CN104031083B - Siloxy alkyl sulfur ether compound and preparation method thereof - Google Patents
Siloxy alkyl sulfur ether compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the chemical field and in particular relates to a siloxy alkyl sulfur ether compound and a preparation method thereof. One the one hand, the compound can be involved into the sulfuration reaction process of a sizing material after being added into the sizing material and soft alkyl chain is connected to sizing material macromolecule to improve the crosslinking density of the sizing material and improve the anti-sulfuration reversion characteristics of the sizing material, and on the other hand, alkoxy/hydroxyl of end group of the compound can be used for improving consistency of an inorganic filler and rubber macromolecule to improve the processing property and the mechanical property of the sizing material. The invention also provides the preparation method of the compound. Under alkaline conditions, a matter with double bunte salt structure is used as a raw material to be reacted with sulfydryl silane to obtain the siloxy alkyl sulfur ether compound. The method is simple in process, low in energy consumption, low in aftertreatment pollution, high in modified efficiency and good in repeatability, and has great industrial application prospect.
Description
Technical field
The present invention relates to chemical field, particularly to a kind of siloxyalkyl sulfide compound and preparation method thereof.
Background technology
White carbon is a kind of important reinforced filling in rubber industry, and company of French Michelin in 1992 is by a large amount of white carbons
For passenger car tire tread glue, manufacture 1st generation energy-conserving and environment-protective tire, become " green tire ".The rolling resistance of green tire
Ratio conventional tyre reduces 20% about, and has the characteristics that heat is low, anti tear and anti-slippery are good.But due to white carbon grain
Footpath is little, easily fly upward and assemble, and is difficult to disperse, therefore limits the application of white carbon in rubber.
Using silane coupler, white carbon is modified, solves the affinity of white carbon and sizing material, improve sizing material
Processing characteristics.Stress at definite elongation, tensile strength, tearing strength and wearability that sizing material can be made improve simultaneously.But, for sulfuration
For rubber, its thermostability and ageing-resistant performance are the another key factors that impact rubber uses again.In tyre industry,
Traditional method for improving sizing material anti-reversion behaviour is to increase accelerator dosage and reduces sulfur consumption simultaneously, can more have
Effect ground, using the sulfur being added, is allowed to more generate monosulfidic bond and cystine linkage, and the generation reducing polysulfide bond is higher to obtain
Stability, such as using efficient vulcanization system, SE curing system etc..Additionally, some companies are proposed offset-type sulfuration body
System, to make up the loss of cross-bond, keeps the crosslink density of sizing material, such as duralink hts (two hydration hexa-methylenes 1,6- bis- sulfur
Thiosulfuric acid disodium salt), perkalink900 (1,3- lemon acid imide methyl) benzene, sr-534 (acrylic ester compound) etc..
Monsanto Chemicals develop after cure stabilizer duralink hts (two hydrations in the 1980s
Hexa-methylene 1,6- bisthiosulfate disodium salt), for improving the stability of polysulfide crosslink bond.The structure of hts is by two parts group
Become, mid portion is six methylene, and two ends have the structure of double bunte salt.In bunte salt structure in Vulcanization Process of Rubber
Sulfur sulfur bonds, the mid portion of hts is got up by carbon-sulfur bond crosslinking with rubber macromolecule, thus reached sulfur sulfide linkage it
Between embedded submissive hexamethylene group.Because the bond energy of carbon-carbon bond be more than polysulfide bond bond energy, carbon-carbon bond not easy fracture, simultaneously again
Suitable with the sulfur chain length of polysulfide bond, so the composite crosslinking structure that hts is formed with rubber macromolecule can improve vulcanite
Heat stability, resistance to ag(e)ing, suppress the generation reverted, vulcanite can be made simultaneously again to have good tensile property, resistance to tired
Labor performance and deflect performance.But the part that can crosslink with rubber macromolecule in hts structure is only its mid portion, that is,
Six methylene and two sulfur at their two ends, this part only accounts for the 37.9% of hts molecular structure.In hts molecular structure also
Water containing 9.2% and 52.9% inorganic salts material, wherein inorganic salts material remains in vulcanite molecule.hts
In effective ingredient only account for 37.9%, and have 52.9% component residue in vulcanite molecule so that the utilization rate of hts relatively
Low, the material simultaneously remaining is likely to vulcanite can be impacted.For improving the utilization rate of hts, many researcheres are by hts
The inorganic salt structure at two ends is modified, and accesses other functions group, such as silanes, and the functional group of access can also improve rubber
The processing characteristics of glue, mechanical property etc..
