CN105199249B - A kind of preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent - Google Patents
A kind of preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The present invention relates to a kind of preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent; preparation including organic modification montmonrillonite, 4 pi-allyls 2; the hydroxyl protection of 6 syringol, 4 pi-allyls 2; the preparation of 6 dimethoxy methyl phenyl ethers anisole modified montmorillonoids, the hydroxyl solution protection of the dimethoxy methyl phenyl ethers anisole modified organo montmorillonite of 4 pi-allyl 2,6, five steps of preparation of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent.Compared with prior art, the present invention improves the damping vibration attenuation effect of elastomeric material.The preparation technology of the composite is economical and practical, and preparation process is simple, and low cost is easily accomplished scale production, with practicality.
Description
Technical field
The present invention relates to a kind of preparation method of modified montmorillonoid material, damped containing modified montmorillonoid more particularly, to one kind
The preparation method of the chlorinated butyl damping rubber of agent.
Background technology
The vehicles such as automobile widely use damping material during damping vibration attenuation.During damping vibration attenuation, high resistant
Damping material is attached to the surface of associated structural component.By damping material internal structure by mechanical energy dissipative, so as to reach vibration damping
Purpose, can reduce to a certain extent noise.The vibration produced in the running of the vehicles such as automobile and noise,
Both the fatigue damage of automotive interior related components had been accelerated, had shortened its service life, while also polluting city to a certain extent
City's environment and it is detrimental to health.Therefore, inexpensive, efficient damping material is developed, its damping vibration attenuation effect is improved, improves vapour
The working environment of the vehicles parts such as car, it is most important for urban safety and economic heath development.
Damping material is a kind of functional material that can be absorbed vibration mechanical energy and it is converted into heat energy and is lost.Can be divided into
Polymer damping material, hybrid inorganic-organic damping material, ceramic damping material, high damping alloy material and piezo-electric damping material
Material etc..Wherein polymer damping material is most study, most widely used class damping material.Rubber-like damping material is high
One of important species of air damping material, it is that the viscoelastic structure having in itself using rubber carries out damping vibration attenuation.
Influence of the clay fillers such as montmorillonite to elastomeric material damping capacity has two aspects：One is that dis-reinforcing filler adds
Membership causes the free volume of material to become big, dilution effect is produced, so as to reduce the damping capacity of material；Two is that addition sheet is filled out
When the elastomeric material of material is deformed by external force effect, laminal filter can be orientated, so that being produced between filler and rubber
Friction, plays a part of noise reduction.Numerous studies show that the addition of nanoclay improves the tensile strength of composite, fracture
Mechanical properties such as elongation, but not notable to the energy dissipation effect of composite, it is therefore desirable to its structure is modified with
Improve its damping vibration attenuation ability.Wang Jincheng etc. is prepared for a kind of Novel pruning shape damping agent using dendritic polymer technology of preparing
(Wang Jincheng, Hao Wenli, Zhao Yi, Pan Xinchen, Guo Xi, Dong Xingyu, a kind of dendriform damping agent and its preparation method and application,
ZL201110347024.0), although damping preferably, but is carried out in the technology using the hydroxyl on silane containing hydrogen and hindered phenol
Graft reaction, consumes part of hydroxyl, causes the hydrogen bond effect of its lifting damping not play completely.Accordingly, it would be desirable to using
Certain technology is protected to the hydroxyl on hindered phenol, lifts its hydrogen bond action effect.
