CN104045664A - Benzothiazole thiol silane prepared from 2-thiol benzothiazole and chloropropyl triethoxysilane - Google Patents

Benzothiazole thiol silane prepared from 2-thiol benzothiazole and chloropropyl triethoxysilane Download PDF

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CN104045664A
CN104045664A CN201410189415.8A CN201410189415A CN104045664A CN 104045664 A CN104045664 A CN 104045664A CN 201410189415 A CN201410189415 A CN 201410189415A CN 104045664 A CN104045664 A CN 104045664A
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benzothiazole
silane
rubber
formula
thiol
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CN104045664B (en
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姚翔
彭华龙
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JIANGSU QIXIANG NEW MATERIAL CO Ltd
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JIANGSU QIXIANG NEW MATERIAL CO Ltd
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Abstract

The invention discloses benzothiazole thiol silane prepared from 2-thiol benzothiazole and chloropropyl triethoxysilane, wherein the benzothiazole thiol silane has a molecular structure formula shown in the specification. A preparation method of the benzothiazole thiol silane comprises the following steps: step C: weighing the 2-thiol benzothiazole and isopropanol, putting in a reaction kettle, adding sodium hydroxide, stirring evenly, adding he chloropropyl triethoxysilane into the solution for reaction for 12 hours, filtering, washing and distilling under vacuum the reaction product to obtain semi-finished silane; and step D: adding the semi-finished silane and polyether into n/isopropyl titanate for reaction for 3 hours to obtain a red brown liquid. The beneficial effects are that: the content of alcohol released by the benzothiazole thiol silane is low, the benzothiazole thiol silane can improve the reinforcing effect and the mechanical properties and dynamic mechanical properties of vulcanized rubber, and can improve the rolling resistance and wet skid resistance of tread rubber, the scorch time is long, the vulcanization speed is fast, and the vulcanization performance of a rubber material can be greatly improved.

Description

Benzothiazole hydrosulphonyl silane prepared by 2-benzothiazolyl mercaptan and chloropropyl triethoxysilane
This case is divisional application, and the denomination of invention of original application is: a kind of low-volatility benzothiazolyl mercaptosilanes and preparation method thereof, the applying date of original application is: July 20 in 2011, the application number of original application is: 201110203136.9
Technical field
The present invention relates to rubber ingredients technical field, benzothiazole hydrosulphonyl silane and preparation method that particularly prepared by a kind of 2-benzothiazolyl mercaptan and chloropropyl triethoxysilane.
Background technology
In rubber compounding, be widely used various fillers as carbon black, white carbon black, potter's clay, calcium carbonate, talcum powder, halloysite, magnesium hydroxide, aluminium hydroxide etc., wherein carbon black, white carbon black etc. belong to reinforcement filler, and potter's clay, calcium carbonate, talcum powder, halloysite, magnesium hydroxide, aluminium hydroxide etc. belong to non-reinforcement filler.Research shows, the interaction of reinforcement filler and rubber cross network can improve the reinforcing effect of filler effectively.Even if be non-reinforcement filler, make to form strong combination between itself and rubber network through suitable surface modification, also can produce the strengthening action that degree is different.Conventionally on market, can play good reinforcing effect for filler filled rubber with silane as two [3-(three ethoxies are silica-based) propyl group] tetrasulfide Si69, two [3-(three ethoxies are silica-based) propyl group] disulphide Si75 etc.
But traditional rubber is short with silane Si69 and its time of scorch of Si75, and function singleness, is difficult to meet the requirement of rubber industry.Publication number is the benzothiazole hydrosulphonyl silane that the Chinese patent of CN101445620A discloses following general formula:
In formula, left side is benzothiazole group, R 1for methylene radical, ethylidene or propylidene, R 2for methyl or ethyl, R 3for methyl, ethyl, methoxy or ethoxy.
This multifunctional assistant collection plasticising, dispersion, promotion, reinforcement etc. are multi-functional, but owing to thering are three alkoxy substituents on this auxiliary agents of silicon atom, and filler mixing period between or can discharge afterwards a large amount of alcohol, polluted the environment of job shop, workman's health is had to infringement to a certain degree; Wherein, normally used Trimethoxy silane and triethoxyl silane can discharge considerable corresponding alcohol-methyl alcohol and ethanol.
In addition, the silane that the silane that the silane of methoxy substitution and oxyethyl group replace replaces than corresponding long-chain alkoxy base has higher reactive behavior, and can be more quickly and filler phase reaction, therefore, can not be because of its volatility completely except de-methoxy and oxyethyl group.