Number of patent application is to disclose a kind of organosilicon polysulfide, in n in ep25570832In purged device
Add hts and water, then sequentially add nahco3, formaldehyde, toluene, temperature control at 20-25 DEG C, Deca 3- mercaptopropyi three second
TMOS, filters after stirring reaction 22h and washes with water, can get organosilicon polysulfide after 25 DEG C of dryings.This is anti-
Add organic solvent (as toluene) during answering, reduce the safety of production process, and can produce useless containing organic solvent
Liquid, pollutes environment.
Content of the invention
Present invention aim to address the poor problem of vulcanizate anti-reversion behaviour, provide a kind of siloxyalkyl sulfur
Ether compound.
The siloxyalkyl sulfide compound structural formula that the present invention provides is as follows:
Wherein, r1For the alkyl for 4-8 for the carbon number, r2、r3Independently selected from one of ethyl, propyl group, r4、r5、r6、
r7、r8、r9Independently selected from one of h, methyl, ethyl.
Preferably, r1For the alkyl for 5-7 for the carbon number.
It is highly preferred that r1The alkyl being 6 for carbon number.In the specific embodiment of the present invention, siloxyalkyl sulfur
Ether compound structural formula is selected from:
Compound of the present invention is added to the vulcanization reaction process that on the one hand can participate in sizing material in sizing material, big in sizing material
Access the alkyl chain of flexibility in molecule, improve the crosslink density of sizing material, improve the anti-reversion behaviour of sizing material；On the other hand,
The alkoxy/hydroxy of compound end group can improve the compatibility of inorganic filler and rubber macromolecule, improves the processability of sizing material
Energy and mechanical property.
The present invention also provides the preparation method of described compound, comprises the following steps:
Step 1, by hydrosulphonyl silane and alkaline solution in 10-30 DEG C of mix homogeneously；
Step 2, the mixed liquor that Deca step 1 obtains in organic thiosulfate aqueous solution, 10-30 DEG C of stirring reaction 2-
6h；
Step 3, sucking filtration step 2 gained reactant liquor, solid product is siloxyalkyl sulfide compound.
Reaction mechanism:
Hydrosulphonyl silane is pre-added in alkaline medium, improves the reactivity of sulfydryl, is then added to organic sulfur for sulfur
In the aqueous solution of hydrochlorate, there is scission of link-binding reaction with the s-s key in organic thiosulfate, thus forming new s-s key.
During the course of the reaction, adopt the internal standard method can be with residual in solution in monitoring reaction course by liquid chromatography (hplc)
The organic thiosulfate staying is it may be determined that react the end time, and calculates conversion ratio.
Preferably, hydrosulphonyl silane is selected from γ mercaptopropyitrimethoxy silane, γ-mercaptopropyi three ethoxy in step 1
One of base silane, 2- mercaptoethyl trimethoxy silane, 2- mercaptoethyl triethoxysilane or two or more mixture.
Preferably, described alkaline solution is alkaline aqueous solution or alkaline alcohol solution；Preferably, alkaline aqueous solution is hydrogen
Sodium hydroxide solution, sodium bicarbonate solution, alkaline buffer solution；Preferably, alkaline buffer solution is molten selected from boric acid-Borax buffering
Liquid, Glycine-NaOH buffer solution, Borax-sodium hydroxide buffer solution, disodium hydrogen phosphate-sodium hydroxide buffer solution,
One of sodium bicarbonate-sodium hydroxide buffer solution；It is highly preferred that alkaline alcohol solution is sodium alkoxide/alcoholic solution, sodium alkoxide is c1-
The fatty sodium alkoxide of c8, alcohol is the fatty alcohol of c1-c8.
It is highly preferred that sodium alkoxide is selected from Feldalat NM, Sodium ethylate, hexamethylene sodium alkoxide, sodium tert-butoxide, normal propyl alcohol sodium, sodium isopropylate；More
Preferably, alcohol is selected from methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, the tert-butyl alcohol, Hexalin.