The content of the invention
The purpose of the present invention is exactly to provide one kind and improve rubber material for the defect for overcoming above-mentioned prior art to exist
The preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent of the damping vibration attenuation effect of material.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent, using following steps：
(1) preparation of organic modification montmonrillonite：
By inorganic montmorillonite, hydrogen containing siloxane and ethanol at 70~90 DEG C and logical N230~40min of stirring, holding 4~
6h, then vacuumizes to remove ethanol, obtains organic modification montmonrillonite；
(2) hydroxyl protection of 4- pi-allyls -2,6- syringol：
By 4- pi-allyl -2,6- syringol, tetrahydrofuran and n-BuLi in N2Under protection, in -70~-80 DEG C
1~3h of strong agitation, then in 40~60 DEG C, 2~4h is reacted with trim,ethylchlorosilane, and product is washed with methyl alcohol, centrifugation,
4~5h of vacuum drying, obtains 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisoles；
(3) preparation of 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole modified montmorillonoid：
By organic modification montmonrillonite, 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole and metallic catalyst in N2Under protection, in
100~120 DEG C of 3~5h of strong agitation, vacuumize removing unreacted reactant, and product is washed with methyl alcohol, and centrifugation, sediment is used again
It is centrifuged again after solvent washing, is steps be repeated alternatively until untill unreacted material is can't detect in cleaning solution, by sediment
2~3h is vacuum dried in 40~60 DEG C, 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified organo montmorillonites are obtained；
(4) the hydroxyl solution protection of 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole modified organo montmorillonite：
By 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified montmorillonoids and hydrogen bromide in N2Under protection, in 80~100 DEG C
1~2h of strong agitation, product is washed with methyl alcohol, centrifugation, is vacuum dried 3~4h, obtains 4- pi-allyl -2,6- dimethoxys
Phenol-modified montmorillonite；
(5) preparation of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent：
Chlorinated scoline matrix, zinc oxide, accelerator, age resistor, 4- pi-allyl -2,6- syringol are modified
In the input mill of montmorillonite, vulcanizing agent and stearic acid, kneaded under conditions of being 30~50 DEG C in temperature, prepared chlorine
Change butyl damping rubber.
The ratio of inorganic montmorillonite, hydrogen containing siloxane and ethanol is 10~20g in step (1)：0.2~0.4mol：10
~20mL.
4- pi-allyl -2,6- syringol, tetrahydrofuran, n-BuLi, the weight of trim,ethylchlorosilane in step (2)
Amount is than being 10~20：80~100：0.2~0.4：10~20.
The weight of organic modification montmonrillonite, 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole and metallic catalyst in step (3)
Than being 50~80：40~60：0.3~0.5, wherein metallic catalyst is iron, cobalt or nickel.
In step (4) the weight ratio of 4- pi-allyls -2,6- dimethoxy methyl phenyl ethers anisole modified montmorillonoids and hydrogen bromide be 10~
20：20~40.
Chlorinated scoline matrix, zinc oxide, accelerator, age resistor, 4- pi-allyl -2,6- dimethoxys in step (5)
Phenol-modified montmorillonite, vulcanizing agent and stearic weight ratio are 100：3~5：1~1.5：1~3：10~15：2~3：0.5~
1.0, wherein vulcanizing agent is sulphur, and accelerator is 2- benzothiazolyl mercaptans, and age resistor is diaryl secondary amine antioxidant.
Because hydrogen containing siloxane not only can carry out addition reaction with double bond, can also be reacted with hydroxyl, it is therefore desirable to
Protection is carried out to the hydroxyl in 4- pi-allyl -2,6- syringol could be so that final product has enough with rubbery system
Hydrogen bond action, could embody its damping vibration attenuation effect.Compared with prior art, 4- pi-allyl -2, in 6- syringol
Hydroxyl, all by methyl-etherified, generates 4- pi-allyl -2 before with hydrogen containing siloxane reaction, 6- dimethoxy methyl phenyl ethers anisoles, and organic
After modified montmorillonoid carries out graft reaction, then with reaction of hydrogen bromide, ether is changed into hydroxyl, therefore, in damping agent of the present invention
Hydroxyl be entirely protected, can there is more hydrogen bond action in guarantee system in this.These hydrogen bond actions and simultaneous
The rubbing action produced by sheet organo montmorillonite constitutes damping vibration attenuation mechanism of the invention together.These mechanism be conducive to by
External influence is converted into heat energy in the mechanical energy on rubber matrix, so as to improve the damping vibration attenuation effect of elastomeric material.This is answered
The preparation technology of condensation material is economical and practical, and preparation process is simple, and low cost is easily accomplished scale production, with practicality.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Used in embodiment《Nano composite polymer/laminated silicate material theory and practice》(QiZongNeng, Shang Wenyu is compiled
Write, Chemical Industry Press, 2002) report method：The interlamellar spacing of organo montmorillonite is tested using small-angle diffraction method；Using saturating
Penetrate the particle size that electron microscopy observes fire retardant powder.
