CN106380643A - Modified zinc oxide and preparation method thereof, and application of modified zinc oxide in rubber products - Google Patents
Modified zinc oxide and preparation method thereof, and application of modified zinc oxide in rubber products Download PDFInfo
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- CN106380643A CN106380643A CN201610910407.7A CN201610910407A CN106380643A CN 106380643 A CN106380643 A CN 106380643A CN 201610910407 A CN201610910407 A CN 201610910407A CN 106380643 A CN106380643 A CN 106380643A
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- zinc oxide
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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
- C08K3/02—Elements
- C08K3/06—Sulfur
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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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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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to a modified zinc oxide and a preparation method thereof, and application of the modified zinc oxide in rubber products. According to the invention, the preparation method simplifies the technical operation and promotes the uniform distribution of zinc oxide; the zinc oxide surface is subjected to modification treatment; tetraethyl orthosilicate is hydrolyzed in the solution to generate silicon dioxide, and the silicon dioxide is coated on the zinc oxide surface, thereby avoiding the direct contact between the latex and zinc oxide; and the modified can be added with sulfur and other materials and mixed and cured, so that the silicon dioxide outside the zinc oxide can be corroded by the alkali during high-temperature vulcanization, thereby fully displaying the vulcanization activation effect. The modified zinc oxide comprises the following components in parts by weight: 8-15 parts of water, 0.01-0.1 part of sodium hydroxide, 2-6 parts of zinc oxide and 0.5-2 parts of tetraethyl orthosilicate. The modified oxidizer is applicable to preparing rubber products. The invention avoids the pipeline blockage caused by high dead rubber tendency by adding common zinc oxide during curing, reduces the disassembly/assembly and cleaning frequency of the mixing machine head, and enhances the production efficiency.
Description
Technical field
The invention belongs to rubber field is and in particular to modified zinc oxide, its preparation method and its in rubber
Application.
Background technology
As a kind of important inorganic activator in rubber industry, its effect is to give full play to organic accelerator to zinc oxide
Effect, reduce accelerator dosage or shorten cure time, it forms activation system with stearic acid, has reinforcement to multiple accelerator
The effect promoting.In existing Deng Lu law popularization technique, zinc oxide pump is entered in latex-air mixture by an injection needle
Add before entering bubble head, be difficult in the short time be uniformly dispersed, not only cause deposition of zinc oxide and dead glue phenomenon serious, Er Qie great
Increased greatly the dismounting of foaming die and cleaning moreover it is possible to lead to pipeline inner pressure excessive, each dispensing piping flow is difficult to essence
Really control, final pipe breakage, material sputtering.Meanwhile, the necessary strict control condition of this technique, otherwise in continuous production, easily
Form gel in the utensil of perfusion and block, in Batch Process, easily cause sizing material and not yet fill mould and produce showing of gel
As reducing production efficiency.
Content of the invention
The present invention is directed to problem above, there is provided a kind of Simplified flowsheet operation, promotes being uniformly distributed, to oxidation of zinc oxide
Zinc surface is modified processing, and generates silicon dioxide by hydrolyzing tetraethyl orthosilicate in the solution, is coated on zinc oxide surface,
Avoid latex and zinc oxide directly contact, stirring can be added when maturation together with the dispensings such as sulfur to mix maturation, make
When obtaining high temperature vulcanized, the silicon dioxide of zinc oxide outer layer is by caustic corrosion thus giving full play to the modified oxidized of sulfuration activation
Zinc, its preparation method and its application in rubber.
The technical scheme is that：
Modified zinc oxide includes each component of following weight portion：Water 8-15 part, sodium hydroxide 0.01-0.1 part, zinc oxide 2-6 part
With tetraethyl orthosilicate 0.5-2 part.
A kind of preparation method of modified zinc oxide, comprises the following steps：
S1, water intaking add sodium hydroxide to adjust PH so that pH value is 9-11；
S2, again zinc oxide to be added to the water dispersed with stirring uniform；
S3, add tetraethyl orthosilicate, stand after continuously stirred 4-8h；Complete.
