CN104710692A - Solubilizer for improving performance of natural rubber-ethylene propylene rubber co-blended rubber and preparation method thereof - Google Patents
Solubilizer for improving performance of natural rubber-ethylene propylene rubber co-blended rubber and preparation method thereof Download PDFInfo
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- 229920000181 Ethylene propylene rubber Polymers 0.000 title claims abstract description 73
- 229920001971 elastomer Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000002904 solvent Substances 0.000 title abstract 3
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 51
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 51
- 229920001194 natural rubber Polymers 0.000 claims abstract description 51
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 44
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000006229 carbon black Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000004033 plastic Substances 0.000 claims abstract description 5
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000806 elastomer Substances 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 29
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 21
- 238000004073 vulcanization Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000009628 steelmaking Methods 0.000 claims description 2
- YQTOVEJEXGTPNM-UHFFFAOYSA-N prop-2-enoic acid;zinc Chemical compound [Zn].OC(=O)C=C YQTOVEJEXGTPNM-UHFFFAOYSA-N 0.000 claims 1
- 230000003019 stabilising effect Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 229920002943 EPDM rubber Polymers 0.000 abstract description 15
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- -1 polyethylene octene Polymers 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007775 late Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
A solubilizer for improving performance of natural rubber-ethylene propylene rubber co-blended rubber. Natural rubber, a polyethylene octene elastomer (POE), ethylene propylene diene rubber, methacrylic acid, white carbon black, zinc oxide, zinc stearate and a peroxide crosslinking agent are subjected to a co-blending reaction in a rubber and plastic internal mixer, and zinc methacrylate generated through in-situ polymerization and pre-crosslinked natural rubber-ethylene propylene rubber molecular chain segments form an interpenetrating network, and thus an olefin elastomer containing the natural rubber-ethylene propylene rubber chain segments is obtained; the material can improve the compatibility of the natural rubber-ethylene propylene rubber co-blended rubber and improve the mechanical properties of the natural rubber-ethylene propylene rubber co-blended rubber. The solubilizer is added into the natural rubber-ethylene propylene rubber co-blended rubber, the tensile strength and tearing strength of the vulcanizate are increased by 10% or more.
Description
Technical field
The present invention relates to a kind of macromolecular material, be mainly used in improving natural rubber and ethylene-propylene rubber(EPR) Blend rubber consistency and improve the material of Blend rubber mechanical property.
Background technology
Natural rubber has very high elasticity, quite high tensile strength and tear strength, and binding property is good, also has good comprehensive process performance, is the best general purpose rubber of over-all properties.Because of in its molecular chain structure containing active higher double bond, the ozone etc. easily and in air reacts, so its heat oxygen aging resistance, ozone resistance are all poor, product is short for work-ing life, and these characteristics limit its application at some special occasions.
Tyre element is because being subdued and various solarization, easy generation flexing fatigue destroys and aging cracking, have a strong impact on Appcarance guality of tyres and use properties, in tyre stock parts, conventional rubber used is as NR, and NR and BR, SBR blend compounds, because all containing unsaturated double-bond in its molecular backbone chain, be subject to the impact of outside environmental elements, so the fatigue aging protected working of tire is abnormal important.Improve the problem that natural rubber is ageing-resistant, flexible resistance is rubber works personnel research always.
EPDM has excellent heat-resisting, resistance to ozone, ageing-resistant and electrical insulating property, and easily and polyolefin plastics blended, owing to there is unrivaled advantage in its raw material, performance and price etc., greatly expand the range of application of ethylene-propylene rubber(EPR), make ethylene-propylene rubber(EPR) in electrical equipment industry, automobile component, the inner tube of a tyre, water-proof material, polyolefinic improvement and additive etc., be obtained for a large amount of application, become the indispensable and irreplaceable a kind of rubber of synthetic materials, but the bad range of application that greatly limit it of EPDM processing characteristics.