Preferably, the mass percentage concentration of step 1 alkaline solution is 10%-30%.
Preferably, organic thiosulfate molecular formula is nao3s2-r-s2o3Na, wherein, r is the full of 2-10 for carbon number
And straight chained alkyl, it is preferably selected from one or more of ethylidene, propylidene, butylidene, hexylidene, octylene, decylene.
Preferably, the mass percentage concentration of organic thiosulfate aqueous solution is 5%-30%.
It is highly preferred that the mol ratio of hydrosulphonyl silane and organic thiosulfate is 1.8:1-2.3:1.
It is highly preferred that the step also including to solid product washing with alcohol and being dried.
Compared with prior art, compound of the present invention, method have the advantage that
1. the toxic compounds such as organic solvent and formaldehyde need not be added in course of reaction, both improve the safety of course of reaction
Property, do not pollute the environment again；
2. in the present invention, hydrosulphonyl silane, after pre-activate process, can improve reaction rate, shortens the response time.
The method that described compound is prepared in present invention offer, in the basic conditions to have the material of double bunte salt structures
React with hydrosulphonyl silane for raw material, obtain siloxyalkyl sulfide compound.Adopted in internal standard method test solution with hts for internal standard
The hts content of residual is about 0.04%, calculates its conversion ratio and is about 99.5%.Methods described process is simple, raw material are easy to get, energy consumption
Low, post processing pollution is little, modification efficiency is high, reproducible, meets the developing direction of safety and environmental friendliness, has and greatly sends out
Exhibition prospect.
Brief description
Fig. 1 is the infrared spectrogram of siloxyalkyl sulfide compound, the siloxyalkyl that wherein a obtains for embodiment 1
Sulfide compound, the siloxyalkyl sulfide compound that b obtains for embodiment 10, the siloxyalkyl sulfur that c obtains for embodiment 8
Ether compound；
In figure, 3430cm-1For the stretching vibration peak of-oh in si-oh, 2973cm-1For-ch3Symmetrical stretching vibration peak,
2927cm-1And 2855cm-1For-ch2- symmetric and anti-symmetric stretching vibration peak, 960～1200cm-1It is si-o (si-o- in region
Si or si-o-c) stretching vibration peak.By analysis as can be seen that containing si-oh ,-ch in compound a2-、si-o(si-
The group such as o-si), illustrates r in compound a4～r9It is h and contain si-o-si structure；In compound b, a small amount of-ch occurs3,
Si-oh intensity has also weakened, and si-o (si-o-si and si-o-c) absworption peak broadens, illustrate to carry in compound b a small amount of-
ch3, r4～r9Middle part is divided into-ch2-ch3；In compound c, si-oh characteristic peak disappears ,-ch3Characteristic peak strengthens, si-o (si-o-c)
Absworption peak narrows, and r in compound c is described4～r9Middle no h, is-ch2-ch3, therefore si-o vibration absorption peak is si- in si-o-c
O causes, and the infrared spectrogram by this compound a, b, c is all corresponding with its structural formula.
Specific embodiment
The invention discloses a kind of siloxyalkyl sulfide compound and preparation method thereof, those skilled in the art can borrow
Mirror present disclosure, is suitably modified technological parameter and realizes.Specifically, all similar replacements and change are to this area
It is it will be apparent that they are considered as including in the present invention for technical staff.The product of the present invention, method and application are
It is described by preferred embodiment, related personnel substantially can be to herein in without departing from present invention, spirit and scope
Described methods and applications are modified or suitably change and combine, and to realize and to apply the technology of the present invention.
In order that those skilled in the art more fully understands technical scheme, with reference to specific embodiment pair
The present invention is described in further detail.
