CN109054343A - A kind of blended vulcanizate and preparation method thereof - Google Patents
A kind of blended vulcanizate and preparation method thereof Download PDFInfo
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- CN109054343A CN109054343A CN201810777418.1A CN201810777418A CN109054343A CN 109054343 A CN109054343 A CN 109054343A CN 201810777418 A CN201810777418 A CN 201810777418A CN 109054343 A CN109054343 A CN 109054343A
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- type polyurethane
- natural rubber
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 claims abstract description 118
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 99
- 229920002635 polyurethane Polymers 0.000 claims abstract description 96
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 95
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 95
- 229920001194 natural rubber Polymers 0.000 claims abstract description 95
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 82
- 238000004073 vulcanization Methods 0.000 claims abstract description 52
- 230000003213 activating effect Effects 0.000 claims abstract description 39
- 238000007670 refining Methods 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229920001971 elastomer Polymers 0.000 claims description 26
- 239000005060 rubber Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 20
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 15
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 11
- 238000003801 milling Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001195 polyisoprene Polymers 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 28
- 229920003225 polyurethane elastomer Polymers 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 238000004513 sizing Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000006698 induction Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- XIVNZHXRIPJOIZ-UHFFFAOYSA-N octadecanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCCCCC(O)=O XIVNZHXRIPJOIZ-UHFFFAOYSA-N 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2407/00—Characterised by the use of natural rubber
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of preparation methods of blended vulcanizate, comprising the following steps: is kneaded again with vulcanizing agent, reinforced filling, activating agent, promotor after blending-type polyurethane is plasticated, obtains blending-type polyurethane masterbatch；It is kneaded again with activating agent, promotor, reinforced filling, vulcanizing agent after natural rubber is plasticated, obtains natural rubber masterbatch；Refining after cure will be blended after blending-type polyurethane masterbatch presulfurization with the natural rubber masterbatch, obtain blended vulcanizate.The application by after presulfurization blending-type polyurethane and caoutchouc vulcanization be blended, improve the blend sulfurized degree of two-phase, to make blended vulcanizate physical mechanical property with higher and preferable dynamic property, applicability of the blending-type polyurethane on tire is considerably increased.
Description
Technical field
The present invention relates to blend rubber processing technique fields more particularly to a kind of blended vulcanizate and preparation method thereof.
Background technique
Millable polyurethane elastomer is the block copolymerization product of polyisocyanates, polyalcohol and chain extender hybrid reaction.
Contain more polarity aliphatic radical and carbamate in the structure of millable polyurethane elastomer, in polyurethane molecular and it is intermolecular can
Hydrogen bond is formed, the polyalcohol of soft segment and the isocyanates of hard section, which are alternately arranged, generates micron-scale phase separation structure.Above structure feature
Make millable polyurethane elastomer that there are intensity height, oil resistant, resistant to chemical etching, the ageing-resistant and excellent properties such as wear-resisting, but its
Molecule interchain strong interaction makes its dynamic heat build up larger and greatly limits its application.
Not only cost is relatively low for natural rubber, but also has preferable mixed refining process performance, also has excellent physical mechanicalness
Can and dynamic property, but natural rubber weatherability, ageing-resistant and wearability it is poor therefore more be used for and other rubber
It is blended, and is widely used in manufacturing in sebific duct, adhesive tape, damping and tire product.
Currently, since the production cost of mixing polyurethane rubber is higher, being moved in the research process of blending-type polyurethane
State heat is larger, with other non-polar rubber poor compatibilities, is unable to synchronic curing when blend sulfurized and is greatly reduced its performance,
To limit the application of this excellent material.A kind of blending is disclosed in the Chinese patent of Publication No. CN104725830A
Uncured polyurethane and other unvulcanized rubber are kneaded together, then are sulfided into rubber product by modified rubber material；It should
For uncured polyurethane with during other blend rubbers, processing performance is poor in method, and does not consider during co-vulcanization
The problem of whether co-vulcanization of diphase rubber matches.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of preparation method of blended vulcanizate, this method can improve mixing
The state of cure (vulcanization) of type polyurethane and natural rubber improves the mechanical property and dynamic mechanical properties of blended vulcanizate.
In view of this, this application provides a kind of preparation methods of blended vulcanizate, comprising the following steps:
It is kneaded again with vulcanizing agent, reinforced filling, activating agent, promotor after blending-type polyurethane is plasticated, obtains mixed milling type
Polyurethane masterbatch；
It is kneaded again with activating agent, promotor, reinforced filling, vulcanizing agent after natural rubber is plasticated, obtains natural rubber mother
Refining glue；
Refining after cure will be blended after blending-type polyurethane masterbatch presulfurization with the natural rubber masterbatch, be blended
Vulcanizate.