Natural rubber and ethylene-propylene rubber(EPR) two kinds of rubber mix can obtain the rubber unvulcanizate having two kinds of rubber performances concurrently, and practicality strengthens greatly.Cross-linked rubber can physical and mechanical properties that comprehensively NR phase is excellent and excellent heat-resisting, the ozone of EPDM and pharmaceutical chemicals performance.But due to the autohension of EPDM and mutual viscosity poor, and the solubleness of vulcanization accelerator between each rubber phase has very big-difference, and blend compounds is difficult to reach synchronic curing, thus brings considerable influence to complete processing, blend compounds performance.Carry out to EPDM the sulfuration compatibilization that graft modification can improve NR/EPDM blend rubber, EPDM graft-modification method mainly contains maleic anhydride (MAH) modification, acrylonitrile modified, acrylate modified etc.And to EPDM carry out blending and modifying (thermal treatment) also can effectively raising NR/EPDM covulcanization.The researchists such as Song Jingfang have studied the sulfuration increase-volume of two kinds of blend rubber from technique.Result shows, best processing condition be second third carbon black rubber master batch after Overheating Treatment, 150 DEG C with blended 4 minutes of natural rubber, then on cold roller, add other Synergist S-421 95 such as zinc oxide, stearic acid.This processing method can make blend compounds obtain excellent over-all properties.In addition, EPDM adopts high-speed vulcanization system, and NR adopts late effect property vulcanization system to save heat treatment time, improves vulcanization rate.The researchist such as to make the country prosperous together discloses the key that NR/EPDM blend compounds reaches covulcanization: select suitable vulcanization accelerator, balance the sulfurate activity between each glue kind, coordinates the vulcanization rate of blend compounds.
Summary of the invention
The present invention relates to and a kind ofly improve expanding material of natural rubber and ethylene-propylene rubber(EPR) Blend rubber performance and preparation method thereof.Wherein adopt natural rubber, polyethylene octene elastomer (POE), terpolymer EP rubber, methacrylic acid, white carbon black, zinc oxide, Zinic stearas, peroxide cross-linking agent is blending reaction in rubber and plastic Banbury mixer, natural rubber and the ethylene-propylene rubber(EPR) molecule segment of in-situ polymerization generation zinc methacrylate and precrosslink form interpenetrating(polymer)networks, thus obtain a kind of olefin type elastomer containing natural rubber and ethylene-propylene rubber(EPR) segment, this material component is substituted ethylene-propylene rubber(EPR) join natural rubber and ethylene-propylene rubber(EPR) sizing material in, obviously can improve the consistency of natural rubber and ethylene-propylene rubber(EPR) and improve the mechanical property of natural rubber and ethylene-propylene rubber(EPR) Blend rubber.In natural rubber and ethylene-propylene rubber(EPR) Blend rubber, add this kind of expanding material, the tensile strength of cross-linked rubber and tear strength improve more than 10%.
Concrete technical scheme is as follows: a kind of expanding material improving natural rubber and ethylene-propylene rubber(EPR) Blend rubber performance, comprise following component (wt.% represents): natural rubber: 10-25%, ethylene-propylene rubber(EPR): 20-30%, ethylene octene elastomerics: 30-50%, methacrylic acid: 3-10%, white carbon black: 3-10%, zinc oxide: 3-10%, Zinic stearas: 0.5-2%, initiator 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane: 0.5-1%.
Preparation method of the present invention comprises the following steps:
(1) first natural rubber is plasticated in Banbury mixer, it is mixing then to add Zinic stearas, methacrylic acid and white carbon black, by for subsequent use for the natural rubber master batch bottom sheet mixed;
(2) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), then add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended; Add the natural rubber master batch that step (1) processes, at Banbury mixer situ reaction 5-10 minute in batches;
(3) above-mentioned Blend rubber mill bottom sheet or in an extruder extruding pelletization namely obtain the material of the present application.
The present invention solves its technical problem and adopts technical scheme more specifically to comprise the steps:
A) first Zinic stearas, methacrylic acid and white carbon black are mixed according to proportioning in homogenizer; Adopt aforesaid method first Zinic stearas, methacrylic acid and white carbon black to be mixed to become powdery and be convenient to processing and disperse;
B) in Banbury mixer first natural smoked sheet rubber plastic steelmaking, temperature 130 DEG C-140 DEG C, plasticates 4 minutes, and the mixture then adding Zinic stearas, methacrylic acid and white carbon black according to proportioning carries out mixing, by for subsequent use for mixing uniform natural rubber master batch bottom sheet;
C) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, because zinc oxide and methacrylic acid reaction in－situ are violent and heat release, so add in batches in batches;
D) mixing time 5-10 minute discharge in Banbury mixer, rotating speed 70r/min, temperature 130 DEG C-140 DEG C;
E) mill bottom sheet is adopted, between 70 DEG C-80 DEG C; Employing forcing machine is extruded, fluxing zone 100 DEG C, outlet section 130 DEG C.