Summary of the invention
The object of the invention is to overcome the shortcoming of prior art, the benzothiazole hydrosulphonyl silane and the preparation method that provide a kind of 2-benzothiazolyl mercaptan and chloropropyl triethoxysilane to prepare.
In order to realize foregoing invention object, the invention provides benzothiazole hydrosulphonyl silane prepared by a kind of 2-benzothiazolyl mercaptan and chloropropyl triethoxysilane, wherein, silane comprises following molecular structural formula:
In order better to realize foregoing invention object, the present invention provides again the preparation method of above-mentioned benzothiazole hydrosulphonyl silane, and wherein, described preparation method comprises the following steps:
Step c: take 0.2mol (33.4g) 2-benzothiazolyl mercaptan and 600g ether, be placed in there-necked flask, add the sodium hydroxide of 0.3mol (12g), stir, again 0.25mol (44.86g) chloroethyl ethyl diethoxy silane is joined in above-mentioned solution, then under nitrogen protection, under room temperature condition, react 3 hours, reaction product after filtration, washing, underpressure distillation, obtain 3-benzothiazolethio-1-propyl group ethyl dimethoxy silane (being work in-process silane);
Steps d: by 76.4g3-benzothiazolethio-1-propyl group ethyl dimethoxy silane and 0.4mol (139.6) polyethers HO-(C 2h 4-O) 5-C 8h 17, add the positive isopropyl ester of 1g metatitanic acid, at 175 DEG C, react 4 hours, obtain brown liquid, yield 82.4%.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
(1) one end of benzothiazole hydrosulphonyl silane molecule of the present invention is only with one or two alkoxyl group, energy and white carbon black in sulfidation, clay, calcium carbonate, halloysite, the surface hydroxyl of the fillers such as magnesium hydroxide is easy to occur alcoholysis reaction, and the amount of its alcohol discharging is very low, the benzothiazole sulfenyl of its other end has the effect the while and rubber molecule chain reaction that promote sulfuration, make filler produce firmly and be combined with rubber molecular chain, improve reinforcing effect, greatly improve mechanical property and the dynamic properties of cross-linked rubber, improve rolling resistance and the anti-slippery of tread rubber.
(2) in benzothiazole hydrosulphonyl silane molecule of the present invention due to the existence of polyethers long-chain, the shielding effect of polyethers long-chain to sulfydryl under compounding rubber processing temperature, be difficult for causing rubber incipient scorch, its time of scorch is long, and benzothiazole has promoter action under curing temperature, vulcanization rate is fast, can greatly improve the curability of sizing material.
Therefore, benzothiazole hydrosulphonyl silane of the present invention is to be applied to natural rubber and various synthetic rubber formula, promotes sulfuration, improves the several functions such as filler reinforcement effect, the dynamic properties that improves cross-linked rubber, anti-incipient scorch, plasticising and have the rubber ingredients of low volatility as having; While being applied to meridian tyre, can obtain the tyre surface of high wet-sliding resistant, low-rolling-resistance; By being adsorbed on the organic or electrodeless carrier of inertia, or carry out pre-reaction with organic or inorganic carrier, can be applied in different fields such as preparing products formed, pneumatic tyre, tire tread, flexible pipe, pulley belt, sealing member and damper element.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below will according to specific embodiment, the present invention is described in further detail.
Embodiment 1
A kind of low-volatility benzothiazolyl mercaptosilanes, wherein, the molecular structural formula of silane is:
The preparation method of above-mentioned silane is:
Step a: take 0.1mol (28.86g) γ-chloropropyl triethoxysilane and 0.2mol (54.8g) polyethers HO-(C 2h 4-O) 2-C 12h 25be placed in there-necked flask, add 0.5g zinc naphthenate, at 70 DEG C, react 2 hours, vacuum removal ethanol, after one hour, obtains polyether-modified chloropropyl silane (being work in-process silane);
Step b: take 0.1mol (16.7g) 2-benzothiazolyl mercaptan and 250g toluene, be placed in flask with three necks,round bottom, add the sodium methylate of 0.1mol (5.4g), stir, mixed solution is heated to 120 DEG C, and from a side mouth of there-necked flask with 0.1m 3the speed of/h passes into nitrogen, more polyether-modified 75.3g chloropropyl silane is joined in above-mentioned solution, then under nitrogen protection 120 DEG C reaction 10 hours; by the product obtaining, filter washing; low boiler cut is removed in underpressure distillation, obtains brown liquid, yield 90.1%.