A kind of application in rubber for modified zinc oxide, by the modified oxidized dose of preparation being used for rubber.
Described rubber includes each component of following weight portion：Heveatex 80-120 part, potassium pyrophosphate 0.1-0.3
Part, sulfur 1-5 part, modified zinc oxide 0.5-3 part, potassium oleate 2-6 part and potassium ricinoleate 0.5-3 part.
The preparation method of described rubber is：
By Heveatex, potassium pyrophosphate, sulfur, modified zinc oxide, potassium oleate and potassium ricinoleate mix and blend, add hydroxide
Potassium adjusts PH so that pH value is 8-12, more than maturation 4h, adds sclerosing agent and carries out mechanical foaming, injection molding, sizing, and sulfuration is done
Dry.
Wherein, curing temperature is 60-100 DEG C, and cure time is 30-40min.
It is an advantage of the invention that：Modified zinc oxide preparation method simple possible, easy to operate.By modified zinc oxide application
In rubber production, can be with optimization technological process, it is to avoid Deng Lu law popularization pump passes through an injection needle and adds zinc oxide easily to block
Forbidden unmanageable shortcoming with flow so that operating condition is easily controlled.Simultaneously, it is to avoid add common oxidation in maturation
Zinc easily produces dead glue, blocking pipeline, decreases dismounting and the cleaning of mixed gear end, reduces cost, improve production efficiency.
The present invention, for Simplified flowsheet, modified zinc oxide hydrolyzes generation in the basic conditions using tetraethyl orthosilicate
Silicon dioxide, is coated on the surface of zinc oxide, while improving zinc oxide dispersibility, zinc oxide surface can be stoped to connect with latex again
Touch, slow down gelation rate in foaming process for the zinc oxide, and when high temperature vulcanized, very thin silicon dioxide layer is in alkalescence condition
Lower dissolving, now just can give full play to sulfurate activity effect.Therefore modified zinc oxide can be added glue together with sulfur
Maturation in breast, compares with existing technique, and zinc oxide dispersion is more uniform, and consumption reduces and is easily controlled, and enormously simplify work
Skill flow process.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph of modified zinc oxide and the distribution diagram of element of present invention preparation.
Specific embodiment
In the present invention, modified zinc oxide includes each component of following weight portion：Water 8-15 part, sodium hydroxide 0.01-0.1 part,
Zinc oxide 2-6 part and tetraethyl orthosilicate 0.5-2 part.
Optimal enforcement mode one is：Described each group is divided into：8 parts of water, 0.02 part of sodium hydroxide, 3 parts of zinc oxide and positive silicic acid
0.5 part of tetra-ethyl ester；The performance of so modified zinc oxide of proportioning is optimal.
Optimal enforcement mode two is：Described each group is divided into：10 parts of water, 0.05 part of sodium hydroxide, 5 parts of zinc oxide and positive silicic acid
1 part of tetra-ethyl ester；The performance of so modified zinc oxide of proportioning is optimal.
Optimal enforcement mode three is：Described each group is divided into：15 parts of water, 0.1 part of sodium hydroxide, 6 parts of zinc oxide and positive silicic acid
2 parts of tetra-ethyl ester；The performance of so modified zinc oxide of proportioning is optimal.
A kind of preparation method of modified zinc oxide, comprises the following steps：
S1, take quantitative water, add sodium hydroxide to adjust PH so that pH value is 9-11；PH value is higher, and tetraethyl orthosilicate hydrolyzes
Speed is faster；
S2, again zinc oxide to be added to the water dispersed with stirring uniform；
S3, add tetraethyl orthosilicate, stand after continuously stirred 4-8h, stirring at least 4h can make tetraethyl orthosilicate hydrolyze
Completely；Complete.
A kind of application in rubber for modified zinc oxide, by the modified oxidized dose of preparation being used for rubber.
Described rubber includes each component of following weight portion：Heveatex 80-120 part, potassium pyrophosphate 0.1-0.3
Part, sulfur 1-5 part, modified zinc oxide 0.5-3 part, potassium oleate 2-6 part and potassium ricinoleate 0.5-3 part.