Embodiment
Embodiment 1:
1) first Zinic stearas, methacrylic acid and white carbon black are mixed according to proportioning in stirrer, proportioning is 1:5:5;
2) first natural rubber is plasticated in Banbury mixer, temperature 130 DEG C-140 DEG C, plasticates 4 minutes, and the mixture then adding Zinic stearas, methacrylic acid and white carbon black according to proportioning carries out mixing, and proportioning is that 2:1 is by for subsequent use for mixing uniform natural rubber master batch bottom sheet;
3) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, proportioning is: 45:22.5:7:1:24.5 in batches;
4) mixing time 5 minutes discharges in Banbury mixer, dump temperature 140 DEG C;
5) mill bottom sheet is adopted, between roller temperature 70 DEG C-80 DEG C.
Embodiment 2:
1) first natural rubber is plasticated in Banbury mixer, temperature 130 DEG C-140 DEG C, plasticates 4 minutes, then adds Zinic stearas, methacrylic acid and white carbon black according to proportioning and carries out mixing, and proportioning is 20:1:5:5, by for subsequent use for mixing uniform natural rubber master batch bottom sheet;
2) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, proportioning is: 45:22:6:1:26 in batches;
3) mixing time 10 minutes discharges in Banbury mixer, dump temperature 130 DEG C; Adopt mill bottom sheet, between roller temperature 70 DEG C-80 DEG C;
4) forcing machine extruding pelletization is adopted, fluxing zone 100 DEG C, outlet section 130 DEG C.
Embodiment 3:
1) first natural rubber is plasticated in Banbury mixer, temperature 130 DEG C-140 DEG C, plasticate 4 minutes, then POE and ethylene-propylene rubber(EPR) is added, the mixture adding Zinic stearas, methacrylic acid and white carbon black according to proportioning after mixing 1 minute carries out mixing, proportioning is 15:45:22:1:5:5, and mixing evenly rear bottom sheet cooling is for subsequent use;
2) in Banbury mixer, add above-mentioned rubber unvulcanizate, between temperature 70 C-80 DEG C, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended, proportioning is: 93:6:1;
3) mixing time 10 minutes discharges in Banbury mixer, dump temperature 130 DEG C; Adopt mill bottom sheet, between roller temperature 70 DEG C-80 DEG C;
4) forcing machine extruding pelletization is adopted, fluxing zone 100 DEG C, outlet section 130 DEG C.
Embodiment 4:
1) first Zinic stearas, methacrylic acid and white carbon black are mixed according to proportioning in stirrer, proportioning is 1:5:5;
2) first natural rubber is plasticated in Banbury mixer, temperature 130 DEG C-140 DEG C, plasticates 4 minutes, and the mixture then adding Zinic stearas, methacrylic acid and white carbon black according to proportioning carries out mixing, and proportioning is that 2:1 is by for subsequent use for mixing uniform natural rubber master batch bottom sheet;
3) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, proportioning is: 45:22:6:1:26 in batches;
4) mixing time 5 minutes discharges in Banbury mixer, dump temperature 140 DEG C;
5) mill bottom sheet is adopted, between roller temperature 70 DEG C-80 DEG C.
Embodiment 5:
Other steps are with embodiment 1 and 4.
Wherein in step 3, in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, proportioning is: 45:20:9:1:25 in batches.
Embodiment 6:
Other steps are with embodiment 1 and 4.
Wherein in step 3, in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, proportioning is: 45:25:8:1:21 in batches.
Material of the present invention has following technical parameter:
Table 1
Table 1 (Continued)
Material of the present invention has following technical parameter:
In tire sidewall glue reference formulation, adopt 20 parts of expanding materials (prepared by embodiment 1) to substitute 20 parts of EPDM, performance is in table 2.Reference formulation is as follows: NR (1# smoked sheet): 60, EPDM:40, zinc oxide: 5, stearic acid: 1.5, anti-aging agent RD: 1, antioxidant MB: 1, captax: 1, accelerant B Z:0.4, carbon black (330): 50, S:2.