Preferably, in the step of obtaining blending-type polyurethane masterbatch, by the number of the blending-type polyurethane in terms of
Amount standard, the vulcanizing agent are 1.0~5.0 parts by weight, and the reinforced filling is 20.0~70.0 parts by weight, and the activating agent is
2.0~5.0 parts by weight, the promotor are 1.0~8.0 parts by weight；In the step of obtaining natural rubber masterbatch, with described
The number of natural rubber is measurement criteria, and the vulcanizing agent is 1.0~5.0 parts by weight, and the reinforced filling is 20.0~70.0
Parts by weight, the activating agent are 2.0~5.0 parts by weight, and the promotor is 1.0~8.0 parts by weight.
Preferably, in described the step of obtaining blending-type polyurethane masterbatch, the vulcanizing agent is sulphur, and the reinforcement is filled out
Material is carbon black N330, and the promotor is made of captax and altax, and the activating agent is by activating agent NH-2 and stearic acid
Zinc composition；In the step of obtaining natural rubber masterbatch, the vulcanizing agent is sulphur, and the reinforced filling is carbon black N330,
The promotor is made of captax and altax, and the activating agent is made of zinc oxide and stearic acid.
Preferably, the ratio of the blending-type polyurethane masterbatch and the natural rubber masterbatch is (50~80) weight
Part: (20~50) parts by weight.
Preferably, the temperature of the presulfurization is 150~170 DEG C, and the time is 3~5min.
Preferably, the step of obtaining blending-type polyurethane masterbatch specifically:
Blending-type polyurethane is plasticated 3~5min, vulcanizing agent, reinforced filling, activating agent and promotor is sequentially added, eats
Left and right cutter 3~4 times after material, bottom sheet it is thin it is logical beat triangle bag 3~5 times, then 1~3 slice of clot, obtains mixed milling type and gathers
Urethane masterbatch.
Preferably, the step of obtaining natural rubber masterbatch specifically:
Natural rubber is plasticated 3~5min, sequentially adds activating agent, promotor, reinforced filling, vulcanizing agent, material feeding is complete
Left and right cutter 3~4 times after finishing, bottom sheet it is thin it is logical beat triangle bag 3~5 times, then 1~3 slice of clot, obtains natural rubber masterbatching
Glue.
Preferably, the step of obtaining blended vulcanizate specifically:
It will be blended in open mill after blending-type polyurethane masterbatch presulfurization with natural rubber masterbatch, then bottom sheet is thin logical
It beats triangle bag 3~5 times, then 1~3 slice of clot, turns refining again after obtained intermediate plate is placed, finally vulcanize, obtain
Blended vulcanizate.
Preferably, the temperature of the vulcanization is 150~170 DEG C, and the time is 4~25min.
Present invention also provides a kind of blended vulcanizates, by the blending-type polyurethane after natural rubber masterbatch and presulfurization
Masterbatch is obtained through over cure；The natural rubber refining glue is by blending-type polyurethane, vulcanizing agent, reinforced filling, activating agent and rush
It is kneaded to obtain into agent, the blending-type polyurethane masterbatch is by natural rubber, vulcanizing agent, reinforced filling, activating agent and promotor
Mixing obtains.
This application provides a kind of preparation methods of blended vulcanizate, are prepared for blending-type polyurethane masterbatching respectively first
Glue and natural rubber masterbatch, then will be blended after blending-type polyurethane masterbatch presulfurization with the natural rubber masterbatch refining after
Vulcanize to get blended vulcanizate is arrived.The application is by carrying out presulfurization to blending-type polyurethane, first to blending-type polyurethane masterbatching
Glue carries out the processing of induction period vulcanization, so that blending-type polyurethane masterbatch is formed activity bigger with accelerative activator base
The rubber molecular chain of group, accelerates a sulfidation of blending-type polyurethane masterbatch, so that blending-type polyurethane masterbatch
Sulfidation more matched with natural rubber, improve the state of cure (vulcanization) and performance of blended vulcanizate.
Detailed description of the invention
Fig. 1 is the vulcanization characteristics song of the blending-type polyurethane of the embodiment of the present invention 1~3 and the natural rubber of comparative example 1~2
Line chart；
Fig. 2 is the stereoscan photograph of blended vulcanizate prepared by embodiment 3 and comparative example 2；
Fig. 3 is the vulcanization characteristics curve graph of blended vulcanizate prepared by embodiment 4 and comparative example 3.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
It is larger for the hot heat of blending-type polyurethane, with other non-polar rubber poor compatibilities, it is blend sulfurized cannot be same
Step vulcanization and the problem of make reduced performance, a kind of preparation method of blended vulcanizate, this method of the embodiment of the present invention pass through elder generation
To blending-type polyurethane masterbatch presulfurization, then refining vulcanization is blended with natural rubber masterbatch, results in blended vulcanizate,
This method effectively compensates for the deficiency that blending-type polyurethane and natural rubber cannot be blend sulfurized, expands blending-type polyurethane
Application range, the shortcomings that improving blended vulcanizate poor mechanical property, tensile strength, the tearing for improving blended vulcanizate are strong
Degree and reduces dynamic heat build up at fatigue life.Specifically, the preparation method of the application blended vulcanizate, specifically include with
Lower step:
It is kneaded again with vulcanizing agent, reinforced filling, activating agent, promotor after blending-type polyurethane is plasticated, obtains mixed milling type
Polyurethane masterbatch；
It is kneaded again with activating agent, promotor, reinforced filling, vulcanizing agent after natural rubber is plasticated, obtains natural rubber mother
Refining glue；
Refining after cure will be blended after blending-type polyurethane masterbatch presulfurization with the natural rubber masterbatch, be blended
Vulcanizate.