The DMA-242 types dynamic mechanical analyzer produced using German Nai Chi companies tests the damping capacity of rubber；
The mechanical property of chlorinated butyl damping rubber is tested using GB 528-83.
Comparative example 1
By chlorinated scoline 100g, zinc oxide 3g, stearic acid 0.5g, captax 1g, antioxidant A 1g and sulphur 2g
According to aforementioned proportion input mill, kneaded under conditions of being 30 DEG C in temperature, that is, obtained common chlorinated butyl rubber
Glue.
Fissipation factor, tensile strength, the elongation at break of common chlorinated butyl damping rubber, are shown in Table 2.
Comparative example 2
By chlorinated scoline 100g, zinc oxide 4g, stearic acid 0.8g, captax 1.2g, antioxidant A 2g and sulphur
During 2.5g etc. is according to aforementioned proportion input mill, kneaded under conditions of being 40 DEG C in temperature, that is, obtained common chlorination fourth
Base rubber.
Fissipation factor, tensile strength, the elongation at break of common chlorinated butyl damping rubber, are shown in Table 2.
Comparative example 3
By chlorinated scoline 100g, zinc oxide 5g, stearic acid 1.0g, captax 1.5g, antioxidant A 3g and sulphur
During 3g etc. is according to aforementioned proportion input mill, kneaded under conditions of being 50 DEG C in temperature, that is, obtained common chlorinated butyl
Rubber.
Fissipation factor, tensile strength, the elongation at break of common chlorinated butyl damping rubber, are shown in Table 2.
Embodiment 1
The inorganic montmorillonites of 10g, 0.2mol hydrogen containing siloxanes and 10mL ethanol are added in three-necked bottle, mixture is at 70 DEG C
With logical N2In the case of stir 40min, and keep 6h, then vacuumize to remove ethanol, obtain organic modification montmonrillonite.Weigh
10g 4- pi-allyl -2,6- syringol, the tetrahydrofuran of 80g and 0.2g n-BuLis in four-neck flask, in N2Protect
Under shield, in -70 DEG C of strong agitations 1 hour.Then in 40 DEG C, reacted 4 hours with 10g trim,ethylchlorosilanes.Product is washed with methyl alcohol
Wash, centrifugation, be vacuum dried 4 hours, obtain 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisoles.The organically-modified illiteracies of 50g is weighed to take off
Soil, 4- pi-allyl -2 of 40g, 6- dimethoxys methyl phenyl ethers anisole and 0.3g iron in four-neck flask, in N2It is strong in 100 DEG C under protection
Strong stirring 3 hours, then vacuumizes removing unreacted reactant, and product is washed with methyl alcohol, centrifugation, and sediment is washed with solvent again
It is centrifuged again afterwards, steps be repeated alternatively until untill unreacted material is can't detect in cleaning solution.Sediment is true in 40 DEG C
Sky is dried 2 hours, obtains 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified organo montmorillonites.10g 4- pi-allyl -2 are weighed,
6- dimethoxy methyl phenyl ethers anisoles modified montmorillonoid, 20g hydrogen bromide in three-neck flask, in N2Under protection, in 80 DEG C of strong agitations 1
Hour, product is washed with methyl alcohol, centrifugation, is vacuum dried 3 hours, obtains damping agent of the invention, 4- pi-allyl -2,6- bis-
Metoxyphenol modified montmorillonoid.By chlorinated scoline 100g, zinc oxide 3g, stearic acid 0.5g, captax 1g, antioxidant A
During 1g, hindered phenol modified organo montmorillonite 10g and sulphur 2g etc. are according to aforementioned proportion input mill, in the bar that temperature is 30 DEG C
Kneaded under part, that is, obtained chlorinated butyl damping rubber of the invention.
The interlamellar spacing and particle size of hindered phenol modified organo montmorillonite are shown in Table 1.
