using EP rubbers seal prepared by the component and this method
To meet in the present invention germany volkswagen company to PV3330 the and PV3307 examination criterias of EP rubbers material and heat safe
It is required that.
Therefore, the constituent and mixing method for how adjusting EP rubbers material can be prepared and meet Germany greatly
The EP rubbers sealing element of many PV3330 and PV3307 standards and resistance to 175 DEG C of high temperature is a problem to be solved.
Invention content
1, it to solve the problems, such as
Constituent and mixing method for existing EP rubbers material cannot be satisfied germany volkswagen PV3330 and
The problem of PV3307 standards require, the present invention provide a kind of low pressure change meeting the requirement of germany volkswagen PV3330 and PV3307 standard
High temperature resistant EP rubbers material and preparation method thereof.
2, technical solution
To solve the above problems, the present invention adopts the following technical scheme that.
A kind of low pressure change high temperature resistant EP rubbers material, including following component in parts by weight：
100 parts of EP rubbers raw rubber
5 parts of zinc oxide
1.2 parts of stearic acid
2 parts of anti-aging agent
4~8 parts of vulcanizing activator Ative CHO
45~55 parts of fast extrude in carbon black
Soften 5~10 parts of plasticizer
1.5~2.0 parts of crosslinking coagent
6.0~8.0 parts of vulcanizing agent.
Preferably, the vulcanizing activator Ative CHO are the sulfurate activity of the calcium hydroxide containing surface modification treatment
Agent.
Preferably, the vulcanizing activator Ative CHO ash is 69~74%, and appearance is white powder.
Preferably, the vulcanizing activator Ative CHO are the crosslinking of Kunshan company of Ya Teman Chemical Co., Ltd.s production
Activator, acid absorbent.
Preferably, the ratio of the crosslinking coagent N308E and vulcanizing agent GF-45 is 1:4.
Preferably, the EP rubbers raw rubber is the bright Keltan 2750 for containing chemical production, and content ingredient contains for ethylene
Measure 48%, ENB Third monomers content 7.8%, narrow molecular weight distribution.
Preferably, the adding proportion of the EP rubbers raw rubber Keltan 2750 and vulcanizing activator Ative CHO is
100：(4~6).
Preferably, the adding proportion of the anti-aging agent 445 and vulcanizing activator Ative CHO are 1：(2~3).
A kind of low pressure becomes the preparation method of high temperature resistant EP rubbers material, includes the following steps：
Step 1, masterbatching rubber system are standby：The formula stock for becoming high temperature resistant EP rubbers material according to above-mentioned low pressure, will remove and hand over
Join all raw material except the Ative CHO of auxiliary agent N308E, vulcanizing agent GF-45 and 1/2 dosage to put into mixer, temperature
Degree reaches 145 DEG C of dumpings and obtains masterbatch；
Step 2, two sections of masterbatch plus sulphur：Masterbatch, crosslinking coagent N308E, the vulcanizing agent GF-45 that step 1 is obtained
It is put into togerther progress mixing in mixer with the Ative CHO of 1/2 dosage and adds sulphur, the dumping when temperature reaches 125~135 DEG C；
Step 3, vulcanization：Mold will be inserted after mixing gum forming after two sections plus sulphur, carried out on vulcanizer (175~
185 DEG C) after the primary vulcanization of × 8min and under the conditions of (150~155 DEG C) × 3h+ (180~185 DEG C) × 1h carry out secondary place
Reason, obtains vulcanizate finished product.