The product called after Si-748 that obtains.Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show the target product that the product of synthesized is above-mentioned molecular structural formula.
The basic recipe of rubber/white carbon black composite material of preparing with product S i-748 is in table 1; Corresponding rubber unvulcanizate curing parameter is in table 2; The mechanical property of the rubber/white carbon black composite material obtaining with benzothiazole hydrosulphonyl silane Si-748 is in table 3; The dynamic properties of preparing rubber/white carbon black composite material cross-linked rubber with Si-748 is in table 4.
Table 1 is prepared five kinds of different experimental formulas of rubber/white carbon black composite material with Si-748
Numbering 1 2 3 4 5
SBR 60 60 60 60 60
NR 40 40 40 40 40
Silica 40 40 40 40 40
ZnO 5.0 5.0 5.0 5.0 5.0
St 2.0 2.0 2.0 2.0 2.0
CZ 1.8 1.8 1.8 1.8 1.8
S 1.6 1.6 1.6 1.6 1.6
Si-748 0 2 4 6 8
Table 2 is prepared the curing parameter of rubber/white carbon black composite material rubber unvulcanizate with Si-748
System Formula 1 Formula 2 Formula 3 Formula 4 Formula 5
t c10(min) 5.3 6.2 6.5 7.1 6.8
t c90(min) 20.0 13.0 11.3 10.0 8.9
t c90-t c10(min) 14.7 6.8 4.8 2.9 2.1
As seen from Table 2, benzothiazole hydrosulphonyl silane Si-748 is joined in matrix material rubber unvulcanizate, along with the increase of addition, obviously reduced sulfurizing time t c90, sizing material time of scorch lengthens, and has the good characteristic that inductive phase is long, vulcanization rate is fast.
Table 3 is prepared the mechanical property of rubber/white carbon black composite material with Si-748
System Formula 1 Formula 2 Formula 3 Formula 4 Formula 5
300% stress at definite elongation (MPa) 3.97 4.50 4.59 5.10 5.40
500% stress at definite elongation (MPa) 6.49 8.54 8.97 10.69 10.61
Tensile strength (MPa) 18.60 22.71 23.35 24.41 25.42
Tear strength (KN/m) 57.46 53.55 58.60 59.51 65.67
Table 3 is mechanical properties of rubber/white carbon black composite material of preparing with benzothiazole hydrosulphonyl silane Si-748, can find out, the mechanical properties such as the stress at definite elongation of the matrix material of preparing with benzothiazole hydrosulphonyl silane Si-748, tensile strength, tear strength significantly improve, and are significantly higher than the cross-linked rubber that does not add Si-748.
Table 4 is prepared the dynamic properties of rubber/white carbon black composite material cross-linked rubber with Si-748
System Formula 1 Formula 2 Formula 3 Formula 4 Formula 5
Tanδat0℃ 0.331 0.425 0.472 0.514 0.564
Tanδat60℃ 0.224 0.185 0.164 0.150 0.141
As known from Table 4: the interpolation of Si-748 can improve rubber/white carbon black composite material of preparing anti-slippery as tread rubber greatly, reduces rolling resistance.
Embodiment 2
A kind of low-volatility benzothiazolyl mercaptosilanes, wherein, the molecular structural formula of silane is:
The preparation method of above-mentioned silane is:
Step a: take 0.1mol (17.1g) γ-chloromethyl Trimethoxy silane and 0.2mol (81.2g) polyethers HO-(C 2h 4-O) 5-C 12h 25be placed in there-necked flask, add 0.5g sodium ethylate, at 165 DEG C, react 7 hours, vacuum removal methyl alcohol, after one hour, obtains polyether-modified chloropropyl silane (being work in-process silane);
Step b: take 0.1mol (16.7g) 2-benzothiazolyl mercaptan and 250g toluene, be placed in flask with three necks,round bottom, add the sodium methylate of 0.1mol (5.4g); stir; mixed solution is heated to 120 DEG C, more above-mentioned 81.4g polyether-modified chloropropyl silane is joined in above-mentioned solution, then under nitrogen protection 50 DEG C reaction 24 hours; by the product obtaining; filter, washing, low boiler cut is removed in underpressure distillation; obtain red-brown aqueous, yield 96.4%.
