CN100487033C - Chloroprene rubber polymer blend and its preparing method - Google Patents
Chloroprene rubber polymer blend and its preparing method Download PDFInfo
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- CN100487033C CN100487033C CNB2005100322025A CN200510032202A CN100487033C CN 100487033 C CN100487033 C CN 100487033C CN B2005100322025 A CNB2005100322025 A CN B2005100322025A CN 200510032202 A CN200510032202 A CN 200510032202A CN 100487033 C CN100487033 C CN 100487033C
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Abstract
This invention relates to chlorobutadiene rubber blend and preparing method thereof. Chlorobutadiene rubber is blended with trans- polyisoprene, so the binding performance of the blend with cord can be improved because of the compliance and easy-to-crystallize characteristic of trans-polyisoprene molecular, at the same time, the flex-crack resistance of cross-link rubber can also be improved. The main feed composition and compounding ratio(part) are: chlorobutadiene rubber 5-100, rubber additive 0-40, trans-polyisoprene 5-50, carbon black or carbon white 5-100,the additional agents such as promoter, sulfuration agent, activator, anti-aging agent and softening agent according to that of regular chlorobutadiene rubber.
Description
(1) technical field
The present invention relates to a kind of modified rubber and modification processing method thereof, be meant the modified rubber and preparation method thereof (international Patent classificating number is C08C19/28) of the compound reaction of a kind of rubber and carbon containing-carbon unsaturated link(age) specifically, especially blend of chloroprene rubber and using trans-polyisoprene and preparation method thereof, this chloroprene rubber polymer blend has excellent adhesion performance, and its sulfide has excellent flexible resistance be full of cracks performance.
(2) background technology
Chloroprene rubber has excellent thermotolerance, weathering resistance, wear resistance, oil-proofness, flame resistivity, is widely used in making goods such as sebific duct, adhesive tape, damping.For bearing the motion of high capacity, high frequency and guarantee work-ing life, chloroprene rubber often adopts framework material to come the performance of Reinforced Rubber, so these rubber item majorities are framework material Reinforced Rubber composite product.Concerning this class rubber item, not only require rubber to have excellent dynamic fatigue property, and require rubber and framework material good bonding.In order to improve the bond properties of chloroprene rubber and framework material, consider to adopt usually following method from the chloroprene rubber material aspect: 1. select suitable rubber, filler, vulcanizing agent type and consumption; 2. add specific adhesionpromoter; 3. carrying out modification handles.But these present methods all come with some shortcomings: promptly adopt the aforesaid method modified chloroprene rubber will make the processing performance and the physical and mechanical properties variation of sizing material.In addition, in the bond properties that improves chloroprene rubber material and framework material, the flex cracking resistance of chloroprene rubber material does not significantly improve, and still can not satisfy the needs in market fully, so the utmost point remains to be improved.Chinese patent ZL02134362.4 discloses a kind of preparation method of chloroprene rubber, but this method is only from taking suitable coating and suitable technological angle that the preparation technology of powder and particle chloroprene rubber is improved, still can not fundamentally solve the bond properties of chloroprene rubber material and framework material, and the problem of the flex cracking resistance of chloroprene rubber material existence.
(3) summary of the invention
The objective of the invention is to address the above problem, and a kind of chloroprene rubber polymer blend is provided, refer in particular to the blend of a kind of chloroprene rubber and using trans-polyisoprene.This kind chloroprene rubber polymer blend has more superior and bond properties framework material than existing chloroprene rubber, and its sulfide has excellent flexible resistance be full of cracks performance.And have other good comprehensive mechanical performances.
Another object of the present invention is to provide a kind of manufacture craft of making above-mentioned chloroprene rubber polymer blend.
The objective of the invention is to be achieved through the following technical solutions.With chloroprene rubber and the blend of blend glue, utilize the kindliness of blend xanthan molecule chain and the adhesive property that easy crystallinity is improved blend and cord, improve the flex cracking resistance performance of its cross-linked rubber simultaneously.
Main raw material composition and quality proportioning included in the inventive method are: 100～60 parts of chloroprene rubbers, 0～40 part of rubber accelerator, 5～50 parts in blend glue, 5～100 parts of carbon black or white carbon blacks, conventional chloroprene rubber kind and consumption that other Synergist S-421 95s such as promotor, vulcanizing agent, promoting agent, anti-aging agent, tenderizer etc. cooperate according to chloroprene rubber.