During preparing blended vulcanizate, the application is kneaded after blending-type polyurethane is plasticated first, is obtained
Blending-type polyurethane masterbatch；It is mixed again with vulcanizing agent, reinforced filling, activating agent, promotor after blending-type polyurethane is plasticated
Refining, obtains blending-type polyurethane masterbatch.In the process, the vulcanizing agent is sulphur, and the reinforced filling is reinforcement and filler
Agent N330, the activating agent are made of activating agent NH-2 with zinc stearate, and the promotor is by captax and altax group
At.Using the number of the blending-type polyurethane as measurement criteria, the content of the promotor is 1.0~8.0 parts by weight, the work
Property agent content be 2.0~5.0 parts by weight, the content of the reinforced filling is 20.0~70.0 parts by weight, the vulcanizing agent
Content is 1.0~5.0 parts by weight；In a particular embodiment, the content of the promotor is 2.0~6.0 parts by weight, the activity
The content of agent is 3.0~4.0 parts by weight, and the content of the reinforced filling is 30.0~60.0 parts by weight, and the vulcanizing agent contains
Amount is 1.0~3.0 parts by weight.Described plasticate with described be kneaded is technological means well known to those skilled in the art, to this
Application is not particularly limited；The application lists a kind of mode of mixing, specifically:
Blending-type polyurethane is plasticated 3~5min, vulcanizing agent, reinforced filling, activating agent and promotor is sequentially added, eats
Left and right cutter 3~4 times after material, bottom sheet it is thin it is logical beat triangle bag 3~5 times, then 1~3 slice of clot, obtains mixed milling type and gathers
Urethane masterbatch.
During preparing natural rubber masterbatch, using the number of the natural rubber as measurement criteria, the promotion
The content of agent is 1.0~8.0 parts by weight, and the content of the activating agent is 2.0~5.0 parts by weight, the content of the reinforced filling
For 20.0~70.0 parts by weight, the content of the vulcanizing agent is 1.0~5.0 parts by weight；In a particular embodiment, the promotor
Content be 2.0~6.0 parts by weight, the content of the activating agent is 3.0~4.5 parts by weight, and the content of the reinforced filling is
30.0~60.0 parts by weight, the content of the vulcanizing agent are 2.0~4.0 parts by weight.The promotor is by captax and promotor
DM composition, the activating agent are made of zinc oxide and stearic acid, and the vulcanizing agent is sulphur, and the reinforced filling is reinforcement and filler
Agent N330.
It is after obtaining blending-type polyurethane masterbatch and natural rubber masterbatch, then blending-type polyurethane masterbatch is pre-
Vulcanization.The application to the blending-type polyurethane masterbatch presulfurization is carried out based on following mechanism.In rubber sulfur cross-linking
In system, vulcanization will pass through following process: induction period first stage-: phase interaction between activating agent, promotor and sulphur
With generating the rubber molecule of more sulphur promotor side groups, activity with higher, but cross-linking reaction has not occurred；Second stage-
Cross-linking reaction: crosslinking between rubber macromolecule and rubber macromolecule with more sulphur promotor side groups and react, and generates crosslinking
Key；Shortization, rearrangement, cracking, the modification of main chain occur for phase III-network maturation stage, cross-bond, and cross-bond tends towards stability.
According to the vulcanization characteristics curve of blending-type polyurethane and natural rubber, the time of scorch of blending-type polyurethane is long, vulcanization speed
Degree is slower, and caoutchouc vulcanization speed is exceedingly fast, and has just substantially completely handed at the end of not having also blending-type polyurethane induction period
Connection, this vulcanization characteristics are that the difference on blending-type polyurethane and two kinds of natural rubber material this body structure is (double in polyurethane
Linkage content is significantly less than natural rubber), this difference makes blending-type polyurethane and natural rubber and the used time leverages two
Kind rubber and its crosslinking degree of interface, so that performance is poor when both rubber blendings.Therefore, because mixed milling type is poly-
The curingprocess rate of urethane is relatively slow and the incipient scorch phase is longer, and caoutchouc vulcanization speed is quickly and the incipient scorch phase is shorter, therefore in order to make
Two kinds of vulcanizations of rubber can synchronize then the application and carry out presulfurization to millable polyurethane elastomer.The mistake of the presulfurization and vulcanization
Journey is suitable, such as herein described presulfurization carries out in vulcanizing press or baking oven.The temperature of the presulfurization be 150~
170 DEG C, the time of the presulfurization is 3~5min；The prevulcanisation time is too long, then blending-type polyurethane has a large amount of crosslinkings
Reticular structure is formed, without can be carried out subsequent processing.