The product called after Si-749 that obtains.Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show the target product that the product of synthesized is above-mentioned molecular structural formula.
The basic recipe of rubber/white carbon black composite material of preparing with product S i-749 is in table 5; Corresponding rubber unvulcanizate curing parameter is in table 6; The mechanical property of the rubber/white carbon black composite material obtaining with benzothiazole hydrosulphonyl silane Si-749 is in table 7; The dynamic properties of preparing rubber/white carbon black composite material cross-linked rubber with Si-749 is in table 8.
Table 5 is prepared five kinds of different experimental formulas of rubber/white carbon black composite material with Si-749
Numbering 6 7 8 9 10
SBR 60 60 60 60 60
NR 40 40 40 40 40
Silica 40 40 40 40 40
ZnO 5.0 5.0 5.0 5.0 5.0
St 2.0 2.0 2.0 2.0 2.0
CZ 1.8 1.8 1.8 1.8 1.8
S 1.6 1.6 1.6 1.6 1.6
Si-749 0 2 4 6 8
Table 6 is prepared the curing parameter of rubber/white carbon black composite material rubber unvulcanizate with Si-749
System Formula 6 Formula 7 Formula 8 Formula 9 Formula 10
t c10(min) 5.3 5.9 6.1 6.5 6.3
t c90(min) 20.0 12.4 11.0 9.8 8.5
t c90-t c10(min) 14.7 6.5 4.9 3.3 2.2
As seen from Table 6, benzothiazole hydrosulphonyl silane Si-749 is joined in matrix material rubber unvulcanizate, along with the increase of addition, obviously reduced sulfurizing time t c90, sizing material time of scorch lengthens, and has the good characteristic that inductive phase is long, vulcanization rate is fast.
Table 7 is prepared the mechanical property of rubber/white carbon black composite material with Si-749
System Formula 6 Formula 7 Formula 8 Formula 9 Formula 10
300% stress at definite elongation (MPa) 3.97 4.30 4.50 4.98 5.23
500% stress at definite elongation (MPa) 6.49 8.32 8.34 11.10 11.02
Tensile strength (MPa) 18.60 22.52 23.27 24.14 26.01
Tear strength (KN/m) 57.46 54.12 60.54 60.45 62.57
Table 7 is mechanical properties of rubber/white carbon black composite material of preparing with benzothiazole hydrosulphonyl silane Si-749, can find out, the mechanical properties such as the stress at definite elongation of the matrix material of preparing with benzothiazole hydrosulphonyl silane Si-749, tensile strength, tear strength significantly improve, and are significantly higher than the cross-linked rubber that does not add Si-749.
Table 8 is prepared the dynamic properties of rubber/white carbon black composite material cross-linked rubber with Si-749
System Formula 6 Formula 7 Formula 8 Formula 9 Formula 10
Tanδat0℃ 0.331 0.434 0.474 0.498 0.521
Tanδat60℃ 0.224 0.180 0.171 0.164 0.152
As known from Table 8: the interpolation of Si-749 can improve rubber/white carbon black composite material of preparing anti-slippery as tread rubber greatly, reduces rolling resistance.
Embodiment 3
A kind of low-volatility benzothiazolyl mercaptosilanes, wherein, the molecular structural formula of silane is:
The preparation method of above-mentioned silane is:
Step a: take 5mol (862.5) γ-r-chloropropyl trimethoxyl silane and 10mol (508g) polyethers HO-(C 2h 4-O) 7-C 13h 27be placed in reactor, add 50g aluminic acid butyl ester, at 180 DEG C, under 0.09Mpa vacuum, react 10 hours, obtain polyether-modified chloropropyl silane (being work in-process silane);
Step b: take 5mol (835g) 2-benzothiazolyl mercaptan and 10kg acetone, be placed in stainless steel vessel, add the sodium hydroxide of 7.5mol (300g); be heated to 80 DEG C; stir, and pass into nitrogen, then will join in above-mentioned solution; then under nitrogen protection 80 DEG C reaction 6 hours; by the product obtaining, sediment to be filtered, low boiler cut is removed in underpressure distillation; obtain red-brown aqueous, yield 81.2%.
The product called after Si-750 that obtains.Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show the target product that the product of synthesized is above-mentioned molecular structural formula.
The basic recipe of rubber/white carbon black composite material of preparing with product S i-750 is in table 9; Corresponding rubber unvulcanizate curing parameter is in table 10; The mechanical property of the rubber/white carbon black composite material obtaining with benzothiazole hydrosulphonyl silane Si-750 is in table 11; The dynamic properties of preparing rubber/white carbon black composite material cross-linked rubber with Si-750 is in table 12.