Embodiment 1
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 15.0g (0.06mol) γ-Mercaptopropyltriethoxysilane (purchased from lark prestige Science and Technology Ltd.), stirring condition
Lower addition 15.0g mass percentage concentration is 30% naoh solution, after stirring 10min pours this solution in Dropping funnel into；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g (0.03mol) two is hydrated hexa-methylene 1, and 6- bisthiosulfate disodium (hts, purchased from flexsys) is added to four-hole boiling flask
In, add 100g water, stir after so that hts is dissolved, the hydrosulphonyl silane solution in Deca Dropping funnel, stirring reaction 4h at 30 DEG C
Afterwards, take sample to pass through liquid chromatography (hplc) from solution, residual in internal standard method test solution is adopted for internal standard with hts
Hts content is about 0.04%, calculates its conversion ratio and is about 99.5%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
The infrared spectrogram of this compound is as shown in Figure 1.
Embodiment 2
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 10.6g (0.054mol) γ mercaptopropyitrimethoxy silane (purchased from lark prestige Science and Technology Ltd.), stirring condition
Lower addition 15.0g mass percentage concentration is 30% naoh solution, after stirring 10min pours this solution in Dropping funnel into；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g (0.03mol) hts is added in four-hole boiling flask, adds 100g water, after stirring makes hts dissolve, in Deca Dropping funnel
Hydrosulphonyl silane solution, after stirring reaction 4h at 30 DEG C, according to the hts of residual in hplc method of testing test solution in embodiment 1
Content is about 0.03%, calculates its conversion ratio and is about 99.5%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
Embodiment 3
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 13.5g (0.06mol) 2- mercaptoethyl triethoxysilane, under stirring condition, addition 15.0g mass percentage concentration is
20% naoh solution, after stirring 10min pours this solution in Dropping funnel into；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g (0.03mol) hts is added in four-hole boiling flask, adds 100g water, after stirring makes hts dissolve, in Deca Dropping funnel
Hydrosulphonyl silane solution, after stirring reaction 4h at 30 DEG C, according to the hts of residual in hplc method of testing test solution in embodiment 1
Content is about 0.05%, calculates its conversion ratio and is about 99.4%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
Embodiment 4
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 15.0g (0.06mol) γ-Mercaptopropyltriethoxysilane, under stirring condition, addition 15.0g mass percentage concentration is
30% nahco3Solution, after stirring 15min pours this solution in Dropping funnel into；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
10.2g (0.026mol) hts is added in four-hole boiling flask, adds 100g water, after stirring makes hts dissolve, in Deca Dropping funnel
Hydrosulphonyl silane solution, after stirring reaction 2h at 30 DEG C, according in hplc method of testing test solution in embodiment 1 residual
Hts content<0.01%, calculates its conversion ratio>99.8%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
Embodiment 5
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 15.0g (0.06mol) γ-Mercaptopropyltriethoxysilane, under stirring condition, addition 15.0g mass percentage concentration is
10% naoh solution, after stirring 30min pours this solution in Dropping funnel into；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g (0.03mol) hts is added in four-hole boiling flask, adds 100g water, after stirring makes hts dissolve, in Deca Dropping funnel
Hydrosulphonyl silane solution, after stirring reaction 6h at 10 DEG C, residual in hplc method of testing test solution from according to embodiment 1
Hts content is about 0.04%, calculates its conversion ratio and is about 99.5%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
Embodiment 6
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 15.0g (0.06mol) γ-Mercaptopropyltriethoxysilane, adds sodium bicarbonate-sodium hydroxide to delay under stirring condition
Rush solution (to weigh 0.14g sodium bicarbonate and 0.06g sodium hydroxide, add 36ml water, be configured to the bicarbonate for 11.0 for the ph value
Sodium-sodium hydroxide buffer solution), after stirring 15min, this solution is poured in Dropping funnel；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g (0.03mol) hts is added in four-hole boiling flask, adds 100g water, after stirring makes hts dissolve, in Deca Dropping funnel
Hydrosulphonyl silane solution, after stirring reaction 5h at 30 DEG C, according to the hts of residual in hplc method of testing test solution in embodiment 1
Content is about 0.06%, calculates its conversion ratio and is about 99.2%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
Embodiment 7
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 15.0g (0.06mol) γ-Mercaptopropyltriethoxysilane, adds sodium dihydrogen phosphate-sodium hydroxide under stirring condition
Buffer solution (weighs 0.2g bis- hypophosphite monohydrate sodium dihydrogen and 0.05g sodium hydroxide, adds 25ml water, be configured to ph value for 12.0
Sodium dihydrogen phosphate-sodium hydroxide buffer solution), stirring 15min after this solution is poured in Dropping funnel；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g (0.03mol) is added in four-hole boiling flask, adds 100g water, the mercapto after stirring makes hts dissolve, in Deca Dropping funnel
Base silane solution, after stirring reaction 5h at 30 DEG C, the hts according to residual in hplc method of testing test solution in embodiment 1 contains
Amount is about 0.04%, calculates its conversion ratio and is about 99.5%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
Embodiment 8
Using the 100ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
4.1g (0.06mol) Sodium ethylate and 20g ethanol, stirring intensification makes Sodium ethylate dissolve, and adds 15.0g γ-mercaptopropyi three ethoxy
Base silane, stirring 2h forms silane/ethanol solution, pours in Dropping funnel；
Using the 250ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g hts is added in four-hole boiling flask, adds 50g water, and 20 DEG C of stirrings make hts dissolve, by above-mentioned silane/ethanol solution Deca
To in hts aqueous solution, stirring reaction 4h, the hts content according to residual in hplc method of testing test solution in embodiment 1 is about
0.04%, calculate its conversion ratio and be about 99.5%.