3, advantageous effect
Compared with the prior art, beneficial effects of the present invention are：
(1) a kind of low pressure of the invention, which becomes in high temperature resistant EP rubbers material, is added to Ative CHO, and principle is：
In the sulfidation of EP rubbers material, the use of peroxide vulcanizing agent makes the life along with acidic molecular in cross-linking process
At, and the acidic molecular has inhibiting effect to cross-linking reaction, and the service efficiency of vulcanizing agent is caused to reduce, and eventually leads to EP rubbers
Buckling performance it is poor, high temperature resistance be deteriorated；And Ative CHO are added in inventive formulation, it is that one kind containing surface
Activator of crosslinking, the vulcanizing activator of the calcium hydroxide of modification, while being also a kind of acid absorbent, use can neutralize suction
The acidic by-products generated in cross-linking reaction are received, the salt for not influencing curability and state of cure (vulcanization) is generated, makes peroxide cure
Agent can be generated between rubber it is more be not easy by the carbon-oxygen bond of oxidation scission, improve peroxide vulcanizing agent and EP rubbers it
Between generate the activity of cross-linking reaction, improve the efficiency of actual of vulcanizing agent, deepened after crosslink density makes cross-linking reaction
The reticular structure of formation is more firm, can still have excellent performance after the high temperature for being resistant to 175 DEG C.
(2) the vulcanizing activator Ative CHO containing modified calcium hydroxide used in the present invention add with traditional handicraft
Add calcium hydroxide or calcium oxide difference lies in, first, easy to absorb moisture is lumpd in air for calcium hydroxide and calcium oxide, and is vulcanized
Ash content is 69%~74% in activating agent AtiveCHO, wherein the calcium hydroxide contained is prevented from caking after modified, the moisture absorption；The
Two, calcium hydroxide and calcium oxide are difficult to disperse in sizing material, and the vulcanizing activator Ative CHO that ash content is 69%~74% exist
Dispersibility in sizing material is more preferable, more uniformly, can preferably absorb acidic materials, improves vulcanizing agent activity.
(2) softening plasticizer is added in inventive formulation, it is generally the case that second can be promoted by softening the addition of plasticizer
The processing performance of third rubber, but softening plasticizer can reduce crosslink density and then make EP rubbers buckling degradation, and Ative
The use of CHO can balance out be added softening plasticizer after caused by reduce crosslink density influence.
(3) present invention uses the crosslinking coagent N308E and vulcanizing agent GF-45 of special ratios relationship, because can be utmostly
The activity for playing vulcanizing agent, promotes that maximum cross-linking reaction occurs between vulcanizing agent and each component, and is EP rubbers material
Material provides the mechanical performance preferably resisted under the conditions of 175 DEG C of high temperature；Reduce the generation of peroxide cure residue,
It is more advantageous to the raising of the heat resistance of EP rubbers material and obtains lower compression set performance.
(4) ratio of the special ratios relationship of vulcanizing agent and crosslinking coagent used in the present invention, Ative CHO and raw rubber
Example and Ative CHO and the special ratios of anti-aging agent between cooperate generate synergistic effect, in conjunction in preparation method not
Synthermal after-treatment technique so that obtained EP rubbers material has resistance to 175 DEG C of high temperature, low pressure becomes the spy of performance
Point.
