CN110713638B - Hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and preparation method thereof - Google Patents
Hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110713638B CN110713638B CN201810755221.8A CN201810755221A CN110713638B CN 110713638 B CN110713638 B CN 110713638B CN 201810755221 A CN201810755221 A CN 201810755221A CN 110713638 B CN110713638 B CN 110713638B
- Authority
- CN
- China
- Prior art keywords
- hydrotalcite
- natural rubber
- composite material
- butadiene rubber
- epoxy natural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- 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
Abstract
The invention discloses a hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and a preparation method thereof. The composite material is prepared from the following raw materials: epoxy natural rubber and styrene butadiene rubber, modified hydrotalcite powder, an anti-aging agent, an accelerator, a vulcanizing agent, stearic acid, zinc oxide and a filler; the modified hydrotalcite powder is prepared by a method comprising the following steps: (1) drying and calcining the hydrotalcite slurry, and then placing the calcined hydrotalcite slurry into an anion solution to obtain laminate stripping hydrotalcite slurry; (2) mixing the laminate stripping hydrotalcite slurry with a coupling agent, performing ultrasonic dispersion and drying to obtain modified hydrotalcite powder; the modified laminate peeled hydrotalcite powder provided by the invention can be used as an excellent reinforcing filler to be introduced into rubber reinforcement, so that the air tightness and the flexing resistance of a rubber composite material are improved, the process is simple, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and a preparation method thereof.
Background
Hydrotalcite is a Layered Double Hydroxide (LDHs), an anionic clay mineral, and an inorganic Layered compound with alkalinity and anion intercalation ability. The source of the plant can be natural exploitation or artificial synthesis. The preparation process is simple, the price is low, and the component structure is controllable, so the preparation method has been developed greatly in recent years. Not only can the anions between the hydrotalcite sheets be replaced, but also the metal cations between the sheets can be replaced by divalent or trivalent metal cations with similar radiuses, thereby obtaining more excellent comprehensive performance. The hydrotalcite is a large-sheet structure with high surface-to-thickness ratio, and the size of the sheet layer can reach micron level. The laminate structure is regular octahedron, metal cation is in the center of the octahedron, hydroxide radical is in the angle of the octahedron, and adjacent octahedron are connected with each other by common edges to form two-dimensionally extended metal hydroxide. The performance characteristics of hydrotalcite mainly comprise six aspects: (1) high aspect ratio sheet materials; (2) alkalinity; (3) the adjustability of the composition of the laminate; (4) exchangeability of anions between layers; (5) flame retardant properties; (6) memory effects and thermal stability. The invention mainly utilizes the high surface-to-thickness ratio characteristic of the hydrotalcite. The hydrotalcite powder is added into the rubber, and the rubber is calendered and oriented on an open mill, so that the gas is effectively blocked from passing through, the crack propagation is effectively resisted, and the air tightness is improved.
The traditional hydrotalcite has single type of functional groups, and cannot well react with the functional groups on the rubber matrix to form a cross-linked network. Therefore, the introduction of the coupling agent for modification increases the reactive functional groups, so that the hydrotalcite and the rubber matrix are combined more tightly, the hydrotalcite migration and agglomeration phenomenon is reduced, the hydrotalcite is dispersed better, and the composite material has better performance. Hydrotalcite modification can be used for pertinently introducing certain functional groups to enhance specific properties. Such as: the surface of the hydrotalcite laminate is modified by acetyl propylamino triethoxysilane, and other complexes are introduced, so that the problems of dispersion of hydrotalcite in a polymer matrix, interface performance between hydrotalcite and the polymer matrix and the like are solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and a preparation method thereof. The hydrotalcite is peeled off at high temperature to be changed into a single-layer plate structure, then the hydrotalcite is modified by a coupling agent, and functional groups on the coupling agent are combined with a rubber matrix, so that the hydrotalcite is favorably dispersed in the rubber matrix. The hydrotalcite is a large-sheet structure, and can block the gas passing path and effectively resist crack propagation when added into the rubber matrix, thereby improving the air tightness and the flexing resistance of the composite material. Orientation is realized through the shearing action of the open mill on the composite material, so that hydrotalcite particles are orderly arranged in a rubber matrix, and the air tightness and the flexibility resistance of the rubber composite material are greatly improved.