The fissipation factor of chlorinated butyl damping rubber, tensile strength, elongation at break, are shown in Table 2.
Embodiment 2
The inorganic montmorillonites of 15g, 0.3mol hydrogen containing siloxanes and 15mL ethanol are added in three-necked bottle, mixture is at 80 DEG C
With logical N2In the case of stir 35min, and keep 5h, then vacuumize to remove ethanol, obtain organic modification montmonrillonite.Weigh
15g 4- pi-allyl -2,6- syringol, the tetrahydrofuran of 90g and 0.3g n-BuLis in four-neck flask, in N2Protect
Under shield, in -75 DEG C of strong agitations 2 hours.Then in 50 DEG C, reacted 3 hours with 15g trim,ethylchlorosilanes.Product is washed with methyl alcohol
Wash, centrifugation, be vacuum dried 4.5 hours, obtain 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisoles.Weigh the organically-modified illiteracies of 65g
De- soil, 4- pi-allyl -2 of 50g, 6- dimethoxys methyl phenyl ethers anisole and 0.4g cobalts in four-neck flask, in N2Under protection, in 110 DEG C
Strong agitation 4 hours, then vacuumizes removing unreacted reactant, and product is washed with methyl alcohol, centrifugation, and sediment is washed with solvent again
It is centrifuged again after washing, is steps be repeated alternatively until untill unreacted material is can't detect in cleaning solution.By sediment in 50 DEG C
Vacuum drying 2.5 hours, obtains 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified organo montmorillonites.Weigh 15g 4- allyls
Base -2,6- dimethoxy methyl phenyl ethers anisoles modified montmorillonoid, 30g hydrogen bromide in three-neck flask, in N2It is strong in 90 DEG C under protection
Stirring 1.5 hours, product is washed with methyl alcohol, centrifugation, is vacuum dried 3.5 hours, obtains damping agent of the invention, 4- allyls
Base -2,6- syringol modified montmorillonoids.By chlorinated scoline 100g, zinc oxide 4g, stearic acid 0.8g, accelerator
During M1.2g, antioxidant A 2g, hindered phenol modified organo montmorillonite 13g and sulphur 2.5g etc. are according to aforementioned proportion input mill,
Kneaded under conditions of being 30~50 DEG C in temperature, that is, obtained chlorinated butyl damping rubber of the invention.
The interlamellar spacing and particle size of hindered phenol modified organo montmorillonite are shown in Table 1.
The fissipation factor of chlorinated butyl damping rubber, tensile strength, elongation at break, are shown in Table 2.
Embodiment 3
The inorganic montmorillonites of 20g, 0.4mol hydrogen containing siloxanes and 20mL ethanol are added in three-necked bottle, mixture is at 90 DEG C
With logical N2In the case of stir 30min, and keep 4h, then vacuumize to remove ethanol, obtain organic modification montmonrillonite.Weigh
20g 4- pi-allyl -2,6- syringol, the tetrahydrofuran of 100g and 0.4g n-BuLis in four-neck flask, in N2Protect
Under shield, in -80 DEG C of strong agitations 3 hours.Then in 60 DEG C, reacted 2 hours with 20g trim,ethylchlorosilanes.Product is washed with methyl alcohol
Wash, centrifugation, be vacuum dried 5 hours, obtain 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisoles.The organically-modified illiteracies of 80g is weighed to take off
Soil, 4- pi-allyl -2 of 60g, 6- dimethoxys methyl phenyl ethers anisole and 0.5g nickel in four-neck flask, in N2It is strong in 120 DEG C under protection
Strong stirring 3 hours, then vacuumizes removing unreacted reactant, and product is washed with methyl alcohol, centrifugation, and sediment is washed with solvent again
It is centrifuged again afterwards, steps be repeated alternatively until untill unreacted material is can't detect in cleaning solution.Sediment is true in 60 DEG C
Sky is dried 2 hours, obtains 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified organo montmorillonites.20g 4- pi-allyl -2 are weighed,
6- dimethoxy methyl phenyl ethers anisoles modified montmorillonoid, 40g hydrogen bromide in three-neck flask, in N2Under protection, in 100 DEG C of strong agitations
1 hour, product was washed with methyl alcohol, centrifugation, was vacuum dried 4 hours, obtained damping agent of the invention, 4- pi-allyl -2,6-
Syringol modified montmorillonoid.By chlorinated scoline 100g, zinc oxide 5g, stearic acid 1.0g, captax 1.5g, anti-
It is 50 in temperature during old agent A 3g, hindered phenol modified organo montmorillonite 15g and sulphur 3g etc. are according to aforementioned proportion input mill
Kneaded under conditions of DEG C, that is, obtained chlorinated butyl damping rubber of the invention.