Table 2 expanding material is on the impact of NR/EPDM Blend rubber performance
As can be seen from the table, after adding expanding material, tensile strength and the tear strength of cross-linked rubber are improved, and the performance after hot oxygen and ozone ageing is all better than the sizing material not adding expanding material.
Claims (7)
1. one kind is improved the expanding material of natural rubber and ethylene-propylene rubber(EPR) Blend rubber performance, it is characterized in that: comprise following component (wt.% represents): natural rubber: 10-25%, ethylene-propylene rubber(EPR): 20-30%, ethylene octene elastomerics: 30-50%, methacrylic acid: 3-10%, white carbon black: 3-10%, zinc oxide: 3-10%, Zinic stearas: 0.5-2%, initiator 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane: 0.5-1%.
2. expanding material according to claim 1, is characterized in that: adopt natural rubber, ethylene-propylene rubber(EPR), POE tertiary blending, dynamic vulcanization precrosslink natural rubber and ethylene-propylene rubber(EPR), form multinomial stabilising system; Methacrylic acid and zinc oxide is adopted to generate zinc methacrylate in the reaction of ethylene octene elastomer substrates situ; Adopt 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane to cause zinc methacrylate polymerization, formed polymethyl acrylic acid zinc and ethylene octene elastomerics, natural rubber, ethylene-propylene rubber(EPR) interpenetrating(polymer)networks compatibilization system.
3. the preparation method of expanding material described in claim 1, comprises the following steps:
(1) first natural rubber is plasticated in Banbury mixer, it is mixing then to add Zinic stearas, methacrylic acid and white carbon black, by for subsequent use for the natural rubber master batch bottom sheet mixed;
(2) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), then add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended; Add the natural rubber master batch that (1) processes, at Banbury mixer situ reaction 5-10 minute in batches;
(3) above-mentioned Blend rubber at mill bottom sheet or extruding pelletization in an extruder.
4. a preparation method for expanding material, comprises the following steps: a) first Zinic stearas, methacrylic acid and white carbon black are mixed according to proportioning in homogenizer; Adopt aforesaid method first Zinic stearas, methacrylic acid and white carbon black to be mixed to become powdery and be convenient to processing and disperse;
B) in Banbury mixer first natural smoked sheet rubber plastic steelmaking, temperature 130 DEG C-140 DEG C, plasticates 4 minutes, and the mixture then adding Zinic stearas, methacrylic acid and white carbon black according to proportioning carries out mixing, by for subsequent use for mixing uniform natural rubber master batch bottom sheet;
C) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, because zinc oxide and methacrylic acid reaction in－situ are violent and heat release, so add in batches in batches;
D) mixing time 5-10 minute discharge in Banbury mixer, rotating speed 70r/min, temperature 130 DEG C-140 DEG C;
E) mill bottom sheet is adopted, between 70 DEG C-80 DEG C; Employing forcing machine is extruded, fluxing zone 100 DEG C, outlet section 130 DEG C.
5. a preparation method for expanding material, comprises the following steps:
1) first Zinic stearas, methacrylic acid and white carbon black are mixed according to proportioning in stirrer, proportioning is 1:5:5;
2) first natural rubber is plasticated in Banbury mixer, temperature 130 DEG C-140 DEG C, plasticates 4 minutes, and the mixture then adding Zinic stearas, methacrylic acid and white carbon black according to proportioning carries out mixing, and proportioning is that 2:1 is by for subsequent use for mixing uniform natural rubber master batch bottom sheet;
3) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, proportioning is: 45:22.5:7:1:24.5 in batches;
4) mixing time 5 minutes discharges in Banbury mixer, dump temperature 140 DEG C;
5) mill bottom sheet is adopted, between roller temperature 70 DEG C-80 DEG C.