The invention aims to provide a hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material.
The composite material is prepared from the following raw materials:
epoxy natural rubber and styrene butadiene rubber, modified hydrotalcite powder, an anti-aging agent, an accelerator, a vulcanizing agent, stearic acid, zinc oxide and a filler;
the components are calculated according to the parts by weight,
100 parts by weight of epoxy natural rubber and styrene-butadiene rubber;
1-3 parts of an anti-aging agent; preferably 0.5 to 1 part by weight;
1-100 parts by weight of modified hydrotalcite powder; preferably 5 to 15 parts by weight;
1-100 parts by weight of a filler; preferably 20 to 50 parts by weight.
The modified hydrotalcite powder is prepared by a method comprising the following steps:
(1) drying and calcining the hydrotalcite slurry, and then placing the calcined hydrotalcite slurry into an anion solution to obtain laminate stripping hydrotalcite slurry; the anion is NO3 -、F-、Cl-、Br-、I-、CO3 2-、SO4 2-Or OH-；
(2) Mixing the laminate stripping hydrotalcite slurry with a coupling agent, performing ultrasonic dispersion and drying to obtain modified hydrotalcite powder;
the usage range ratio of the hydrotalcite to the coupling agent is (0.5-500): 1; preferably (10-50): 1.
In particular, the amount of the solvent to be used,
(1) drying the hydrotalcite slurry in an oven at 60-100 ℃ to powder, placing the hydrotalcite powder in a muffle furnace at 500-600 ℃ to calcine for 1-5 h to obtain a metal composite oxide, and finally placing the metal composite in an anion solution to obtain laminate-stripped hydrotalcite slurry;
(2) the laminate stripping hydrotalcite slurry is mixed with a coupling agent and ultrasonically dispersed for 10min to 3h at 30kHz to 120kHz and 40 ℃ to 60 ℃; and (3) drying the mixed slurry in an oven at the temperature of 60-100 ℃ for 10-50 h to obtain the modified hydrotalcite powder.
Wherein the content of the first and second substances,
the coupling agent is a silane coupling agent, a phosphate coupling agent or an aluminate coupling agent.
The dosage ratio of the epoxy natural rubber to the styrene butadiene rubber is 10: 90-90: 10; preferably 40: 60-60: 40.
the epoxy degree of the epoxy natural rubber is 5-75%. The lower the epoxy degree of the epoxy natural rubber is, the fewer epoxy groups are, the poorer the air tightness is, and the better the flex resistance is; the higher the epoxy degree, the more epoxy groups, the better the air-tightness and the poorer the flex resistance. Comprehensively considering, the epoxy natural rubber with the epoxy degree of 5-75 percent is selected.
The filler is one or a combination of carbon black, white carbon black, organic resin, argil, calcium carbonate, fly ash, fibers, silicates and metal powder;
the accelerator can be one or a combination of accelerators conventional in the field, preferably thiazole accelerators, sulfenamide accelerators, thiurams, thiourea accelerators, aldehyde ammonia accelerators, dithiocarbamates, guanidines or xanthates; the dosage is also conventional, and the preferred dosage is 1-5 parts by weight;
the anti-aging agent can be a conventional anti-aging agent in the field, and is preferably quinoline, paraphenylenediamine or naphthylamine;
the vulcanizing agent can adopt a conventional vulcanizing agent in the field, and preferably sulfur or peroxide vulcanizing agent;
the zinc oxide and the stearic acid are used in conventional amounts, and 1-5 parts by weight is preferred in the invention.
Conventional auxiliaries can be added into the formula of the application according to actual conditions, such as: a plasticizer, a lubricant, a dispersant, a resin, and a filler. The dosage is also conventional dosage, and the skilled person can determine the dosage according to actual conditions.
The second purpose of the invention is to provide a preparation method of the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material.
The method comprises the following steps:
the components are mixed and vulcanized according to the using amount to prepare the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material.
Among them, it is preferable that,
the vulcanization pressure is 15 Mpa-50 Mpa, the vulcanization temperature is 145 ℃ -170 ℃, and the vulcanization time is 5 min-40 min.