Optimal enforcement mode one is：Described each group is divided into：80 parts of Heveatex, 0.1 part of potassium pyrophosphate, 2 parts of sulfur, modification
0.5 part of zinc oxide, 2 parts of potassium oleate and 0.5 part of potassium ricinoleate；The resilience of so rubber of proportioning is preferable.
Optimal enforcement mode two is：Described each group is divided into：100 parts of Heveatex, 0.1 part of potassium pyrophosphate, 4 parts of sulfur, change
1.5 parts of zinc oxide of property, 4 parts of potassium oleate and 1.8 parts of potassium ricinoleate；The resilience of so rubber of proportioning is preferable.
Optimal enforcement mode three is：Described each group is divided into：120 parts of Heveatex, 0.3 part of potassium pyrophosphate, 5 parts of sulfur, change
3 parts of zinc oxide of property, 5 parts of potassium oleate and 2 parts of potassium ricinoleate；The resilience of so rubber of proportioning is preferable.
The preparation method of described rubber is：
By Heveatex, potassium pyrophosphate, sulfur, modified zinc oxide, potassium oleate and potassium ricinoleate mix and blend, add hydroxide
Potassium adjusts PH so that pH value is 8-12, more than maturation 4h, adds sclerosing agent and carries out mechanical foaming, injection molding, sizing, and sulfuration is done
Dry.Adding potassium hydroxide to adjust pH value is 10 about, so can reach the isoelectric point, IP of potassium oleate, easily foam, be also beneficial to
Corrode silicon dioxide in sulfidation.
Wherein, curing temperature is 60-100 DEG C, and cure time is 30-40min, so so that rubber full cure.
In the present invention：Sulfur belongs to vulcanizing agent, produces cross-linking reaction with rubber so as to form space network, makes rubber
Glue is changed into elastomeric material from plastic material, has the use value of preciousness；
Potassium ricinoleate, as latex foam stabilizer, can prevent latex foam from rupturing, maintain foam stabilization；
As foaming agent, can be dissolved in water makes Scatter Light of Bubble Interface in Water tension force reduce to potassium oleate, forms protective layer around bubble, thus
Produce foam；
Potassium pyrophosphate belongs to anion surfactant, as dispersant, chelating agen, can chelate the metal ions such as calcium, magnesium.
Modified zinc oxide, as vulcanization accelerator, can promote the sulfuration of cellular rubber.
In concrete application,
First, the preparation of modified zinc oxide：Take the water of 100g, add sodium hydroxide to adjust PH to 11, then 50g zinc oxide is added
In water, dispersed with stirring uniformly, adds the tetraethyl orthosilicate of 10g, stops, obtaining product after continuously stirred 5h.
Secondly, by Heveatex, potassium pyrophosphate, sulfur, modified zinc oxide, potassium oleate and potassium ricinoleate mix and blend,
Add potassium hydroxide to adjust pH=10, maturation 5 hours, add sclerosing agent foaming, injection molding, sizing, 80 DEG C of steam box, vulcanize 30min,
It is dried.
As shown in figure 1, the scanning electron microscope of modified zinc oxide prepared using the inventive method and distribution diagram of element.Wherein scheme
（a）For the scanning electron microscope (SEM) photograph of modified zinc oxide, scheme（b）、（c）、（d）It is the scattergram of element Zn, O, Si respectively, with figure（a）Right
Should be evenly distributed, show zinc oxide by coated with silica it is seen then that element Zn, O, Si all exist in a large number.
Claims (6)
1. a kind of modified zinc oxide is it is characterised in that include each component of following weight portion：Water 8-15 part, sodium hydroxide 0.01-
0.1 part, zinc oxide 2-6 part and tetraethyl orthosilicate 0.5-2 part.
2. a kind of preparation method of the modified zinc oxide described in claim 1 is it is characterised in that comprise the following steps：
S1, water intaking add sodium hydroxide to adjust PH so that pH value is 9-11；
S2, again zinc oxide to be added to the water dispersed with stirring uniform；
S3, add tetraethyl orthosilicate, stand after continuously stirred 4-8h；Complete.