(5) 3 mesolow of the embodiment of the present invention becomes sealing element made of high temperature resistant EP rubbers material and is surveyed through PV3330 standards
Examination, after 150 DEG C × aging for 24 hours, compression set 32.6%, it is ＜ to meet germany volkswagen PV3330 compression sets
40% requirement, and it is not added with the comparative example 1 of vulcanizing activator Ative CHO under equal conditions, compression set is
53.8%, the standard that germany volkswagen PV3330 compression sets are ＜ 40% cannot be met；3 mesolow of embodiment becomes high temperature resistant
Sealing element made of EP rubbers material is through PV3307 standard testings, and after 150 DEG C × aging for 24 hours, compression set is
35.6%, meet germany volkswagen PV3307 compression sets and is the requirement of ＜ 42%, and it is not added with vulcanizing activator Ative
Under equal conditions, it is permanent cannot to meet germany volkswagen PV3307 compressions to the comparative example 1 of CHO for compression set 63.5%
It is deformed into the standard of ＜ 42%；
(6) a kind of low pressure of the invention becomes high temperature resistant EP rubbers material preparation method, and the masterbatch of special formulation is advanced
The single treatment of row (150~155 DEG C) × 3h, then by the after-treatment of (180~185 DEG C) × 1h, friendship can be effectively removed
The remaining small-molecule substance of connection reaction, further deepens crosslink density, obtains better low compression set performance；
(7) a kind of low pressure of the invention becomes high temperature resistant EP rubbers material preparation method, using by vulcanizing activator Ative
CHO is divided to be added for two batches, and the masterbatch containing 1/2 dosage Ative CHO is only added first and puts into mixer, obtains mother
Refining glue, reason are that the 1/2Ative CHO being first added not only can be very good to be dispersed in masterbatch, but also because its own has point
Homogenizing agent effect is dissipated, the other half Ative CHO and vulcanizing agent being added after can promoting quickly disperse when adding sulphur, obtain mother
Refining glue；The Ative CHO of masterbatch, crosslinking coagent N308E, vulcanizing agent GF-45 and 1/2 dosage are put into togerther mixing again later
Mixing is carried out in machine and adds sulphur, greatly reduces jitter time of the vulcanizing agent in masterbatch, makes vulcanization accelerator and other cooperations
Agent can be uniformly dispersed in sizing material, be more advantageous to the raising of EP rubbers material compression set performance.
(8) key characteristic that the material standard being directed in the present invention requires has 1, high temperature resistance, 175 DEG C × 168h heat empty
It is almost the same before technical requirement and aging after gas aging.
Specific implementation mode
The present invention is further described below with reference to specific embodiment.
EP rubbers raw rubber is the bright Keltan 2750 for containing chemical production in following embodiments；N550 is Cabot Co., Ltd
The N550 fast extrude in carbon black of production；Zinc oxide is the indirect process zinc oxide of Zhenjiang plain boiled water Chemical Co., Ltd. production；Stearic acid is
The production of Malaysian south grease company；Anti-aging agent 445 is the anti-aging agent 445 of Jiangsu Huada Chemical Group Co., Ltd.'s production
(No. CAS：10081-67-1)；The supplier for softening plasticizer S2550 is that Shanghai Son forms chemical industry；Crosslinking coagent N308E, vulcanizing agent
The supplier of GF-45 is Shaanxi Lang Rui companies, and Ative CHO are the crosslinking of Kunshan company of Ya Teman Chemical Co., Ltd.s production
Activator acid absorbent.
Embodiment 1
A kind of low pressure of the present embodiment becomes high temperature resistant EP rubbers material, including following component：
100 parts of EP rubbers raw rubber, 5 parts of zinc oxide, 1.2 parts of stearic acid, 445 2 parts of anti-aging agent, 6 parts of Ative CHO,
55 parts of fast extrude in carbon black N550,10 parts of softening plasticizer S2550,1.5 parts of crosslinking coagent N308E and vulcanizing agent GF-45 6.0
Part.
By above-mentioned quality proportioning, low pressure become the preparation method of high temperature resistant EP rubbers material into：
Step 1, masterbatching rubber system are standby：The formula stock for becoming high temperature resistant EP rubbers material according to low pressure will remove crosslinking and help
All raw material except the Ative CHO of agent N308E, vulcanizing agent GF-45 and 1/2 dosage is put into mixer, and temperature reaches
Masterbatch is obtained to 145 DEG C of dumpings；
Step 2, two sections of masterbatch plus sulphur：Masterbatch, crosslinking coagent N308E, the vulcanizing agent GF-45 that step 1 is obtained
It is put into togerther progress mixing in mixer with the Ative CHO of 1/2 dosage and adds sulphur, the dumping when temperature reaches 125 DEG C；
Step 3, vulcanization：Mold will be inserted after mixing gum forming after two sections plus sulphur, carried out on vulcanizer 185 DEG C ×
After-treatment is carried out after the primary vulcanization of 8min and under the conditions of 150 DEG C × 3h+185 DEG C × 1h, obtains vulcanizate finished product.