The traditional unmodified hydrotalcite has few types of reactive functional groups on the surface, and the reactive functional groups are introduced after the surface is grafted and modified by a coupling agent, so that the hydrotalcite is indirectly combined with the functional groups (such as epoxy groups) on the rubber matrix more tightly. The un-stripped hydrotalcite has a double-layer structure, so that rubber molecules are easy to have intercalation; and the orientation of the double-layer hydrotalcite in the rubber is different, gas easily permeates from the layers, and the two phenomena can cause the gas tightness enhancement of the hydrotalcite to be unobvious, so that the hydrotalcite is stripped, and is added into the composite material in a single-layer structure to further improve the gas tightness. The hydrotalcite after stripping has larger specific surface area. However, too much hydrotalcite is added to introduce interface defects, which degrades various properties.
Epoxidized natural rubber (RNR) is prepared by modifying Natural Rubber (NR) by epoxidation reaction, and a part of double bonds on the rubber molecular chain is oxidized. After epoxidation, the polarity of rubber macromolecules is increased, and intermolecular force is enhanced. Thus, ENR retains the basic structural and performance characteristics of NR while producing many unique properties, including excellent air barrier properties, excellent oil resistance, compatibility and wet skid resistance, low rolling resistance and good adhesion to other materials. At present, the ENR is mainly applied to products with high requirements on oil resistance and air tightness, such as tyre covers, inner liners of tubeless tyres and the like, and can be used with other high polymer materials to prepare various composite materials. Because the tire inner liner needs certain flexing resistance and the epoxy natural rubber has poor performance in the aspect, the styrene-butadiene rubber and the modified hydrotalcite are used together.
Styrene Butadiene Rubber (SBR) is a polystyrene butadiene copolymer. The flame-retardant and flame-retardant modified polyvinyl chloride cable has the characteristics of good weather resistance, ozone aging resistance, self-extinguishing property, good oil resistance, excellent tensile strength, elongation and elasticity and the like. The rubber can be used together with natural rubber and various synthetic rubbers, is widely applied to the fields of production of tires, adhesive tapes, rubber tubes, wires and cables, medical appliances, various rubber products and the like, is the largest universal synthetic rubber variety, and is one of the earliest rubber varieties for realizing industrial production. Because of poor air tightness, the epoxy natural rubber with better air tightness and the modified laminate are used for stripping the hydrotalcite.
The invention can adopt the following technical scheme:
the preparation of the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material comprises the following steps:
a. preparing modified laminate stripping hydrotalcite powder:
and (2) drying 5-500 g of hydrotalcite slurry in a drying oven at 60-100 ℃ to obtain powder, placing the hydrotalcite powder in a muffle furnace at 500-600 ℃ to calcine for 1-5 h to obtain metal composite oxide (LDO for short), and finally placing the LDO in a specific anion solution to obtain laminate peeling hydrotalcite slurry.
Taking out 5-500 g of laminate stripping hydrotalcite slurry, mixing with 1-10 g of coupling agent, and performing ultrasonic dispersion for 10 min-3 h at 30-120 kHz and 40-60 ℃. And (3) fully contacting the hydrotalcite with the coupling agent, and then drying the mixed slurry in an oven at the temperature of 60-100 ℃ for 10-50 h to obtain the coupling agent grafted modified laminate exfoliated hydrotalcite powder.
The raw material components of the invention comprise silane coupling agent KH550, silane coupling agent KH570, silane coupling agent KH580, silane coupling agent Si-69, phosphate coupling agent and aluminate coupling agent. .
b. A preparation method of a high-performance hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material comprises the following steps:
based on 100 parts of the total mass of the epoxy natural rubber and the styrene butadiene rubber,
the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material comprises the following components in parts by weight:
the preparation method comprises the following steps: adding epoxy natural rubber and styrene-butadiene rubber in a certain ratio (10: 90-90: 10) into an open mill or an internal mixer, then adding stearic acid and zinc oxide for mixing for a period of time, then adding an anti-aging agent, adding a modified laminate, peeling hydrotalcite powder, adding a filler, finally adding an accelerator and a crosslinking agent to prepare hydrotalcite/epoxy natural rubber/styrene-butadiene rubber mixed rubber, and rolling and orienting for 1-10 times on the open mill. And preparing the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material through vulcanization, and finally carrying out performance test.
The preparation method of the epoxy natural rubber and the epoxy natural rubber/styrene butadiene rubber composite material has simple system and process and is easy to expand.