After blending-type polyurethane masterbatch presulfurization, then it is blended with natural rubber masterbatch refining after cure to get
To blended vulcanizate.In the process, the ratio of blending-type polyurethane masterbatch and the natural rubber masterbatch be (50~
80) parts by weight: (20~50) parts by weight, in a particular embodiment, the blending-type polyurethane masterbatch and the natural rubber
The ratio of masterbatch is 70:30 or 50:50.The blending refining and the vulcanization are process well known to those skilled in the art, are pressed
According to the present invention specifically:
It will be blended in open mill after blending-type polyurethane masterbatch presulfurization with natural rubber masterbatch, then bottom sheet is thin logical
It beats triangle bag 3~5 times, then 1~3 slice of clot, turns refining again after obtained intermediate plate is placed, finally vulcanize, obtain
Blended vulcanizate.
During vulcanization, the temperature of the vulcanization is 150~170 DEG C, and the time of the vulcanization is 4~25min.
This application provides the preparation methods of blended vulcanizate, pre- by using induction period is carried out to blending-type polyurethane
Vulcanization can be very good the curingprocess rate gap great disparity for solving the problems, such as blending-type polyurethane and natural rubber, greatly improve
The state of cure (vulcanization) of two-phase；The physical mechanical property that blending-type polyurethane/natural rubber is blended is improved well, simultaneously
It improves tensile strength, tearing strength and the fatigue life of vulcanization blend compounds and reduces dynamic heat build up performance；The simple process,
Quality is stablized, and reduces manufacturing cost, greatly expands application of the blending-type polyurethane on blend compounds.
For a further understanding of the present invention, below with reference to embodiment to blended vulcanizate provided by the invention and its preparation side
Method is described in detail, and protection scope of the present invention is not limited by the following examples.
1 the present embodiment of embodiment is the test of presulfurization blending-type polyurethane vulcanization characteristics, comprising the following steps:
(1) it plasticates
To plasticate 3 minutes in 100 parts of addition open mills of blending-type polyurethane；
(2) it is kneaded
Sizing material after plasticating is subjected to packet roller 2 minutes, then be added 2 parts of sulphur, wait eat powder after carbon black is added
N33030 parts, after eating powder, left and right cutter 3 times, cutter time interval is 4 seconds, is turned refining 3 times；Then activating agent is sequentially added
1 part of NH-2,2 parts of zinc stearate, 2 parts of captax, 4 parts of altax；It eats after powder left and right cutter 3 times, it is thin logical to make a call to three
Angle is wrapped 4 times, then 3 slices of clot；
(3) measurement of vulcanization characteristics
The sizing material being kneaded is taken out into part using the test of no rotor vulcameter progress vulcanization characteristics, test condition is
160℃×30min；As shown in FIG. 1, FIG. 1 is blending-type polyurethane masterbatch, natural rubber masterbatch and blended vulcanizates
Vulcanization characteristics curve graph；
(4) presulfurization
By the vulcanization characteristics curve measured in step (3), determine blending-type polyurethane masterbatch presulfurization condition be
The vulcanization that 4min × 160 DEG C are carried out in vulcanizing press then took out open mill cooling；
(5) measurement of presulfurization rubber vulcanization characteristic
Presulfurization blending-type polyurethane sizing material obtained in step (4) is taken to carry out the survey of vulcanization characteristics with no rotor vulcameter
Examination, test condition are 160 DEG C × 30min, as shown in Figure 1；
2 the present embodiment of embodiment is the test of caoutchouc vulcanization characteristic, comprising the following steps:
(1) it plasticates
To plasticate 3 minutes in 100 parts of addition open mills of natural rubber；
(2) it is kneaded
Blended rubber after mixing is plasticated carries out packet roller 2 minutes, then sequentially adds 1 part of captax, altax
2 parts, 3 parts of zinc oxide, 1.5 parts of stearic acid；After material feeding, left and right cutter 3 times, cutter time interval is 4 seconds, is turned refining 3 times；So
Afterwards be added carbon black N33030 part, eat after powder left and right cutter 3 times, it is thin lead to beat triangle bag 4 times；Then 2 parts of sulphur are added, powder is eaten
After left and right cutter 3 times, turn refining 2 times, bottom sheet it is thin it is logical beat triangle bag 4 times, then 3 slices of clot；
(3) test of vulcanization characteristics
The sizing material being kneaded is taken out to the test that vulcanization characteristics is partially carried out with no rotor vulcameter, test condition 160
℃×30min；As shown in Figure 1.