Embodiment 2
A kind of low pressure of the present embodiment becomes high temperature resistant EP rubbers material, including following component：
100 parts of EP rubbers raw rubber, 5 parts of zinc oxide, 1.2 parts of stearic acid, 445 2 parts of anti-aging agent, 8 parts of Ative CHO,
50 parts of fast extrude in carbon black N550,7 parts of softening plasticizer S2550,1.8 parts of crosslinking coagent N308E and vulcanizing agent GF-45 7.2
Part.
By above-mentioned quality proportioning, low pressure become the preparation method of high temperature resistant EP rubbers material into：
Step 1, masterbatching rubber system are standby：The formula stock for becoming high temperature resistant EP rubbers material according to low pressure will remove crosslinking and help
All raw material except the Ative CHO of agent N308E, vulcanizing agent GF-45 and 1/2 dosage is put into mixer, and temperature reaches
Masterbatch is obtained to 145 DEG C of dumpings；
Step 2, two sections of masterbatch plus sulphur：Masterbatch, crosslinking coagent N308E, the vulcanizing agent GF-45 that step 1 is obtained
It is put into togerther progress mixing in mixer with the Ative CHO of 1/2 dosage and adds sulphur, the dumping when temperature reaches 130 DEG C；
Step 3, vulcanization：Mold will be inserted after mixing gum forming after two sections plus sulphur, carried out on vulcanizer 175 DEG C ×
After-treatment is carried out after the primary vulcanization of 8min and under the conditions of 155 DEG C × 3h+180 DEG C × 1h, obtains vulcanizate finished product.
Embodiment 3
A kind of low pressure of the present embodiment becomes high temperature resistant EP rubbers material, including following component：
100 parts of EP rubbers raw rubber, 5 parts of zinc oxide, 1.2 parts of stearic acid, 445 2 parts of anti-aging agent, 4 parts of Ative CHO,
45 parts of fast extrude in carbon black N550,5 parts of softening plasticizer S2550,2.0 parts of crosslinking coagent N308E and vulcanizing agent GF-45 8.0
Part.
By above-mentioned quality proportioning, low pressure become the preparation method of high temperature resistant EP rubbers material into：
Step 1, masterbatching rubber system are standby：The formula stock for becoming high temperature resistant EP rubbers material according to low pressure will remove crosslinking and help
All raw material except the Ative CHO of agent N308E, vulcanizing agent GF-45 and 1/2 dosage is put into mixer, and temperature reaches
Masterbatch is obtained to 145 DEG C of dumpings；
Step 2, two sections of masterbatch plus sulphur：Masterbatch, crosslinking coagent N308E, the vulcanizing agent GF-45 that step 1 is obtained
It is put into togerther progress mixing in mixer with the Ative CHO of 1/2 dosage and adds sulphur, the dumping when temperature reaches 135 DEG C；
Step 3, vulcanization：Mold will be inserted after mixing gum forming after two sections plus sulphur, carried out on vulcanizer 180 DEG C ×
After-treatment is carried out after the primary vulcanization of 8min and under the conditions of 153 DEG C × 3h+183 DEG C × 1h, obtains vulcanizate finished product.
Comparative example 1
In comparative example 1 in addition to being not added with Ative CHO, other formula components and preparation method are same as Example 3.
Comparative example 2
Chinese Patent Application No. 201710492764.0, the Examples 1 to 4 in the prior art of publication number CN107090133A
The rubber material of preparation, using germany volkswagen PV3307 standards to the rubber material carry out compression set performance test, 150
DEG C × hot air aging for 24 hours after, PV3307 compression sets be 42.6%~45.6%, be all higher than 42%.