That chloroprene rubber of the present invention comprises sulphur modified chloroprene rubber, mercaptan modified chloroprene rubber and the xanthan modified chloroprene rubber of all size and these rubber different ratioss and use rubber.
That rubber accelerator of the present invention comprises natural rubber, polyisoprene rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR), isoprene-isobutylene rubber, epichlorohydrin rubber, viton, silicon rubber, thiorubber, urethanes, regenerated rubber of various kinds, specification etc. and these rubber different ratioss and use rubber.
Blend glue of the present invention comprises the whole bag of tricks synthetic using trans-polyisoprene and natural gutta-percha, gutta-percha and Ba Lata glue etc.
Carbon black of the present invention comprises N100 series, N200 series, N300 series, N400 series, N500 series, N600 series, N700 series, the carbon black of various kinds such as N800 series, N900 series, Sweet natural gas semi-reinforcing hydrocarbon black, Sweet natural gas thermally oxidized black and mixed gas carbon black and specification; White carbon black comprises the precipitated silica or the thermal silica of various specific surface areas, particle diameter; And the carbon black of various kinds and specification and various kinds and the specification white carbon black and usefulness.
Vulcanizing agent and consumption thereof used among the present invention are not particularly limited, the vulcanizing agent and the consumption thereof of practicality in the time of can adopting common chloroprene rubber to make, but better with metal oxide, as zinc oxide, magnesium oxide, plumbous oxide, tri-lead tetroxide etc., these oxide compounds can two or more also be used.By chloroprene rubber 100 weight parts, consumption 3-15 part of vulcanizing agent is better.In addition, it is used in combination with following vulcanization accelerator, can more effectively vulcanizes.
Above-mentioned vulcanization accelerator comprises Thiourea, guanidine class, thiurams or thiazoles, but better with the Thiourea vulcanization accelerator.These vulcanization accelerators can two or more also be used.By chloroprene rubber 100 weight parts, it is better that this class is vulcanized promoted consumption 0.5-5 part.
If necessary, various auxiliary agents can be added, as tenderizer, processing aid, anti-aging agent, lubricant, filler etc. in chloroprene rubber polymer blend of the present invention.
Chloroprene rubber polymer blend of the present invention has fabulous processing characteristics, can carry out mixing with general rubber preparing device by the mode identical with common chloroprene rubber, vulcanize with ordinary process, but the pretreatment technology of chloroprene rubber polymer blend of the present invention and condition are different.Specifically, manufacture craft comprises the steps and processing condition:
The first step in general rubber preparing device, is plasticated using trans-polyisoprene 2～30 minutes in 60～100 ℃ of temperature ranges, again with the chloroprene rubber blend.
Second step prepared rubber unvulcanizate by common refining gluing method.
The 3rd step vulcanized the rubber unvulcanizate age overnight 1～60 minute in 100～200 ℃ according to common rubber vulcanization process.
Chloroprene rubber polymer blend of the present invention can be used to prepare various cross-linked rubber goods, especially has broad application prospects in rubber item industries such as sebific duct, adhesive tape, dampings.
(4) embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.Certainly, the present invention never is subjected to the restriction of these specific embodiments.
Embodiment 1 sulphur modified chloroprene rubber and using trans-polyisoprene blend
According to the prescription batching of table 1, again by following prepared:
1, with using trans-polyisoprene in general rubber preparing device, in 100 ℃ of temperature ranges, plasticated 2 minutes, press the blend of table 1 proportioning with chloroprene rubber again;
2, calendering process prepares rubber unvulcanizate routinely;
3,, vulcanized 30 minutes in 150 ℃ according to common rubber vulcanization process with behind the rubber unvulcanizate age overnight.
The physical and mechanical properties of gained cross-linked rubber is listed in table 2.As seen from the table, (2#, 3# are chloroprene rubber and using trans-polyisoprene blend after sulphur modified chloroprene rubber and the using trans-polyisoprene blend, 1# is conventional chloroprene rubber), the traditional performance of cross-linked rubber changes little, and bond properties and flexible resistance obviously improve.Table 1 basic recipe
Table 2 cured properties
Embodiment 2 sulphur modified chloroprene rubber/natural rubbers/natural gutta-percha blend
According to the prescription batching of table 3, again by following prepared:
1, with natural gutta-percha in general rubber preparing device, in 60 ℃ of temperature ranges, plasticated 30 minutes, press the blend of table 1 proportioning with chloroprene rubber again;
2, calendering process prepares rubber unvulcanizate routinely;
3,, vulcanized 1 minute in 150 ℃ according to common rubber vulcanization process with behind the rubber unvulcanizate age overnight.