The preparation method of embodiment 3 presulfurization blending-type polyurethane and natural rubber masterbatch blended vulcanizate, including with
Lower step:
1, the preparation of masterbatch
(1) preparation of blending-type polyurethane masterbatch
To plasticate 3 minutes in 100 parts of addition open mills of blending-type polyurethane；Sizing material after plasticating is subjected to packet roller 2
Minute, then be added 2 parts of sulphur, wait eat powder after be added carbon black N33030 parts, after eating powder, left and right cutter 3 times, cutter
Time interval is 4 seconds, is turned refining 3 times, then sequentially adds 1 part of activating agent NH-2,2 parts of zinc stearate, 2 parts of captax, promotes
DM4 parts of agent；Eat after powder left and right cutter 3 times, it is thin it is logical beat triangle bag 4 times, then 3 slices of clot, obtain the poly- ammonia of mixed milling type
The masterbatch of ester；
(2) preparation of natural rubber masterbatch
To plasticate 3 minutes in 100 parts of addition open mills of natural rubber；Blended rubber after mixing is plasticated wraps
Roller 2 minutes, then sequentially add 1 part of captax, 2 parts of altax, 3 parts of zinc oxide, 1.5 parts of stearic acid；Material feeding finishes
Afterwards, left and right cutter 3 times, cutter time interval are 4 seconds, are turned refining 3 times；Then blended rubber bottom sheet is thin logical, carbon black N330 is added
It 30 parts, eats after powder left and right cutter 3 times, it is thin logical to beat triangle bag 4 times；Then 2 parts of sulphur are added, left and right cutter after powder is eaten
3 times, turn refining 2 times, bottom sheet it is thin it is logical beat triangle bag 4 times, then 3 slices of clot, obtain the masterbatch of natural rubber；
2, presulfurization
The sizing material that 3/4 is taken out from polyurethane masterbatch carries out presulfurization；Presulfurization condition be in vulcanizing press into
Then open mill cooling was taken out in the vulcanization of row 4min × 160 DEG C, spare；
3, blending-type polyurethane and natural rubber are blended
1/4 of natural rubber masterbatch obtained in step (1) is taken to be blended with the blending-type polyurethane after presulfurization,
Make the ratio 70/30 of blending-type polyurethane and natural rubber, after being blended uniformly, bottom sheet it is thin it is logical beat triangle bag 3~5 times, then
1~3 slice of clot again；
(4) vulcanize
After above-mentioned film is placed 8 hours, then turn refining 3~5 times, vulcanizes 8 points at 160 DEG C on vulcanizing press
Clock obtains the blended vulcanizate made of blending-type polyurethane and natural rubber.It include blending sulphur manufactured in the present embodiment in Fig. 1
Change the vulcanization characteristics curve of glue；Fig. 2 is the stereoscan photograph of the blended vulcanizate of the present embodiment and the preparation of comparative example 2, Fig. 2
(a) stereoscan photograph of the blended vulcanizate prepared for comparative example 2, Fig. 2 (b) are blended vulcanizate manufactured in the present embodiment
Stereoscan photograph；As shown in Figure 2, phase interface is more smooth after presulfurization, the two-phase of presulfurization treated blended vulcanizate
Compatibility is more preferable.