The interlamellar spacing and particle size of hindered phenol modified organo montmorillonite are shown in Table 1.
The fissipation factor of chlorinated butyl damping rubber, tensile strength, elongation at break, are shown in Table 2.
The interlamellar spacing and particle size of the hindered phenol modified organo montmorillonite of table 1
| Embodiment | Interlamellar spacing (nm) | Particle diameter (nm) |
| 1 | 1.5 | 80 |
| 2 | 1.8 | 90 |
| 3 | 2.2 | 100 |
Fissipation factor, tensile strength, the elongation at break of the chlorinated butyl damping rubber of table 2
| Embodiment | tanδ | Tensile strength/MPa | Elongation at break/% |
| Comparative example 1 | 0.3 | 5.2 | 180 |
| Comparative example 2 | 0.4 | 5.3 | 190 |
| Comparative example 3 | 0.5 | 5.5 | 230 |
| Embodiment 1 | 1.2 | 8.2 | 300 |
| Embodiment 2 | 1.3 | 8.9 | 350 |
| Embodiment 3 | 1.5 | 9.1 | 450 |
From Table 2, it can be seen that the chlorinated butyl damping rubber containing modified montmorillonoid damping agent of the invention is with the addition of, by
There is the rubbing action of more hydrogen bond action and montmorillonite layer in system, the fissipation factor of composite has very great Cheng
The raising of degree.In addition, the strengthening action of these hydrogen bond actions and montmorillonite layer causes that the mechanical property of material is also obtained
It is obvious to improve.
Embodiment 4
The preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent, using following steps：
(1) preparation of organic modification montmonrillonite：
By the inorganic montmorillonites of 20g, 0.4mol hydrogen containing siloxanes and 20mL ethanol at 90 DEG C and logical N2Stirring 30min, protects
6h is held, then vacuumizes to remove ethanol, obtain organic modification montmonrillonite；
(2) hydroxyl protection of 4- pi-allyls -2,6- syringol：
By 4- pi-allyl -2,6- syringol 20g, tetrahydrofuran 100g and n-BuLi 0.4g in N2Under protection,
In -80 DEG C of strong agitation 3h, then in 60 DEG C, 2h is reacted with 20g trim,ethylchlorosilanes, product is washed with methyl alcohol, centrifugation,
Vacuum drying 5h, obtains 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisoles；
(3) preparation of 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole modified montmorillonoid：
By organic modification montmonrillonite 80g, 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole 60g and metallic nickel 0.5g in N2Protect
Under shield, in 120 DEG C of strong agitation 3h, removing unreacted reactant is vacuumized, product is washed with methyl alcohol, and centrifugation, sediment is used again
It is centrifuged again after solvent washing, is steps be repeated alternatively until untill unreacted material is can't detect in cleaning solution, by sediment
2h is vacuum dried in 60 DEG C, 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified organo montmorillonites are obtained；
(4) the hydroxyl solution protection of 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole modified organo montmorillonite：
By 4- pi-allyl -2,6- dimethoxys methyl phenyl ethers anisole modified montmorillonoid 20g and hydrogen bromide 40g in N2Under protection, in 100
DEG C strong agitation 1h, product is washed with methyl alcohol, centrifugation, is vacuum dried 4h, obtains 4- pi-allyl -2,6- syringol
Modified montmorillonoid；
(5) preparation of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent：
By chlorinated scoline matrix 100g, zinc oxide 5g, 2- benzothiazolyl mercaptan accelerator 1.5g, secondary diarylamine
Class age resistor 3g, 4- pi-allyl -2,6- syringol modified montmorillonoids 15g, vulcanizing agent 3g and stearic acid 1g input mills
In machine, kneaded under conditions of being 50 DEG C in temperature, prepared chlorinated butyl damping rubber.