6. a preparation method for expanding material, comprises the following steps:
1) first natural rubber is plasticated in Banbury mixer, temperature 130 DEG C-140 DEG C, plasticates 4 minutes, then adds Zinic stearas, methacrylic acid and white carbon black according to proportioning and carries out mixing, and proportioning is 20:1:5:5, by for subsequent use for mixing uniform natural rubber master batch bottom sheet;
2) in Banbury mixer, add POE and ethylene-propylene rubber(EPR), between temperature 70 C-80 DEG C, within mixing 1 minute, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended later; Add the above-mentioned natural rubber master batch processed, proportioning is: 45:22:6:1:26 in batches;
3) mixing time 10 minutes discharges in Banbury mixer, dump temperature 130 DEG C; Adopt mill bottom sheet, between roller temperature 70 DEG C-80 DEG C;
4) forcing machine extruding pelletization is adopted, fluxing zone 100 DEG C, outlet section 130 DEG C.
7. a preparation method for expanding material, comprises the following steps:
1) first natural rubber is plasticated in Banbury mixer, temperature 130 DEG C-140 DEG C, plasticate 4 minutes, then POE and ethylene-propylene rubber(EPR) is added, the mixture adding Zinic stearas, methacrylic acid and white carbon black according to proportioning after mixing 1 minute carries out mixing, proportioning is 15:45:22:1:5:5, and mixing evenly rear bottom sheet cooling is for subsequent use;
2) in Banbury mixer, add above-mentioned rubber unvulcanizate, between temperature 70 C-80 DEG C, add zinc oxide and 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane is evenly blended, proportioning is: 93:6:1;
3) mixing time 10 minutes discharges in Banbury mixer, dump temperature 130 DEG C; Adopt mill bottom sheet, between roller temperature 70 DEG C-80 DEG C;
Adopt forcing machine extruding pelletization, fluxing zone 100 DEG C, outlet section 130 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987326A (en) * | 2017-12-18 | 2018-05-04 | 南漳富元鼎航空器材配件有限公司 | Ethylene propylene diene rubber and natural rubber and compounded rubber and preparation method thereof |
| CN111978604A (en) * | 2020-08-26 | 2020-11-24 | 徐工集团工程机械有限公司 | Anti-cracking rubber and crawler belt |
| CN115286847A (en) * | 2022-08-29 | 2022-11-04 | 岭南师范学院 | Zinc methacrylate/natural rubber composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001014464A1 (en) * | 1999-08-23 | 2001-03-01 | Liu, Guixing | Thermoplastic elastomer produced from waste rubber powder/plastic and the article made therefrom |
| CN1465614A (en) * | 2002-06-11 | 2004-01-07 | 毅 邵 | Composite polyolefine thermoplastic vulcanizate |
| KR20040064754A (en) * | 2003-01-10 | 2004-07-21 | 한국타이어 주식회사 | Rubber composition for tire sidewall |
| CN102851012A (en) * | 2012-09-19 | 2013-01-02 | 青岛开世密封工业有限公司 | Water swellable rubber in high-concentration salt solution and preparation method thereof |
-
2015
- 2015-02-09 CN CN201510066284.9A patent/CN104710692B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001014464A1 (en) * | 1999-08-23 | 2001-03-01 | Liu, Guixing | Thermoplastic elastomer produced from waste rubber powder/plastic and the article made therefrom |
| CN1465614A (en) * | 2002-06-11 | 2004-01-07 | 毅 邵 | Composite polyolefine thermoplastic vulcanizate |
| KR20040064754A (en) * | 2003-01-10 | 2004-07-21 | 한국타이어 주식회사 | Rubber composition for tire sidewall |
| CN102851012A (en) * | 2012-09-19 | 2013-01-02 | 青岛开世密封工业有限公司 | Water swellable rubber in high-concentration salt solution and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 齐兴国等: "原位改性三元乙丙橡胶炭黑混炼胶与天然橡胶共混胶的性能", 《合成橡胶工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987326A (en) * | 2017-12-18 | 2018-05-04 | 南漳富元鼎航空器材配件有限公司 | Ethylene propylene diene rubber and natural rubber and compounded rubber and preparation method thereof |
| CN111978604A (en) * | 2020-08-26 | 2020-11-24 | 徐工集团工程机械有限公司 | Anti-cracking rubber and crawler belt |
| CN115286847A (en) * | 2022-08-29 | 2022-11-04 | 岭南师范学院 | Zinc methacrylate/natural rubber composite material and preparation method thereof |
| CN115286847B (en) * | 2022-08-29 | 2023-07-14 | 岭南师范学院 | Zinc methacrylate/natural rubber composite material and preparation method thereof |
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