Stopped reaction, sucking filtration, washing with alcohol solid matter, drying obtains clear yellow viscous material to constant weight, obtains final product siloxy
Alkyl thioether compound, its molecular formula is:
The infrared spectrogram of this compound is as shown in Figure 1.
Embodiment 9
Using the 100ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
3.2g (0.06mol) Feldalat NM and 20g methanol, stirring intensification makes Feldalat NM dissolve, and adds 15.0g γ-mercaptopropyi three ethoxy
Base silane, stirring 2h forms silane/methanol solution, pours in Dropping funnel；
Using the 250ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g hts is added in four-hole boiling flask, adds 50g water, and 20 DEG C of stirrings make hts dissolve, by above-mentioned silane/methanol solution Deca
To in hts aqueous solution, stirring reaction 4h, the hts content according to residual in hplc method of testing test solution in embodiment 1 is about
0.04%, calculate its conversion ratio and be about 99.5%.
Stopped reaction, sucking filtration, washing with alcohol solid matter, drying obtains clear yellow viscous material to constant weight, obtains final product siloxy
Alkyl thioether compound, its molecular formula is:
Embodiment 10
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 15.0g (0.06mol) γ-Mercaptopropyltriethoxysilane, under stirring condition, addition 15.0g mass percentage concentration is
30% naoh/ ethanol solution, after stirring 10min pours this solution in Dropping funnel into；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g (0.03mol) hts is added in four-hole boiling flask, adds 100g water, after stirring makes hts dissolve, in Deca Dropping funnel
Hydrosulphonyl silane solution, after stirring reaction 4h at 30 DEG C, takes sample to pass through the hts content of residual in hplc test solution from solution
It is about 0.04%, calculate its conversion ratio and be about 99.5%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
The infrared spectrogram of this compound is as shown in Figure 1.
Embodiment 11
Using the 100ml there-necked flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, to container
Middle addition 7.5g (0.03mol) γ-Mercaptopropyltriethoxysilane and 6.7g (0.03mol) 2- mercaptoethyl triethoxysilicane
Alkane, adds the naoh solution that 15.0g mass percentage concentration is 30%, pours this solution into and drip after stirring 10min under stirring condition
In liquid funnel；
Using the 200ml four-hole boiling flask equipped with agitating device, thermometer and reflux condenser as reaction vessel, weigh
11.7g (0.03mol) hts is added in four-hole boiling flask, adds 100g water, after stirring makes hts dissolve, in Deca Dropping funnel
Hydrosulphonyl silane solution, after stirring reaction 4h at 30 DEG C, takes sample to pass through liquid chromatography (hplc) from solution, is interior with hts
Mark is about 0.04% using the hts content of residual in internal standard method test solution, calculates its conversion ratio and is about 99.5%.