Embodiment 5
The preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent, using following steps：
(1) preparation of organic modification montmonrillonite：
By the inorganic montmorillonites of 10g, 0.2mol hydrogen containing siloxanes and 10mL ethanol at 70 DEG C and logical N2Stirring 40min, protects
4h is held, then vacuumizes to remove ethanol, obtain organic modification montmonrillonite；
(2) hydroxyl protection of 4- pi-allyls -2,6- syringol：
By 4- pi-allyl -2,6- syringol 10g, tetrahydrofuran 80g and n-BuLi 0.2g in N2Under protection,
In -70 DEG C of strong agitation 1h, then in 40 DEG C, 4h is reacted with 10g trim,ethylchlorosilanes, product is washed with methyl alcohol, centrifugation,
Vacuum drying 4h, obtains 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisoles；
(3) preparation of 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole modified montmorillonoid：
By organic modification montmonrillonite 50g, 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole 40g and metal Co catalysts 0.3g
In N2Under protection, in 100 DEG C of strong agitation 5h, removing unreacted reactant is vacuumized, product is washed with methyl alcohol, centrifugation, precipitated
Thing is centrifuged again after being washed with solvent again, steps be repeated alternatively until untill unreacted material is can't detect in cleaning solution, will
Sediment is vacuum dried 3h in 40 DEG C, obtains 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified organo montmorillonites；
(4) the hydroxyl solution protection of 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole modified organo montmorillonite：
By 4- pi-allyl -2,6- dimethoxys methyl phenyl ethers anisole modified montmorillonoid 10g and hydrogen bromide 20g in N2Under protection, in 80
DEG C strong agitation 2h, product is washed with methyl alcohol, centrifugation, is vacuum dried 3h, obtains 4- pi-allyl -2,6- syringol
Modified montmorillonoid；
(5) preparation of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent：
By chlorinated scoline matrix 100g, zinc oxide 3g, 2- benzothiazolyl mercaptan accelerator 1g, secondary diarylamine class
Age resistor 1g, 4- pi-allyl -2,6- syringol modified montmorillonoids 10g, sulphur 2g and stearic acid 0.5g input mills
In, kneaded under conditions of being 30~50 DEG C in temperature, prepare chlorinated butyl damping rubber.
Claims (8)
1. a kind of preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent, it is characterised in that the method is adopted
Use following steps：
(1) preparation of organic modification montmonrillonite：
By inorganic montmorillonite, hydrogen containing siloxane and ethanol at 70~90 DEG C and logical N230~40min of stirring, keeps 4~6h, so
After vacuumize to remove ethanol, obtain organic modification montmonrillonite；
(2) hydroxyl protection of 4- pi-allyls -2,6- syringol：
By 4- pi-allyl -2,6- syringol, tetrahydrofuran and n-BuLi in N2It is strong in -70~-80 DEG C under protection
1~3h of stirring, then in 40~60 DEG C, 2~4h is reacted with trim,ethylchlorosilane, and product is washed with methyl alcohol, centrifugation, vacuum
4~5h is dried, 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisoles are obtained；
(3) preparation of 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole modified montmorillonoid：
By organic modification montmonrillonite, 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole and metallic catalyst in N2Under protection, in 100~
120 DEG C of 3~5h of strong agitation, vacuumize removing unreacted reactant, and product is washed with methyl alcohol, and centrifugation, sediment uses solvent again
It is centrifuged again after washing, is steps be repeated alternatively until untill unreacted material is can't detect in cleaning solution, by sediment in 40
~60 DEG C of 2~3h of vacuum drying, obtain 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified organo montmorillonites；
(4) the hydroxyl solution protection of 4- pi-allyls -2,6- dimethoxys methyl phenyl ethers anisole modified organo montmorillonite：
By 4- pi-allyl -2,6- dimethoxy methyl phenyl ethers anisole modified montmorillonoids and hydrogen bromide in N2It is strong in 80~100 DEG C under protection
1~2h of stirring, product is washed with methyl alcohol, and centrifugation is vacuum dried 3~4h, obtains 4- pi-allyl -2,6- syringol
Modified montmorillonoid；
(5) preparation of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent：
Chlorinated scoline matrix, zinc oxide, accelerator, age resistor, the modified illiteracy of 4- pi-allyl -2,6- syringol are taken off
In the input mill of soil, vulcanizing agent and stearic acid, kneaded under conditions of being 30~50 DEG C in temperature, prepared chlorination fourth
Base damping rubber.