4 the present embodiment of embodiment is blend sulfurized for the presulfurization blending-type polyurethane and natural rubber of a kind of different proportion
Preparation method, comprising the following steps:
1, the preparation of masterbatch
(1) preparation of blending-type polyurethane masterbatch
To plasticate 3 minutes in 100 parts of addition open mills of blending-type polyurethane；Sizing material after plasticating is subjected to packet roller 2
Minute, then be added 2 parts of sulphur, wait eat powder after be added carbon black N33030 parts, after eating powder, left and right cutter 3 times, cutter
Time interval is 4 seconds, is turned refining 3 times, then sequentially adds 1 part of activating agent NH-2,2 parts of zinc stearate, 2 parts of captax, promotes
DM4 parts of agent；Eat after powder left and right cutter 3 times, it is thin it is logical beat triangle bag 4 times, then 3 slices of clot, obtain the poly- ammonia of mixed milling type
The masterbatch of ester；
(2) preparation of natural rubber masterbatch
To plasticate 3 minutes in 100 parts of addition open mills of natural rubber；Blended rubber after mixing is plasticated wraps
Roller 2 minutes, then sequentially add 1 part of captax, 2 parts of altax, 3 parts of zinc oxide, 1.5 parts of stearic acid；Material feeding finishes
Afterwards, left and right cutter 3 times, cutter time interval are 4 seconds, are turned refining 3 times；Then blended rubber bottom sheet is thin logical, carbon black N330 is added
It 30 parts, eats after powder left and right cutter 3 times, it is thin logical to beat triangle bag 4 times；Then 2 parts of sulphur are added, left and right cutter after powder is eaten
3 times, turn refining 2 times, bottom sheet it is thin it is logical beat triangle bag 4 times, then 3 slices of clot, obtain the masterbatch of natural rubber；
2, presulfurization
The blending-type polyurethane masterbatch of preparation is subjected to presulfurization；Presulfurization condition is to carry out in vulcanizing press
Then open mill cooling was taken out in the vulcanization of 4min × 160 DEG C, spare；
3, blending-type polyurethane and natural rubber are blended
It takes natural rubber masterbatch obtained in step 1 to be blended with the blending-type polyurethane after presulfurization, makes to be kneaded
The ratio of type polyurethane and natural rubber is 50/50, after being blended uniformly, bottom sheet it is thin it is logical beat triangle bag 3~5 times, then clot 1 again
~3 slices；
4, vulcanize
After above-mentioned film is placed 8 hours, then turn refining 3~5 times, vulcanizes 6 points at 160 DEG C on vulcanizing press
Clock obtains the blended vulcanizate made of blending-type polyurethane and natural rubber.Fig. 3 is that embodiment 4 is total to prepared by comparative example 3
The curability curve graph of mixed vulcanizate.
The comparative test of comparative example 1 is the vulcanization characteristics test of the blending-type polyurethane of non-presulfurization, comprising the following steps:
(1) it plasticates
To plasticate 3 minutes in 100 parts of addition open mills of blending-type polyurethane；
(2) it is kneaded
Sizing material after plasticating is subjected to packet roller 2 minutes, then be added 2 parts of sulphur, wait eat powder after carbon black is added
N33030 parts, after eating powder, left and right cutter 3 times, cutter time interval is 4 seconds, is turned refining 3 times；Then activating agent is sequentially added
1 part of NH-2,2 parts of zinc stearate, 2 parts of captax, 4 parts of altax；It eats after powder left and right cutter 3 times, it is thin logical to make a call to three
Angle is wrapped 4 times, then 3 slices of clot；
(3) measurement of vulcanization characteristics
The sizing material being kneaded is taken out to the test that vulcanization characteristics is partially carried out with no rotor vulcameter, test condition 160
DEG C × 30min, as shown in Figure 1.
The comparative experiments of comparative example 2 is blending-type polyurethane and the blend sulfurized preparation of natural rubber of a kind of non-presulfurization
Method, comprising the following steps:
1, the preparation of masterbatch
(1) preparation of blending-type polyurethane masterbatch
To plasticate 3 minutes in 100 parts of addition open mills of blending-type polyurethane；Sizing material after plasticating is subjected to packet roller 2
Minute, then be added 2 parts of sulphur, wait eat powder after be added carbon black N33030 parts, after eating powder, left and right cutter 3 times, cutter
Time interval is 4 seconds, is turned refining 3 times；Then 1 part of activating agent NH-2 is sequentially added, 2 parts of zinc stearate, 2 parts of captax, is promoted
4 parts of agent DM；Eat after powder left and right cutter 3 times, it is thin it is logical beat triangle bag 4 times, then 3 slices of clot, obtain the poly- ammonia of mixed milling type
The masterbatch of ester；
(2) preparation of natural rubber masterbatch
To plasticate 3 minutes in 100 parts of addition open mills of natural rubber；Blended rubber after mixing is plasticated wraps
Roller 2 minutes, then sequentially add 1 part of captax, 2 parts of altax, 3 parts of zinc oxide, 1.5 parts of stearic acid；Material feeding finishes
Afterwards, left and right cutter 3 times, cutter time interval are 4 seconds, are turned refining 3 times；Then blended rubber bottom sheet is thin logical, carbon black N330 is added
It 30 parts, eats after powder left and right cutter 3 times, it is thin logical to beat triangle bag 4 times；Then 2 parts of S are added, left and right cutter 3 after powder is eaten
It is secondary, turn refining 2 times, bottom sheet it is thin it is logical beat triangle bag 4 times, then 3 slices of clot, obtain the masterbatch of natural rubber；
2, blending-type polyurethane and natural rubber are blended
Take 1/4 of natural rubber masterbatch obtained in step 1 with take the 3/4 of blending-type polyurethane masterbatch to be total to
It is mixed, make the ratio 70/30 of blending-type polyurethane and natural rubber；After being blended uniformly, bottom sheet it is thin it is logical beat triangle bag 3~5 times, so
1~3 slice of clot again afterwards；
3, vulcanize
After above-mentioned film is placed 8 hours, then turn refining 3~5 times, vulcanizes 12 at 160 DEG C on vulcanizing press
Minute, obtain the blended vulcanizate made of blending-type polyurethane and natural rubber.It include the blending of this comparative example preparation in Fig. 1
The vulcanization characteristics curve graph of vulcanizate；After comprehensive observing Fig. 1 is it is found that presulfurization is processed, curingprocess rate is obviously accelerated, and curve is more
The inflection point for smoothly mismatching and being formed without two-phase curingprocess rate illustrates that two-phase can better synchronic curing；Torque simultaneously is higher
Two-phase state of cure (vulcanization) is bigger after illustrating presulfurization.