The physical and mechanical properties of gained cross-linked rubber is listed in table 4.As seen from the table, after sulphur modified chloroprene rubber/natural rubber and the using trans-polyisoprene blend, the traditional performance of cross-linked rubber, temperature limit of brittleness, heat aging performance change little, and bond properties and flexible resistance obviously improve.
Table 3 basic recipe
Table 4 cured properties
Embodiment 3 mercaptan modified chloroprene rubbers and gutta-percha blend
According to the prescription batching of table 5, again by following prepared:
1, with gutta-percha in general rubber preparing device, in 60～100 ℃ of temperature ranges, plasticated 2～30 minutes, press the blend of table 1 proportioning with chloroprene rubber again;
2, calendering process prepares rubber unvulcanizate routinely;
3,, vulcanized 100 minutes in 150 ℃ according to common rubber vulcanization process with behind the rubber unvulcanizate age overnight.
The physical and mechanical properties of gained cross-linked rubber is listed in table 6.As seen from the table, after mercaptan modified chloroprene rubber and the using trans-polyisoprene blend, the traditional performance of cross-linked rubber changes little, and bond properties and flexible resistance obviously improve.
Table 5 basic recipe
Table 6 cured properties
By above-mentioned enforcement and Comparative Examples as can be known, chloroprene rubber polymer blend of the present invention and framework material have excellent adhesion performance, its sulfide has excellent flexible resistance be full of cracks performance, and has other good comprehensive mechanical performances, can extensively adopt in rubber industry.
Claims (8)
1. chloroprene rubber polymer blend, it is characterized in that: included main raw material composition and the quality proportioning of blend glue is in the described blend: 100～60 parts of chloroprene rubbers, 0～40 part of rubber accelerator, 5～50 parts in blend glue, 5～100 parts of carbon black or white carbon blacks, other Synergist S-421 95s comprise conventional variety and the consumption that promotor, vulcanizing agent, promoting agent, anti-aging agent, tenderizer cooperate according to chloroprene rubber.
2. according to the described chloroprene rubber polymer blend of claim 1, it is characterized in that: that described chloroprene rubber comprises sulphur modified chloroprene rubber, mercaptan modified chloroprene rubber and the xanthan modified chloroprene rubber of various kinds and specification and these rubber different ratioss and use rubber.
3. according to the described chloroprene rubber polymer blend of claim 1, it is characterized in that: described rubber accelerator comprise various kinds, specification natural rubber, polyisoprene rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR), isoprene-isobutylene rubber, epichlorohydrin rubber, viton, silicon rubber, thiorubber, urethanes, regenerated rubber and these rubber different ratioss and use rubber.
4. according to the described chloroprene rubber polymer blend of claim 1, it is characterized in that: described blend glue comprises the whole bag of tricks synthetic using trans-polyisoprene and natural gutta-percha, gutta-percha and Ba Lata glue.
5. according to the described chloroprene rubber polymer blend of claim 1, it is characterized in that: carbon black comprises N100 series, N200 series, N300 series, N400 series, N500 series, N600 series, N700 series, the carbon black of N800 series, N900 series, Sweet natural gas semi-reinforcing hydrocarbon black, Sweet natural gas thermally oxidized black and various kinds of mixed gas carbon black and specification.
6. according to claim 1 or 5 described chloroprene rubber polymer blends, it is characterized in that: white carbon black comprises the precipitated silica or the thermal silica of various specific surface areas, particle diameter.
7. according to the described chloroprene rubber polymer blend of claim 1, it is characterized in that: carbon black or white carbon black comprise that the sooty of various kinds and specification is single or also use, the white carbon black of various kinds and specification single or and usefulness, and the white carbon black of the carbon black of various kind and specification and various kind and specification and usefulness.
8. chloroprene rubber polymer blend preparation method as claimed in claim 1, it is characterized in that: described chloroprene rubber polymer blend prepares according to following method:
The manufacture craft of described blend comprises the steps and processing condition:
The first step in general rubber preparing device, is plasticated blend glue 2～30 minutes in 60～100 ℃ of temperature ranges, again with the chloroprene rubber blend.
Second step prepared rubber unvulcanizate by common refining gluing method.
The 3rd step vulcanized the rubber unvulcanizate age overnight 1～60 minute in 100～200 ℃ according to common rubber vulcanization process.
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