CN106496676A - Chitin modified silica and the preparation method of native rubber composite material - Google Patents
Chitin modified silica and the preparation method of native rubber composite material Download PDFInfo
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- CN106496676A CN106496676A CN201611043366.2A CN201611043366A CN106496676A CN 106496676 A CN106496676 A CN 106496676A CN 201611043366 A CN201611043366 A CN 201611043366A CN 106496676 A CN106496676 A CN 106496676A
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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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
- 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
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Abstract
The present invention relates to China Synthetic Rubber Industry technical field, and in particular to the preparation method of a kind of chitin modified silica and native rubber composite material.Chitin modified silica and the preparation method of native rubber composite material, comprise the steps：（1）Chitin modified silica；（2）The coprecipitated glue of natural rubber；（3）Chitin modified silica and native rubber composite material.The present invention is prepared for chitin modified silica and native rubber composite material using sol-gal process and coprecipitation, and its curing efficiency is improved；The tensile property of composite is improved, and ageing-resistant performance also increases, while aging after-drawing Strength Changes are little；Silica distribution uniform under synergy.
Description
Technical field
The present invention relates to China Synthetic Rubber Industry technical field, and in particular to a kind of chitin modified silica and natural rubber
The preparation method of glue composite.
Background technology
Natural rubber (natural rubber) has splendid elasticity and good mechanical property, is therefore widely used in daily life
Living, communications and transportation and national defense industry.In the industrial production, for reduces cost, increase the physicochemical property of rubber and use the longevity
Life, generally by various inorganic fillers, such as silica etc. is filled in rubber matrix.Silica particle diameter is little, and specific surface area is big,
Preferable enhancing effect is can reach under little consumption.However, the shortcoming of silica is that surface-active is higher, it is difficult in rubber
It is uniformly dispersed, forms internal stress centrostigma, cause the mechanical properties decrease of elastomeric material.In order to improve the enhancing of silica
Effect, can start with terms of silica surface modified, interpolation coupling agent and regulation processing technology etc. are several and solve.
Traditional chemical modifier and dispersant can cause certain pollution during production and use to environment.Cause
This, solving the contradiction between the low-cost high-efficiency enhancing of rubber and environmental protection becomes the emphasis of concern, and this mainly includes improving
Rubber chemicals, prepare the methods such as modifying agent using environment-friendly novel technology of preparing.Wherein, it is near to be modified using natural polymer
The focus that studies over year.Shitosan is the product of chitin deacetylase, is widely present in shrimp crab in nature, shell biological
In, with good biocompatibility and biodegradable performance.Before this, Toskasa etc. is drawn and is prepared for by sol-gel process
It is used as the shitosan/PEO/silicon dioxide composite material of bone material, as a result shows between shitosan and silica
Hydrogen bond be largely fixed the performance of material.Zhang Lina etc. is prepared for shitosan/titanium dioxide using reverse microemulsion process
Silicon composite nanoparticle, as a result shows so that formed compound receives
Rice corpuscles is in the spherical of rule and with good monodispersity and microcellular structure.
Content of the invention
It is contemplated that proposing the preparation method of a kind of chitin modified silica and native rubber composite material.
Technical program of the present invention lies in：
Chitin modified silica and the preparation method of native rubber composite material, comprise the steps：
（1）Chitin modified silica
18 ~ 20mL concentrated ammonia liquors, 30 ~ 32 mL absolute ethyl alcohols and 50 mL water are sequentially added under room temperature in there-necked flask, and machinery is stirred
Mix 5 ~ 10min and obtain alkaline precursor aqueous solution；100 mL TEOs and ethanol solution is prepared in beaker, is added to shitosan
And 10 ~ 12min of ultrasound, it is ensured that shitosan is uniformly dispersed in the solution；Into alkaline precursor aqueous solution is poured TEOS and ethanol solution
There-necked flask in, while increasing agitator speed to 550 ~ 600 r/min, stop after 3 ~ 4 h of stirring, by the sediment for obtaining
Disperse in distilled water, and replace washing with distilled water with absolute ethyl alcohol, obtain shitosan and silica neutrality aqueous dispersions；
（2）The coprecipitated glue of natural rubber
200 g Heveatexes are added in beaker, are simultaneously introduced shitosan and silica dispersions, to glue after 2 ~ 3h of stirring
The CaCl that mass fraction is for 5 ~ 8% is added dropwise in breast2The aqueous solution, settles latex breakdown of emulsion；The blob of viscose for obtaining is cut into small pieces, with steaming
AgNO of the mass fraction that distilled water is added in washing to filtrate for l%3, the aqueous solution without white precipitate occur, finally blob of viscose is put
Enter in 50 ~ 60 DEG C of baking ovens and dry, obtain the coprecipitated glue of natural rubber；
（3）Chitin modified silica and native rubber composite material
Elastomeric compound basic recipe (mass parts)：Coprecipitated glue 100, stearic acid l, zinc oxide 5, antioxidant D 1, captax 1.2 promote
Enter agent DM0.3, Vulcanization accelerator TMTD 0.2, Sulfur 2.5；
Rubber and above-mentioned elastomeric compound on opening rubber mixing machine are plasticated and are kneaded, room temperature is parked after 22 ~ 24 h in flat board
Elastomeric compound is vulcanized on vulcanizer, obtain chitin modified silica and native rubber composite material.