The rubber composite material prepared by the invention has excellent characteristics and performances, such as: good air tightness, flexibility resistance and mechanical property.
The modified laminate peeled hydrotalcite powder provided by the invention can be used as an excellent reinforcing filler to be introduced into rubber reinforcement, so that the air tightness and the flexing resistance of a rubber composite material are improved, the process is simple, and the industrial production is easy to realize.
Detailed Description
The present invention will be further described with reference to the following examples.
Various hydrotalcites (LDHs) prepared by self;
coprecipitation methods, such as magnesium aluminum hydrotalcite preparation: with 0.2mol Mg (NO)3)2·6H2O and 0.05
molAl(NO3)3·9H2O is prepared into a salt solution by using NaOH and Na2O3Preparing into alkaline solution, dripping the two solutions into a beaker at a speed of 1 drop/s, keeping the temperature at 40 ℃, keeping the pH value between 9 and 10, stirring for 1h after dripping is finished, crystallizing at 60 ℃ for 12h, and pumpingAnd filtering, washing to neutrality, and drying the precipitate to obtain Mg/Al hydrotalcite.
Epoxy natural rubber, self-made;
the epoxidation reaction is carried out in a 1L three-necked bottle, firstly deionized water is used for diluting the natural concentration of epoxy to 20%, a stabilizing agent (OPEO) is added while stirring for stabilization for 15min, then a certain amount of formic acid and a certain amount of hydrogen peroxide are slowly added, the temperature is kept at 40 ℃ for 1 h-16 h (different time and different epoxy degrees) until the reaction is finished, and the temperature of a sample is reduced to room temperature by a cold water bath. The composition was washed with an amount of methanol to neutralize excess formic acid. The excess liquid was squeezed out with a filter cloth. Drying in a 50 ℃ oven for 24 h.
Styrene butadiene rubber 1502, a commercially available product;
carbon black N660, degussa N660; accelerators, anti-aging agents, stearic acid and zinc oxide, all of which are Hibei Yanbang chemical technology Co., Ltd;
sulfur, linyi star chemical ltd; various fillers and commercial products.
Comparative example 1
a. Preparation of epoxy natural rubber/styrene-butadiene rubber composite (without hydrotalcite filler):
the formula is as follows: the following raw material components by mass
The preparation method comprises the following steps: 50: 50 parts of epoxidized natural rubber (35% epoxy degree) and styrene-butadiene rubber are added into an internal mixer, then 2g of stearic acid and 3g of zinc oxide are added for mixing for a period of time, then 0.5g of antioxidant RD is added, finally 2.5g of accelerator DM and 2g of sulfur are added to prepare an epoxidized natural rubber/styrene-butadiene rubber mixed rubber, and the mixed rubber is rolled and oriented for 3 times on an open mill. Under the vulcanization pressure of 15 MPa; the vulcanization temperature is 145 ℃; and (3) preparing the epoxy natural rubber/styrene butadiene rubber composite material under the condition of 5min of vulcanization time, and finally carrying out performance test.
Example 1
a. Preparing modified laminate stripping hydrotalcite powder:
taking 5g of magnesium-aluminum waterDrying the talc slurry in a 60 ℃ oven to be powder, then placing the magnesium-aluminum hydrotalcite powder in a 500 ℃ muffle furnace to be calcined for 1h to obtain magnesium-aluminum metal composite oxide (LDO for short), and finally placing the magnesium-aluminum LDO in a furnace with OH-And obtaining laminate stripping magnesium aluminum hydrotalcite slurry in the anion solution.
Taking out 5g of magnesium-aluminum laminate stripped hydrotalcite slurry, mixing with 1g of silane coupling agent KH550, and ultrasonically dispersing at 120kHz and 60 ℃ for 3 h. And (3) fully contacting the hydrotalcite with the coupling agent, and then placing the mixed slurry in a drying oven at 100 ℃ for drying for 50h to obtain the coupling agent grafted modified laminate stripped magnesium aluminum hydrotalcite powder.