The comparative experiments of comparative example 3 is that a kind of blending-type polyurethane of the non-presulfurization of different proportion and natural rubber are blended
The preparation method of vulcanizate, comprising the following steps:
1, the preparation of masterbatch
(1) preparation of blending-type polyurethane masterbatch
To plasticate 3 minutes in 100 parts of addition open mills of blending-type polyurethane；Sizing material after plasticating is subjected to packet roller 2
Minute, then be added 2 parts of sulphur, wait eat powder after be added carbon black N33030 parts, after eating powder, left and right cutter 3 times, cutter
Time interval is 4 seconds, is turned refining 3 times；Then 1 part of activating agent NH-2 is sequentially added, 2 parts of zinc stearate, 2 parts of captax, is promoted
4 parts of agent DM；Eat after powder left and right cutter 3 times, it is thin it is logical beat triangle bag 4 times, then 3 slices of clot, obtain the poly- ammonia of mixed milling type
The masterbatch of ester；
(2) preparation of natural rubber masterbatch
To plasticate 3 minutes in 100 parts of addition open mills of natural rubber；Blended rubber after mixing is plasticated wraps
Roller 2 minutes, then sequentially add 1 part of captax, 2 parts of altax, 3 parts of zinc oxide, 1.5 parts of stearic acid；Material feeding finishes
Afterwards, left and right cutter 3 times, cutter time interval are 4 seconds, are turned refining 3 times；Then blended rubber bottom sheet is thin logical, carbon black N330 is added
It 30 parts, eats after powder left and right cutter 3 times, it is thin logical to beat triangle bag 4 times；Then 2 parts of S are added, left and right cutter 3 after powder is eaten
It is secondary, turn refining 2 times, bottom sheet it is thin it is logical beat triangle bag 4 times, then 3 slices of clot, obtain the masterbatch of natural rubber；
2, blending-type polyurethane and natural rubber are blended
It takes blending-type polyurethane masterbatch obtained in step 1 to be blended with natural rubber masterbatch, keeps mixed milling type poly-
Urethane and the ratio of natural rubber are 50/50, after being blended uniformly, bottom sheet it is thin it is logical beat triangle bag 3~5 times, then clot 1~3 again
Secondary slice；
3, vulcanize
After above-mentioned film is placed 8 hours, then turn refining 3~5 times, vulcanizes 8 points at 160 DEG C on vulcanizing press
Clock obtains the blended vulcanizate made of blending-type polyurethane and natural rubber.
The comprehensive vulcanization characteristics for listing sample prepared by Examples 1 to 3 and comparative example 1~2 of table 1；Table 2 lists implementation
The comprehensive performance of sample prepared by example 3 and comparative example 2.
Natural rubber prepared by the blending-type polyurethane and comparative example 1~2 of 1 Examples 1 to 3 of table preparation
The vulcanization characteristics tables of data of glue blending blend compounds
The comprehensive of blend compounds is blended in natural rubber prepared by the blending-type polyurethane and comparative example 2 of the preparation of 2 embodiment 3 of table
It can tables of data
The comprehensive vulcanization characteristics for listing sample prepared by embodiment 4 and comparative example 3 of table 3；Table 4 list embodiment 4 with
The comprehensive performance of sample prepared by comparative example 3.
The vulcanization that blend compounds are blended in natural rubber prepared by the blending-type polyurethane and comparative example 3 of 3 embodiment 4 of table preparation is special
Property tables of data
The comprehensive of blend compounds is blended in natural rubber prepared by the blending-type polyurethane and comparative example 3 of the preparation of 4 embodiment 4 of table
It can tables of data
By 1~table of table 4 it is found that the present invention improves the co-vulcanization degree of blending-type polyurethane and natural rubber well,
And the physical mechanical property that blending-type polyurethane/natural rubber is blended preferably is improved, while improving vulcanization and being used in combination
The tensile strength of glue, tearing strength and fatigue life and reduce dynamic heat build up performance.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of preparation method of blended vulcanizate, comprising the following steps:
It is kneaded again with vulcanizing agent, reinforced filling, activating agent, promotor after blending-type polyurethane is plasticated, obtains the poly- ammonia of mixed milling type
Ester masterbatch；
It is kneaded again with activating agent, promotor, reinforced filling, vulcanizing agent after natural rubber is plasticated, obtains natural rubber masterbatch；
Refining after cure will be blended after blending-type polyurethane masterbatch presulfurization with the natural rubber masterbatch, obtain blend sulfurized
Glue.