Table 9 is prepared five kinds of different experimental formulas of rubber/white carbon black composite material with Si-750
Numbering 11 12 13 14 15
SBR 60 60 60 60 60
NR 40 40 40 40 40
Silica 40 40 40 40 40
ZnO 5.0 5.0 5.0 5.0 5.0
St 2.0 2.0 2.0 2.0 2.0
CZ 1.8 1.8 1.8 1.8 1.8
S 1.6 1.6 1.6 1.6 1.6
Si-750 0 2 4 6 8
Table 10 is prepared the curing parameter of rubber/white carbon black composite material rubber unvulcanizate with Si-750
System Formula 11 Formula 12 Formula 13 Formula 14 Formula 15
t c10(min) 5.3 6.1 6.2 6.7 6.9
t c90(min) 20.0 12.4 11.7 10.4 9.2
t c90-t c10(min) 14.7 6.3 5.5 3.7 2.3
As seen from Table 10, benzothiazole hydrosulphonyl silane Si-750 is joined in matrix material rubber unvulcanizate, along with the increase of addition, obviously reduced sulfurizing time t c90, sizing material time of scorch lengthens, and has the good characteristic that inductive phase is long, vulcanization rate is fast.
Table 11 is prepared the mechanical property of rubber/white carbon black composite material with Si-750
System Formula 11 Formula 12 Formula 13 Formula 14 Formula 15
300% stress at definite elongation (MPa) 3.97 4.30 4.67 4.78 5.10
500% stress at definite elongation (MPa) 6.49 8.12 8.75 9.84 10.15
Tensile strength (MPa) 18.60 22.21 22.74 23.45 24.18
Tear strength (KN/m) 57.46 54.55 57.20 59.28 60.78
Table 11 is mechanical properties of rubber/white carbon black composite material of preparing with benzothiazole hydrosulphonyl silane Si-750, can find out, the mechanical properties such as the stress at definite elongation of the matrix material of preparing with benzothiazole hydrosulphonyl silane Si-750, tensile strength, tear strength significantly improve, and are significantly higher than the cross-linked rubber that does not add Si-750.
Table 12 is prepared the dynamic properties of rubber/white carbon black composite material cross-linked rubber with Si-750
System Formula 11 Formula 12 Formula 13 Formula 14 Formula 15
Tanδat0℃ 0.331 0.378 0.399 0.437 0.512
Tanδat60℃ 0.224 0.180 0.171 0.168 0.157
As known from Table 12: the interpolation of Si-750 can improve rubber/white carbon black composite material of preparing anti-slippery as tread rubber greatly, reduces rolling resistance.
Embodiment 4
A kind of low-volatility benzothiazolyl mercaptosilanes, wherein, the molecular structural formula of silane is:
The preparation method of above-mentioned silane is:
Step a: take 0.25mol (49.13g) chloropropyl ethyl dimethoxy silane and 0.5mol (181.5) polyethers-O-(C 2h 4-O) 5-C 9h 19, add 20g titanium isopropylate, at 45 DEG C, under 0.08Mpa vacuum, react 1 hour, obtain polyether-modified chloropropyl silane (being work in-process silane);
Step b: take 0.2mol (33.4g) 2-benzothiazolyl mercaptan and 500g sherwood oil; be placed in there-necked flask, add the sodium hydroxide of 0.3mol (12g), stir; and pass into nitrogen; again above-mentioned 210g polyether-modified chloropropyl silane is joined in above-mentioned solution, then under nitrogen protection, under room temperature condition, react 24 hours, by the product obtaining; sediment is filtered; low boiler cut is removed in underpressure distillation, obtains red-brown aqueous, yield 75.4%.
The product called after Si-751 that obtains.Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show the target product that the product of synthesized is above-mentioned molecular structural formula.
The basic recipe of rubber/white carbon black composite material of preparing with product S i-751 is in table 13; Corresponding rubber unvulcanizate curing parameter is in table 14; The mechanical property of the rubber/white carbon black composite material obtaining with benzothiazole hydrosulphonyl silane Si-751 is in table 15; The dynamic properties of preparing rubber/white carbon black composite material cross-linked rubber with Si-751 is in table 16.