3. a kind of application in rubber for the modified zinc oxide described in claim 1 is it is characterised in that by modified oxidized dose
Preparation for rubber.
4. a kind of application in rubber for the modified zinc oxide according to claim 4 is it is characterised in that described rubber
Product includes each component of following weight portion：Heveatex 80-120 part, potassium pyrophosphate 0.1-0.3 part, sulfur 1-5 part, modification
Zinc oxide 0.5-3 part, potassium oleate 2-6 part and potassium ricinoleate 0.5-3 part.
5. a kind of application in rubber for the modified zinc oxide according to claim 4 is it is characterised in that described rubber
The preparation method of product is：
By Heveatex, potassium pyrophosphate, sulfur, modified zinc oxide, potassium oleate and potassium ricinoleate mix and blend, add hydroxide
Potassium adjusts PH so that pH value is 8-12, more than maturation 4h, adds sclerosing agent and carries out mechanical foaming, injection molding, sizing, and sulfuration is done
Dry.
6. a kind of application in rubber for the modified zinc oxide according to claim 5 it is characterised in that wherein, sulfur
Change temperature and be 60-100 DEG C, cure time is 30-40min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610910407.7A CN106380643B (en) | 2016-10-19 | 2016-10-19 | A kind of modified zinc oxide, its preparation method and its application in rubber |
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| CN201610910407.7A CN106380643B (en) | 2016-10-19 | 2016-10-19 | A kind of modified zinc oxide, its preparation method and its application in rubber |
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| CN106380643B CN106380643B (en) | 2018-03-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788978A (en) * | 2021-10-19 | 2021-12-14 | 江苏金世缘乳胶制品股份有限公司 | Production process for preparing natural latex sponge by using high-temperature die |
| CN118006051A (en) * | 2024-04-08 | 2024-05-10 | 寿光福麦斯轮胎有限公司 | Rubber composition for tire inner liner and preparation method thereof |
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| CN1511889A (en) * | 2002-12-27 | 2004-07-14 | 北京服装学院 | Surface modified nano zinc oxide water dispersion and its preparing method and use |
| JP2006299126A (en) * | 2005-04-21 | 2006-11-02 | Nissan Motor Co Ltd | Method for modifying surface of nano-filler, polymer nano-composite and method for producing polymer nano-composite |
| CN101543466A (en) * | 2009-04-23 | 2009-09-30 | 河南大学 | Nano zinc oxide surface modifying method |
| CN103923642A (en) * | 2014-04-18 | 2014-07-16 | 佛山市金帮光电科技股份有限公司 | Preparation method of inorganic ZnO-based quantum dot modified organic silicon resin |
-
2016
- 2016-10-19 CN CN201610910407.7A patent/CN106380643B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511889A (en) * | 2002-12-27 | 2004-07-14 | 北京服装学院 | Surface modified nano zinc oxide water dispersion and its preparing method and use |
| JP2006299126A (en) * | 2005-04-21 | 2006-11-02 | Nissan Motor Co Ltd | Method for modifying surface of nano-filler, polymer nano-composite and method for producing polymer nano-composite |
| CN101543466A (en) * | 2009-04-23 | 2009-09-30 | 河南大学 | Nano zinc oxide surface modifying method |
| CN103923642A (en) * | 2014-04-18 | 2014-07-16 | 佛山市金帮光电科技股份有限公司 | Preparation method of inorganic ZnO-based quantum dot modified organic silicon resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788978A (en) * | 2021-10-19 | 2021-12-14 | 江苏金世缘乳胶制品股份有限公司 | Production process for preparing natural latex sponge by using high-temperature die |
| CN118006051A (en) * | 2024-04-08 | 2024-05-10 | 寿光福麦斯轮胎有限公司 | Rubber composition for tire inner liner and preparation method thereof |
| CN118006051B (en) * | 2024-04-08 | 2024-08-23 | 寿光福麦斯轮胎有限公司 | Rubber composition for tire inner liner and preparation method thereof |
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| CN106380643B (en) | 2018-03-27 |
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