The performance test detection data of 1 rubber material of the present invention of table
It can be seen that by table 1, the performance of EP rubbers material produced by the present invention is substantially better than technical indicator value, and implements
The comprehensive performance of example 3 is optimal., will be such to comparative example 1 when being added without Ative CHO, it does not obtain and meets resistance to 175 DEG C of height
Temperature and the EP rubbers material with low compression set.
Comparative example 1 is with embodiment 3 using PV3330 and PV3307 standard compressions permanent deformation data explanation, Ative CHO
Addition be affected to the compression set performance of EP rubbers material, the state of cure (vulcanization) of EP rubbers material can be made to add
It is deep, while heat aging property is improved again, there is the performance of preferable physical property.
Comparative example 2, using PV3330 and PV3307 standard compressions permanent deformation data explanation, is being not added with embodiment 3
In the case of AtiveCHO vulcanizing activators, the compression set performance of traditional handicraft formula EP rubbers material is difficult to reach
The standard of compression set ＜ 42%.
Claims (8)
1. a kind of low pressure becomes high temperature resistant EP rubbers material, which is characterized in that including following component in parts by weight：
2. a kind of low pressure according to claim 1 becomes high temperature resistant EP rubbers material, which is characterized in that the sulfurate activity
Agent Ative CHO are the vulcanizing activator of the calcium hydroxide containing surface modification treatment.
3. a kind of low pressure according to claim 2 becomes high temperature resistant EP rubbers material, which is characterized in that the sulfurate activity
Agent Ative CHO ash is 69~74%.
4. a kind of low pressure according to claim 3 becomes high temperature resistant EP rubbers material, which is characterized in that the crosslinking coagent
The ratio of N308E and vulcanizing agent GF-45 are 1:4.
5. a kind of low pressure according to claim 4 becomes high temperature resistant EP rubbers material, which is characterized in that the EP rubbers
Raw rubber is the bright Keltan 2750 for containing chemical production, and content ingredient is ethylene contents 48%, ENB Third monomer contents
7.8%.
6. a kind of low pressure according to claim 5 becomes high temperature resistant EP rubbers material, which is characterized in that the EP rubbers
The adding proportion of raw rubber Keltan 2750 and vulcanizing activator Ative CHO are 100：(4~6).
7. a kind of low pressure according to claim 6 becomes high temperature resistant EP rubbers material, which is characterized in that the anti-aging agent
The adding proportion of 445 and vulcanizing activator Ative CHO is 1：(2~3).
8. a kind of low pressure becomes the preparation method of high temperature resistant EP rubbers material, include the following steps：
Step 1, masterbatching rubber system are standby：According to the formula stock described in any one of claim 1~7, crosslinking coagent will be removed
All raw material except the Ative CHO of N308E, vulcanizing agent GF-45 and 1/2 dosage is put into mixer, and temperature reaches
145 DEG C of dumpings obtain masterbatch；
Step 2, two sections of masterbatch plus sulphur：Masterbatch, crosslinking coagent N308E, the vulcanizing agent GF-45 and 1/2 that step 1 is obtained
The Ative CHO of dosage are put into togerther progress mixing in mixer and add sulphur, the dumping when temperature reaches 125~135 DEG C；
Step 3, vulcanization：Mold will be inserted after mixing gum forming after two sections plus sulphur, (175~185 DEG C) are carried out on vulcanizer
After-treatment is carried out after the primary vulcanization of × 8min and under the conditions of (150~155 DEG C) × 3h+ (180~185 DEG C) × 1h, is obtained
To vulcanizate finished product.
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| CN113462087A (en) * | 2021-06-25 | 2021-10-01 | 启东市亿方密封科技有限公司 | High-temperature-resistant material combining ethylene propylene glycol and ethionamide and preparation method thereof |
| CN114634676A (en) * | 2022-04-29 | 2022-06-17 | 重庆丰海坤翔实业(集团)有限公司 | A kind of ethylene-propylene rubber wiper strip and preparation method thereof |
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