Described concentrated ammonia liquor mass fraction 28 ~ 30%.
The volume fraction 9 ~ 10% of TEOs in described TEOs and ethanol solution.
The method have technical effect that：
The present invention is prepared for chitin modified silica and natural rubber composite wood using sol-gel process and coprecipitation
Material, its curing efficiency are improved；The tensile property of composite is improved, and ageing-resistant performance also increases, while always
Change after-drawing Strength Changes little；Silica distribution uniform under synergy.
Specific embodiment
Chitin modified silica and the preparation method of native rubber composite material, comprise the steps：
Embodiment 1
（1）Chitin modified silica
18mL concentrated ammonia liquors, 30mL absolute ethyl alcohols and 50 mL water, 5 min of mechanical agitation is sequentially added under room temperature in there-necked flask
Obtain alkaline precursor aqueous solution；100 mL TEOs and ethanol solution is prepared in beaker, is added to shitosan ultrasound
10min, it is ensured that shitosan is uniformly dispersed in the solution；The there-necked flask for pouring TEOS and ethanol solution into alkaline precursor aqueous solution
In, while increasing agitator speed to 550 r/min, stop after 3 h of stirring, the sediment for obtaining disperseed in distilled water,
And replace washing with distilled water with absolute ethyl alcohol, obtain shitosan and silica neutrality aqueous dispersions；
（2）The coprecipitated glue of natural rubber
200 g Heveatexes are added in beaker, are simultaneously introduced shitosan and silica dispersions, to latex after 2 h of stirring
Middle dropwise addition mass fraction is 5% CaCl2The aqueous solution, settles latex breakdown of emulsion；The blob of viscose for obtaining is cut into small pieces, distilled water is used
AgNO of the mass fraction added in washing to filtrate for l%3, the aqueous solution without white precipitate occur, blob of viscose is put into 50 finally
Dry in DEG C baking oven, obtain the coprecipitated glue of natural rubber；
（3）Chitin modified silica and native rubber composite material
Elastomeric compound basic recipe (mass parts)：Coprecipitated glue 100, stearic acid l, zinc oxide 5, antioxidant D 1, captax 1.2 promote
Enter agent DM0.3, Vulcanization accelerator TMTD 0.2, Sulfur 2.5；
Rubber and above-mentioned elastomeric compound on opening rubber mixing machine are plasticated and are kneaded, room temperature is parked after 22 h in compression molding
Elastomeric compound is vulcanized on machine, obtain chitin modified silica and native rubber composite material.
Wherein, described concentrated ammonia liquor mass fraction 28%.The volume fraction of TEOs in described TEOs and ethanol solution
9%.
Embodiment 2
（1）Chitin modified silica
20mL concentrated ammonia liquors, 32 mL absolute ethyl alcohols and 50 mL water, mechanical agitation 10min is sequentially added under room temperature in there-necked flask
Obtain alkaline precursor aqueous solution；100 mL TEOs and ethanol solution is prepared in beaker, is added to shitosan ultrasound
12min, it is ensured that shitosan is uniformly dispersed in the solution；The there-necked flask for pouring TEOS and ethanol solution into alkaline precursor aqueous solution
In, while increasing agitator speed to 600 r/min, stop after 4 h of stirring, the sediment for obtaining disperseed in distilled water,
And replace washing with distilled water with absolute ethyl alcohol, obtain shitosan and silica neutrality aqueous dispersions；
（2）The coprecipitated glue of natural rubber
200 g Heveatexes are added in beaker, are simultaneously introduced shitosan and silica dispersions, to latex after stirring 3h
Middle dropwise addition mass fraction is 8% CaCl2The aqueous solution, settles latex breakdown of emulsion；The blob of viscose for obtaining is cut into small pieces, distilled water is used
AgNO of the mass fraction added in washing to filtrate for l%3, the aqueous solution without white precipitate occur, blob of viscose is put into 60 finally
Dry in DEG C baking oven, obtain the coprecipitated glue of natural rubber；
（3）Chitin modified silica and native rubber composite material
Elastomeric compound basic recipe (mass parts)：Coprecipitated glue 100, stearic acid l, zinc oxide 5, antioxidant D 1, captax 1.2 promote
Enter agent DM0.3, Vulcanization accelerator TMTD 0.2, Sulfur 2.5；
Rubber and above-mentioned elastomeric compound on opening rubber mixing machine are plasticated and are kneaded, room temperature is parked after 24 h in compression molding
Elastomeric compound is vulcanized on machine, obtain chitin modified silica and native rubber composite material.