2. the preparation method of a kind of chlorinated butyl damping rubber containing modified montmorillonoid damping agent according to claim 1,
Characterized in that, the ratio of inorganic montmorillonite, hydrogen containing siloxane and ethanol is 10~20g in step (1)：0.2~0.4mol：
10~20mL.
3. the preparation method of a kind of chlorinated butyl damping rubber containing modified montmorillonoid damping agent according to claim 1,
Characterized in that, 4- pi-allyl -2,6- syringol, tetrahydrofuran, n-BuLi, trim,ethylchlorosilane in step (2)
Weight ratio be 10~20：80~100：0.2~0.4：10~20.
4. the preparation method of a kind of chlorinated butyl damping rubber containing modified montmorillonoid damping agent according to claim 1,
Characterized in that, organic modification montmonrillonite, 4- pi-allyl -2 in step (3), 6- dimethoxys methyl phenyl ethers anisole and metallic catalyst
Weight ratio is 50~80：40~60：0.3~0.5.
5. the preparation side of a kind of chlorinated butyl damping rubber containing modified montmorillonoid damping agent according to claim 1 or 4
Method, it is characterised in that the metallic catalyst described in step (3) is iron, cobalt or nickel.
6. the preparation method of a kind of chlorinated butyl damping rubber containing modified montmorillonoid damping agent according to claim 1,
Characterized in that, the weight ratio of 4- pi-allyl -2 in step (4), 6- dimethoxy methyl phenyl ethers anisole modified montmorillonoids and hydrogen bromide is 10
~20：20~40.
7. the preparation method of a kind of chlorinated butyl damping rubber containing modified montmorillonoid damping agent according to claim 1,
Characterized in that, chlorinated scoline matrix, zinc oxide, accelerator, age resistor, 4- pi-allyl -2,6- dimethoxies in step (5)
The phenol-modified montmorillonite of base, vulcanizing agent and stearic weight ratio are 100：3~5：1~1.5：1~3：10~15：2~3：0.5
~1.0.
8. the preparation side of a kind of chlorinated butyl damping rubber containing modified montmorillonoid damping agent according to claim 1 or 7
Method, it is characterised in that the vulcanizing agent described in step (5) is sulphur, described accelerator is 2- benzothiazolyl mercaptans, described
Age resistor be diaryl secondary amine antioxidant.
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| JP2003113271A (en) * | 2001-10-01 | 2003-04-18 | Tokai Rubber Ind Ltd | High damping rubber composition |
| CN1693350A (en) * | 2004-05-09 | 2005-11-09 | 张�诚 | Polymer based damping material |
| CN1303144C (en) * | 2004-06-24 | 2007-03-07 | 华东理工大学 | High performance butyl-rubber damping material |
| CN101463167A (en) * | 2007-12-20 | 2009-06-24 | 天津市振海橡胶科技发展有限公司 | Visco-elastic damping material |
| CN102030951A (en) * | 2010-12-03 | 2011-04-27 | 中国科学院长春应用化学研究所 | Method for preparing chlorinated butyl rubber damping material |
| CN102061040B (en) * | 2010-12-28 | 2015-02-11 | 山东美晨科技股份有限公司 | Raw material for preparing high-damping rubber for automobile damping products |
| CN102504338B (en) * | 2011-11-07 | 2013-02-13 | 上海工程技术大学 | Branch-shaped damping agent and preparation method and use thereof |
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