Table 13 is prepared five kinds of different experimental formulas of rubber/white carbon black composite material with Si-751
Numbering 16 17 18 19 20
SBR 60 60 60 60 60
NR 40 40 40 40 40
Silica 40 40 40 40 40
ZnO 5.0 5.0 5.0 5.0 5.0
St 2.0 2.0 2.0 2.0 2.0
CZ 1.8 1.8 1.8 1.8 1.8
S 1.6 1.6 1.6 1.6 1.6
Si-751 0 2 4 6 8
Table 14 is prepared the curing parameter of rubber/white carbon black composite material rubber unvulcanizate with Si-751
System Formula 16 Formula 17 Formula 18 Formula 19 Formula 20
t c10(min) 5.3 5.7 6.1 6.4 6.6
t c90(min) 20.0 11.8 10.4 9.2 7.8
t c90-t c10(min) 14.7 6.1 4.3 2.8 1.2
From table 14, benzothiazole hydrosulphonyl silane Si-751 is joined in matrix material rubber unvulcanizate, along with the increase of addition, obviously reduce sulfurizing time t c90, sizing material time of scorch lengthens, and has the good characteristic that inductive phase is long, vulcanization rate is fast.
Table 15 is prepared the mechanical property of rubber/white carbon black composite material with Si-751
System Formula 16 Formula 17 Formula 18 Formula 19 Formula 20
300% stress at definite elongation (MPa) 3.97 4.84 4.89 4.95 5.10
500% stress at definite elongation (MPa) 6.49 8.52 9.17 10.24 10.61
Tensile strength (MPa) 18.60 19.89 21.48 23.41 24.12
Tear strength (KN/m) 57.46 55.54 57.10 59.55 60.74
Table 15 is mechanical properties of rubber/white carbon black composite material of preparing with benzothiazole hydrosulphonyl silane Si-751, can find out, the mechanical properties such as the stress at definite elongation of the matrix material of preparing with benzothiazole hydrosulphonyl silane Si-751, tensile strength, tear strength significantly improve, and are significantly higher than the cross-linked rubber that does not add Si-751.
Table 16 is prepared the dynamic properties of rubber/white carbon black composite material cross-linked rubber with Si-751
System Formula 16 Formula 17 Formula 18 Formula 19 Formula 20
Tanδat0℃ 0.331 0.421 0.424 0.458 0.505
Tanδat60℃ 0.224 0.180 0.161 0.158 0.147
As known from Table 16: the interpolation of Si-751 can improve rubber/white carbon black composite material of preparing anti-slippery as tread rubber greatly, reduces rolling resistance.
Embodiment 5
A benzothiazole hydrosulphonyl silane prepared by 2-benzothiazolyl mercaptan and chloroethyl ethyl diethoxy silane, wherein, the molecular structural formula of silane:
The preparation method of above-mentioned silane is:
Step c: take 0.2mol (33.4g) 2-benzothiazolyl mercaptan and 600g ether, be placed in there-necked flask, add the sodium hydroxide of 0.3mol (12g), stir, again 0.25mol (44.86g) chloroethyl ethyl diethoxy silane is joined in above-mentioned solution, then under nitrogen protection, under room temperature condition, react 3 hours, reaction product after filtration, washing, underpressure distillation, obtain 3-benzothiazolethio-1-propyl group ethyl dimethoxy silane (being work in-process silane);
Steps d: by 76.4g3-benzothiazolethio-1-propyl group ethyl dimethoxy silane and 0.4mol (139.6) polyethers HO-(C 2h 4-O) 5-C 8h 17, add the positive isopropyl ester of 1g metatitanic acid, at 175 DEG C, react 4 hours, obtain brown liquid, yield 82.4%.
The product called after Si-752 that obtains; Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show the target product that the product of synthesized is above-mentioned molecular structural formula.
The basic recipe of rubber/white carbon black composite material of preparing with product S i-752 is in table 17; Corresponding rubber unvulcanizate curing parameter is in table 18; The mechanical property of the rubber/white carbon black composite material obtaining with benzothiazole hydrosulphonyl silane Si-752 is in table 19; The dynamic properties of preparing rubber/white carbon black composite material cross-linked rubber with Si-752 is in table 20.