Wherein, described concentrated ammonia liquor mass fraction 30%.The volume fraction of TEOs in described TEOs and ethanol solution
10%.
Claims (3)
1. the preparation method of chitin modified silica and native rubber composite material, it is characterised in that：Comprise the steps：
（1）Chitin modified silica
18 ~ 20mL concentrated ammonia liquors, 30 ~ 32 mL absolute ethyl alcohols and 50 mL water are sequentially added under room temperature in there-necked flask, and machinery is stirred
Mix 5 ~ 10min and obtain alkaline precursor aqueous solution；100 mL TEOs and ethanol solution is prepared in beaker, is added to shitosan
And 10 ~ 12min of ultrasound, it is ensured that shitosan is uniformly dispersed in the solution；Into alkaline precursor aqueous solution is poured TEOS and ethanol solution
There-necked flask in, while increasing agitator speed to 550 ~ 600 r/min, stop after 3 ~ 4 h of stirring, by the sediment for obtaining
Disperse in distilled water, and replace washing with distilled water with absolute ethyl alcohol, obtain shitosan and silica neutrality aqueous dispersions；
（2）The coprecipitated glue of natural rubber
200 g Heveatexes are added in beaker, are simultaneously introduced shitosan and silica dispersions, to glue after 2 ~ 3h of stirring
The CaCl that mass fraction is for 5 ~ 8% is added dropwise in breast2The aqueous solution, settles latex breakdown of emulsion；The blob of viscose for obtaining is cut into small pieces, with steaming
AgNO of the mass fraction that distilled water is added in washing to filtrate for l%3, the aqueous solution without white precipitate occur, finally blob of viscose is put
Enter in 50 ~ 60 DEG C of baking ovens and dry, obtain the coprecipitated glue of natural rubber；
（3）Chitin modified silica and native rubber composite material
Elastomeric compound basic recipe (mass parts)：Coprecipitated glue 100, stearic acid l, zinc oxide 5, antioxidant D 1, captax 1.2 promote
Enter agent DM0.3, Vulcanization accelerator TMTD 0.2, Sulfur 2.5；
Rubber and above-mentioned elastomeric compound on opening rubber mixing machine are plasticated and are kneaded, room temperature is parked after 22 ~ 24 h in flat board
Elastomeric compound is vulcanized on vulcanizer, obtain chitin modified silica and native rubber composite material.
2. the preparation method of chitin modified silica according to claim 1 and native rubber composite material, its are special
Levy and be：Described concentrated ammonia liquor mass fraction 28 ~ 30%.
3. the preparation method of chitin modified silica according to claim 1 and native rubber composite material, its are special
Levy and be：The volume fraction 9 ~ 10% of TEOs in described TEOs and ethanol solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611043366.2A CN106496676A (en) | 2016-11-24 | 2016-11-24 | Chitin modified silica and the preparation method of native rubber composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111792649A (en) * | 2020-07-15 | 2020-10-20 | 浙江爱津生物技术有限公司 | Preparation method of modified silica gel membrane for nucleic acid detection |
| CN115403680A (en) * | 2022-08-24 | 2022-11-29 | 华南理工大学 | Nano silicon dioxide/chitosan hybrid material loaded anti-aging agent and preparation and application thereof |
-
2016
- 2016-11-24 CN CN201611043366.2A patent/CN106496676A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111792649A (en) * | 2020-07-15 | 2020-10-20 | 浙江爱津生物技术有限公司 | Preparation method of modified silica gel membrane for nucleic acid detection |
| CN115403680A (en) * | 2022-08-24 | 2022-11-29 | 华南理工大学 | Nano silicon dioxide/chitosan hybrid material loaded anti-aging agent and preparation and application thereof |
| CN115403680B (en) * | 2022-08-24 | 2023-03-21 | 华南理工大学 | Nano silicon dioxide/chitosan hybrid material loaded anti-aging agent and preparation and application thereof |
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Application publication date: 20170315 |