2. preparation method according to claim 1, which is characterized in that in the step of obtaining blending-type polyurethane masterbatch
In, using the number of the blending-type polyurethane as measurement criteria, the vulcanizing agent is 1.0~5.0 parts by weight, the reinforced filling
For 20.0~70.0 parts by weight, the activating agent is 2.0~5.0 parts by weight, and the promotor is 1.0~8.0 parts by weight；?
In the step of to natural rubber masterbatch, using the number of the natural rubber as measurement criteria, the vulcanizing agent is 1.0~5.0
Parts by weight, the reinforced filling are 20.0~70.0 parts by weight, and the activating agent is 2.0~5.0 parts by weight, and the promotor is
1.0~8.0 parts by weight.
3. preparation method according to claim 1 or 2, which is characterized in that the blending-type polyurethane masterbatch of obtaining
In step, the vulcanizing agent is sulphur, and the reinforced filling is carbon black N330, and the promotor is by captax and altax
Composition, the activating agent are made of activating agent NH-2 and zinc stearate；In the step of obtaining natural rubber masterbatch, the sulphur
Agent is sulphur, and the reinforced filling is carbon black N330, and the promotor is made of captax and altax, the activity
Agent is made of zinc oxide and stearic acid.
4. preparation method according to claim 1, which is characterized in that the blending-type polyurethane masterbatch and described natural
The ratio of rubber masterbatch is (50~80) parts by weight: (20~50) parts by weight.
5. preparation method according to claim 1, which is characterized in that the temperature of the presulfurization is 150~170 DEG C, when
Between be 3~5min.
6. preparation method according to claim 1, which is characterized in that the step of obtaining blending-type polyurethane masterbatch is specific
Are as follows:
Blending-type polyurethane is plasticated 3~5min, sequentially adds vulcanizing agent, reinforced filling, activating agent and promotor, material feeding is complete
Left and right cutter 3~4 times after finishing, bottom sheet it is thin it is logical beat triangle bag 3~5 times, then 1~3 slice of clot, obtains blending-type polyurethane
Masterbatch.
7. preparation method according to claim 1, which is characterized in that the step of obtaining natural rubber masterbatch specifically:
Natural rubber is plasticated 3~5min, activating agent, promotor, reinforced filling, vulcanizing agent are sequentially added, after material feeding
Left and right cutter 3~4 times, bottom sheet it is thin it is logical beat triangle bag 3~5 times, then 1~3 slice of clot, obtains natural rubber masterbatch.
8. preparation method according to claim 1, which is characterized in that the step of obtaining blended vulcanizate specifically:
It will be blended in open mill after blending-type polyurethane masterbatch presulfurization with natural rubber masterbatch, then bottom sheet is thin logical makes a call to three
Angle is wrapped 3~5 times, and then 1~3 slice of clot, turns refining again after obtained intermediate plate is placed, finally vulcanize, be blended
Vulcanizate.
9. preparation method according to claim 1 or claim 7, which is characterized in that the temperature of the vulcanization is 150~170 DEG C, when
Between be 4~25min.
10. a kind of blended vulcanizate, by the blending-type polyurethane masterbatch after natural rubber masterbatch and presulfurization through over cure
It obtains；The natural rubber refining glue is kneaded to obtain by blending-type polyurethane, vulcanizing agent, reinforced filling, activating agent and promotor, institute
Blending-type polyurethane masterbatch is stated to be kneaded to obtain by natural rubber, vulcanizing agent, reinforced filling, activating agent and promotor.
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| CN110499016A (en) * | 2019-09-06 | 2019-11-26 | 广东工业大学 | A kind of blending-type polyurethane and natural rubber blended vulcanizate and preparation method thereof |
| CN110527061A (en) * | 2019-09-04 | 2019-12-03 | 广东工业大学 | A kind of silica in situ filling blending-type polyurethane elastomer and preparation method thereof |
| CN112500613A (en) * | 2019-09-15 | 2021-03-16 | 天津纽威特橡胶制品股份有限公司 | High-wear-resistance prefabricated rubber track material and preparation method thereof |
| CN113999519A (en) * | 2021-11-16 | 2022-02-01 | 万华化学集团股份有限公司 | Polyurethane modified natural rubber and preparation method thereof |
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| CN110499016A (en) * | 2019-09-06 | 2019-11-26 | 广东工业大学 | A kind of blending-type polyurethane and natural rubber blended vulcanizate and preparation method thereof |
| CN112500613A (en) * | 2019-09-15 | 2021-03-16 | 天津纽威特橡胶制品股份有限公司 | High-wear-resistance prefabricated rubber track material and preparation method thereof |
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