Table 17 is prepared five kinds of different experimental formulas of rubber/white carbon black composite material with Si-752
Numbering 21 22 23 24 25
SBR 60 60 60 60 60
NR 40 40 40 40 40
Silica 40 40 40 40 40
ZnO 5.0 5.0 5.0 5.0 5.0
St 2.0 2.0 2.0 2.0 2.0
CZ 1.8 1.8 1.8 1.8 1.8
S 1.6 1.6 1.6 1.6 1.6
Si-752 0 2 4 6 8
Table 18 is prepared the curing parameter of rubber/white carbon black composite material rubber unvulcanizate with Si-752
System Formula 21 Formula 22 Formula 23 Formula 24 Formula 25
t c10(min) 5.3 5.5 6.5 7.8 6.9
t c90(min) 20.0 13.8 12.3 10.5 9.1
t c90-t c10(min) 14.7 7.3 5.8 2.7 2.2
From table 18, benzothiazole hydrosulphonyl silane Si-752 is joined in matrix material rubber unvulcanizate, along with the increase of addition, obviously reduce sulfurizing time t c90, sizing material time of scorch lengthens, and has the good characteristic that inductive phase is long, vulcanization rate is fast.
Table 19 is prepared the mechanical property of rubber/white carbon black composite material with Si-752
System Formula 21 Formula 22 Formula 23 Formula 24 Formula 25
300% stress at definite elongation (MPa) 3.97 4.00 4.19 5.12 5.43
500% stress at definite elongation (MPa) 6.49 8.58 8.67 9.49 10.50
Tensile strength (MPa) 18.60 23.64 23.89 24.50 25.89
Tear strength (KN/m) 57.46 51.24 57.60 60.11 61.77
Table 19 is mechanical properties of rubber/white carbon black composite material of preparing with benzothiazole hydrosulphonyl silane Si-752, can find out, the mechanical properties such as the stress at definite elongation of the matrix material of preparing with benzothiazole hydrosulphonyl silane Si-752, tensile strength, tear strength significantly improve, and are significantly higher than the cross-linked rubber that does not add Si-752.
Table 20 is prepared the dynamic properties of rubber/white carbon black composite material cross-linked rubber with Si-752
System Formula 21 Formula 22 Formula 23 Formula 24 Formula 25
Tanδat0℃ 0.331 0.412 0.424 0.456 0.494
Tanδat60℃ 0.224 0.195 0.178 0.164 0.160
As known from Table 20: the interpolation of Si-752 can improve rubber/white carbon black composite material of preparing anti-slippery as tread rubber greatly, reduces rolling resistance.
Embodiment 6
A benzothiazole hydrosulphonyl silane prepared by 2-benzothiazolyl mercaptan and chloropropyl triethoxysilane, wherein, the molecular structural formula of silane:
The preparation method of above-mentioned silane is:
Step c: take 20mol (3340g) 2-benzothiazolyl mercaptan and 3kg Virahol, be placed in reactor, add the sodium hydroxide of 25mol (1000g), stir, again 25mol (4913g) chloropropyl triethoxysilane is joined in above-mentioned solution, then under nitrogen protection, at 80 DEG C, react 12 hours, reaction product after filtration, washing, underpressure distillation, obtain 3-benzothiazolethio-1-propyl-triethoxysilicane;
Steps d: by 7328g3-benzothiazolethio-1-propyl-triethoxysilicane and 20mol (8160g) polyethers HO-(C 2h 4-O) 6-C 9h 19, add the positive isopropyl ester of 100g metatitanic acid, at 200 DEG C, react 3 hours, obtain brown liquid.Yield 71.6%.
The product called after Si-753 that obtains; Infrared spectra (FTIR), gas chromatography-mass spectrum (GC-MS), ultimate analysis and nucleus magnetic resonance (NMR) result show the target product that the product of synthesized is above-mentioned molecular structural formula.
The basic recipe of rubber/white carbon black composite material of preparing with product S i-753 is in table 21; Corresponding rubber unvulcanizate curing parameter is in table 22; The mechanical property of the rubber/white carbon black composite material obtaining with benzothiazole hydrosulphonyl silane Si-753 is in table 23; The dynamic properties of preparing rubber/white carbon black composite material cross-linked rubber with Si-753 is in table 24.