b. A preparation method of a high-performance hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material comprises the following steps:
the formula is as follows: the following raw material components by mass
The preparation method comprises the following steps: 10: 90 g of epoxidized natural rubber (5% epoxy degree) and styrene-butadiene rubber are added into an internal mixer, then 5g of stearic acid and 5g of zinc oxide are added for mixing for a period of time, then 1g of antioxidant SP is added, 1g of modified laminate is added to strip magnesium aluminum hydrotalcite powder and 100g of carbon black N990 filler is added, finally 5g of accelerator DZ and 5g of sulfur are added to prepare hydrotalcite/epoxidized natural rubber/styrene-butadiene rubber compound, and the hydrotalcite/epoxidized natural rubber/styrene-butadiene rubber compound is rolled and oriented on an open mill for 1 time. Under the vulcanization pressure of 20 MPa; the vulcanization temperature is 150 ℃; and preparing the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material under the condition of 10min of vulcanization time, and finally carrying out performance test.
Example 2
a. Preparing modified laminate stripping hydrotalcite powder:
100g of magnesium-chromium hydrotalcite slurry is dried to be powder in a 70 ℃ oven, then the magnesium-chromium hydrotalcite powder is placed in a 520 ℃ muffle furnace to be calcined for 2 hours to obtain magnesium-chromium metal composite oxide (LDO for short), and finally the magnesium-chromium LDO is placed in a muffle furnace with CO3 2-Obtaining laminate stripping magnesium chromium hydrotalcite serous fluid in the anion solution.
100g of the magnesium-chromium laminate stripping hydrotalcite slurry is taken out and mixed with 3g of silane coupling agent KH560, and the mixture is subjected to ultrasonic dispersion for 2.5 hours at 100kHz and 55 ℃. And (3) fully contacting the hydrotalcite with the coupling agent, and then placing the mixed slurry in a 90 ℃ oven for drying for 40h to obtain the coupling agent grafted modified laminate peeled magnesium-chromium hydrotalcite powder.
b. A preparation method of a high-performance hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material comprises the following steps:
the formula is as follows: the following raw material components by mass
The preparation method comprises the following steps: 20:80 of epoxy natural rubber (15 percent of epoxy degree) and styrene butadiene rubber are added into an open mill, then 4g of stearic acid and 2g of zinc oxide are added for mixing for a period of time, then 1.5g of age inhibitor D is added, 20g of modified laminate stripped magnesium chromium hydrotalcite powder is added, 80g of carbon black N660 filler is added, finally 3g of accelerator D and 4g of sulfur are added to prepare hydrotalcite/epoxy natural rubber/styrene butadiene rubber mixed rubber, and rolling and orientation are carried out for 3 times on the open mill. Under a vulcanization pressure of 25 MPa; the vulcanization temperature is 155 ℃; preparing the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material under the condition of 15min of vulcanization time, and finally carrying out performance test.
Example 3
a. Preparing modified laminate stripping hydrotalcite powder:
drying 200g of lithium aluminum hydrotalcite slurry in an oven at 80 ℃ to obtain powder, placing the lithium aluminum hydrotalcite powder in a muffle furnace at 540 ℃ to calcine the powder for 3 hours to obtain a lithium aluminum metal composite oxide (LDO for short), and finally placing the lithium aluminum LDO in NO3 -And obtaining laminate stripping lithium aluminum hydrotalcite slurry in the anion solution.
200g of the lithium aluminum laminate-peeled hydrotalcite slurry was taken out and mixed with 5g of silane coupling agent KH570, and ultrasonically dispersed at 80kHz and 50 ℃ for 2 hours. And (3) fully contacting the hydrotalcite with the coupling agent, and then placing the mixed slurry in an oven at 80 ℃ for drying for 30h to obtain the coupling agent grafted modified laminate stripped lithium aluminum hydrotalcite powder.
b. A preparation method of a high-performance hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material comprises the following steps:
the formula is as follows: the following raw material components by mass
The preparation method comprises the following steps: adding 60 parts of epoxy natural rubber (25 percent of epoxy degree) and styrene-butadiene rubber into an open mill, adding 3g of stearic acid and 3g of zinc oxide, mixing for a period of time, then adding 2g of an anti-aging agent, adding 40g of modified laminate stripped lithium aluminum hydrotalcite powder, adding 60g of carbon black N440 filler, finally adding 4g of an accelerator M and 3g of sulfur to prepare hydrotalcite/epoxy natural rubber/styrene-butadiene rubber compound, and rolling and orienting for 5 times on the open mill. Under the vulcanization pressure of 30 MPa; the vulcanization temperature is 160 ℃; preparing the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material under the condition of vulcanizing time of 20min, and finally carrying out performance test.