Stop stirring, above-mentioned solution sucking filtration uses washing with alcohol solid matter, the solid after washing is placed in 45 DEG C of baking ovens
Middle drying, to constant weight, obtains final product siloxyalkyl sulfide compound, and its molecular formula is:
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (14)
1. a kind of preparation method of siloxyalkyl sulfide compound, comprises the following steps:
Step 1, by hydrosulphonyl silane and alkaline solution in 10-30 DEG C of mix homogeneously；
Step 2, the mixed liquor that Deca step 1 obtains in organic thiosulfate aqueous solution, 10-30 DEG C of stirring reaction 2-6h；
Step 3, sucking filtration step 2 gained reactant liquor, solid product is siloxyalkyl sulfide compound,
The structural formula of described siloxyalkyl sulfide compound is as follows:
Wherein, r1For the alkyl for 4-8 for the carbon number, r2、r3Independently selected from one of ethyl, propyl group, r4、r5、r6、r7、
r8、r9Independently selected from one of h, methyl, ethyl.
2. preparation method according to claim 1 is it is characterised in that r1For the alkyl for 5-7 for the carbon number.
3. preparation method according to claim 1 is it is characterised in that r1The alkyl being 6 for carbon number.
4. preparation method according to claim 1 is it is characterised in that its structural formula is selected from:
5. preparation method according to claim 1 is it is characterised in that hydrosulphonyl silane is selected from γ-mercaptopropyi three in step 1
Methoxy silane, γ-Mercaptopropyltriethoxysilane, 2- mercaptoethyl trimethoxy silane, 2- mercaptoethyl triethoxy
One of silane or two or more mixture.
6. preparation method according to claim 1 is it is characterised in that alkaline solution is alkaline aqueous solution or alkaline alcohol is molten
Liquid.
7. preparation method according to claim 6 is it is characterised in that described alkaline aqueous solution is sodium hydroxide solution, carbon
Sour hydrogen sodium solution, alkaline buffer solution；
Described alkaline alcohol solution is sodium alkoxide/alcoholic solution, and sodium alkoxide is the fatty sodium alkoxide of c1-c8, and alcohol is the fatty alcohol of c1-c8.
8. preparation method according to claim 7 is it is characterised in that described alkaline buffer solution delays selected from boric acid-Borax
Rush solution, Glycine-NaOH buffer solution, Borax-sodium hydroxide buffer solution, disodium hydrogen phosphate-sodium hydroxide buffer
One of solution, sodium bicarbonate-sodium hydroxide buffer solution；
Described sodium alkoxide is selected from Feldalat NM, Sodium ethylate, hexamethylene sodium alkoxide, sodium tert-butoxide, normal propyl alcohol sodium, sodium isopropylate；
Described alcohol is selected from methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, the tert-butyl alcohol, Hexalin.
9. preparation method according to claim 1 is it is characterised in that the mass percentage concentration of step 1 alkaline solution is
10%-30%.
10. preparation method according to claim 1 is it is characterised in that organic thiosulfate molecular formula is nao3s2-r-
s2o3Na, wherein, r is the straight chain saturated alkyl of 2-10 for carbon number.
11. preparation methoies according to claim 10 it is characterised in that described r be selected from ethylidene, propylidene, butylidene,
One or more of hexylidene, octylene, decylene.
12. preparation methoies according to claim 1 are it is characterised in that the percent mass of organic thiosulfate aqueous solution
Concentration is 5%-30%.
13. preparation methoies according to claim 1 it is characterised in that hydrosulphonyl silane and organic thiosulfate mole
Than for 1.8:1-2.3:1.
14. preparation methoies according to claim 1 are it is characterised in that also including to solid product washing with alcohol and doing
Dry step.
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| CN104592315B (en) * | 2014-12-29 | 2017-09-15 | 北京彤程创展科技有限公司 | A kind of thio metallic compound nano material of siloxy and preparation method thereof |
| CN113563375A (en) * | 2021-08-25 | 2021-10-29 | 福建佰易科技有限公司 | Synthesis of alpha-type silane coupling agent containing asymmetric disulfide structure |
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| JP2008297357A (en) * | 2007-05-29 | 2008-12-11 | Bridgestone Corp | Rubber composition and tire using the same |
| JP2010189613A (en) * | 2009-02-20 | 2010-09-02 | Bridgestone Corp | Tire |
| EP2557083A1 (en) * | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Networked organosilicon polysulphides |
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