Table 21 is prepared five kinds of different experimental formulas of rubber/white carbon black composite material with Si-753
Numbering 26 27 28 29 30
SBR 60 60 60 60 60
NR 40 40 40 40 40
Silica 40 40 40 40 40
ZnO 5.0 5.0 5.0 5.0 5.0
St 2.0 2.0 2.0 2.0 2.0
CZ 1.8 1.8 1.8 1.8 1.8
S 1.6 1.6 1.6 1.6 1.6
Si-753 0 2 4 6 8
Table 22 is prepared the curing parameter of rubber/white carbon black composite material rubber unvulcanizate with Si-753
System Formula 26 Formula 27 Formula 28 Formula 29 Formula 30
t c10(min) 5.3 6.5 6.8 7.7 7.2
t c90(min) 20.0 15.4 13.2 12.1 10.4
t c90-t c10(min) 14.7 8.9 6.4 4.4 3.2
From table 22, benzothiazole hydrosulphonyl silane Si-753 is joined in matrix material rubber unvulcanizate, along with the increase of addition, obviously reduce sulfurizing time t c90, sizing material time of scorch lengthens, and has the good characteristic that inductive phase is long, vulcanization rate is fast.
Table 23 is prepared the mechanical property of rubber/white carbon black composite material with Si-753
System Formula 26 Formula 27 Formula 28 Formula 29 Formula 30
300% stress at definite elongation (MPa) 3.97 4.8 5.47 5.86 6.16
500% stress at definite elongation (MPa) 6.49 9.24 9.88 11.11 12.78
Tensile strength (MPa) 18.60 23.85 25.05 26.41 26.48
Tear strength (KN/m) 57.46 60.42 62.74 61.42 61.33
Table 23 is mechanical properties of rubber/white carbon black composite material of preparing with benzothiazole hydrosulphonyl silane Si-753, can find out, the mechanical properties such as the stress at definite elongation of the matrix material of preparing with benzothiazole hydrosulphonyl silane Si-753, tensile strength, tear strength significantly improve, and are significantly higher than the cross-linked rubber that does not add Si-753.
Table 24 is prepared the dynamic properties of rubber/white carbon black composite material cross-linked rubber with Si-753
System Formula 26 Formula 27 Formula 28 Formula 29 Formula 30
Tanδat0℃ 0.331 0.512 0.574 0.600 0.619
Tanδat60℃ 0.224 0.204 0.195 0.182 0.160
As known from Table 24: the interpolation of Si-753 can improve rubber/white carbon black composite material of preparing anti-slippery as tread rubber greatly, reduces rolling resistance.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (3)

  1. Benzothiazole hydrosulphonyl silane prepared by 1.2-benzothiazolyl mercaptan and chloropropyl triethoxysilane, is characterized in that, described silane comprises following molecular structural formula:
  2. 2. benzothiazole hydrosulphonyl silane as claimed in claim 1, is characterized in that, the preparation method of described benzothiazole hydrosulphonyl silane comprises the following steps:
    Step c: take 20mol (3340g) 2-benzothiazolyl mercaptan and 3kg Virahol, be placed in reactor, add the sodium hydroxide of 25mol (1000g), stir, again 25mol (4913g) chloropropyl triethoxysilane is joined in above-mentioned solution, then under nitrogen protection, at 80 DEG C, react 12 hours, reaction product after filtration, washing, underpressure distillation, obtain 3-benzothiazolethio-1-propyl-triethoxysilicane;
    Steps d: by 7328g3-benzothiazolethio-1-propyl-triethoxysilicane and 20mol (8160g) polyethers HO-(C 2h 4-O) 6-C 9h 19, add the positive isopropyl ester of 100g metatitanic acid, at 200 DEG C, react 3 hours, obtain brown liquid; Yield 71.6%.
  3. 3. the preparation method of benzothiazole hydrosulphonyl silane as claimed in claim 1, is characterized in that, described preparation method comprises the following steps:
    Step c: take 20mol (3340g) 2-benzothiazolyl mercaptan and 3kg Virahol, be placed in reactor, add the sodium hydroxide of 25mol (1000g), stir, again 25mol (4913g) chloropropyl triethoxysilane is joined in above-mentioned solution, then under nitrogen protection, at 80 DEG C, react 12 hours, reaction product after filtration, washing, underpressure distillation, obtain 3-benzothiazolethio-1-propyl-triethoxysilicane;
    Steps d: by 7328g3-benzothiazolethio-1-propyl-triethoxysilicane and 20mol (8160g) polyethers HO-(C 2h 4-O) 6-C 9h 19, add the positive isopropyl ester of 100g metatitanic acid, at 200 DEG C, react 3 hours, obtain brown liquid; Yield 71.6%.
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CN111057269A (en) * 2019-12-18 2020-04-24 怡维怡橡胶研究院有限公司 2-thiothiazolinyl or 2-thioimidazolinyl terminated mercaptosilane coupling agent and synthesis method and application thereof

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