Example 4
a. Preparing modified laminate stripping hydrotalcite powder:
drying 300g of zinc-aluminum hydrotalcite slurry in a 85 ℃ oven to powder, then placing the zinc-aluminum hydrotalcite powder in a 560 ℃ muffle furnace to calcine for 4 hours to obtain a zinc-aluminum metal composite oxide (LDO for short), and finally placing the zinc-aluminum LDO in SO4 2-And obtaining the zinc-aluminum laminate stripping hydrotalcite slurry in the anion solution.
300g of zinc-aluminum laminate stripping hydrotalcite slurry is taken out and mixed with 7g of silane coupling agent KH580, and ultrasonic dispersion is carried out for 1.5h at 60kHz and 45 ℃. And (3) fully contacting the hydrotalcite with the coupling agent, and drying the mixed slurry in an oven at 70 ℃ for 20 hours to obtain the coupling agent grafted modified laminate stripped zinc-aluminum hydrotalcite powder.
b. A preparation method of a high-performance hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material comprises the following steps:
the formula is as follows: the following raw material components by mass
The preparation method comprises the following steps: 60:40 epoxy natural rubber (45% epoxy degree) and styrene-butadiene rubber are added into an internal mixer, then 2g of stearic acid and 3g of zinc oxide are added for mixing for a period of time, then 2.5g of anti-aging agent 2246 is added, 60g of modified laminate is added to strip zinc-aluminum hydrotalcite powder and 40g of carbon black N220 filler is added, finally 3g of accelerator DM and 5g of sulfur are added to prepare hydrotalcite/epoxy natural rubber/styrene-butadiene rubber mixed rubber, and the hydrotalcite/epoxy natural rubber/styrene-butadiene rubber mixed rubber is rolled and oriented for 7 times on an open mill. Under the vulcanization pressure of 35 MPa; the vulcanization temperature is 165 ℃; preparing the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material under the condition of 25min of vulcanization time, and finally carrying out performance test.
Example 5
a. Preparing modified laminate stripping hydrotalcite powder:
drying 400g of calcium-magnesium hydrotalcite slurry in a 90 ℃ oven to obtain powder, placing the calcium-magnesium hydrotalcite powder in a 580 ℃ muffle furnace to calcine for 4.5 hours to obtain calcium-magnesium metal composite oxide (LDO for short), and finally placing the LDO in Cl-And obtaining laminate stripping calcium-magnesium hydrotalcite slurry in the anion solution.
400g of the calcium-magnesium laminate-peeled hydrotalcite slurry was taken out and mixed with 9g of a silane coupling agent Si-69, and subjected to ultrasonic dispersion at 40kHz and 40 ℃ for 1 hour. And (3) fully contacting the hydrotalcite with the coupling agent, and then placing the mixed slurry in a 65 ℃ drying oven for drying for 15h to obtain the coupling agent grafted modified laminate peeled calcium-magnesium hydrotalcite powder.
b. A preparation method of a high-performance hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material comprises the following steps:
the formula is as follows: the following raw material components by mass
The preparation method comprises the following steps: 80:20 of natural rubber epoxide (65% of epoxy degree) and styrene butadiene rubber are added into an open mill, 1g of stearic acid and 2g of zinc oxide are added for mixing for a period of time, then 2.5g of antioxidant RD is added, 80g of modified laminate is added to strip calcium magnesium hydrotalcite powder and 20g of carbon black N110 filler is added, finally 2g of accelerator H and 2g of sulfur are added to prepare hydrotalcite/natural rubber epoxide/styrene butadiene rubber compound, and rolling and orientation are carried out on the open mill for 9 times. Under the vulcanization pressure of 40 MPa; the vulcanization temperature is 170 ℃; preparing the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material under the condition of vulcanizing for 30min, and finally carrying out performance test.
Example 6
a. Preparing modified laminate stripping hydrotalcite powder:
oven drying 500g Mg-Fe hydrotalcite slurry in 100 deg.C oven to obtain powder, calcining in 600 deg.C muffle furnace for 5 hr to obtain Mg-Fe metal composite oxide (LDO), and placing the LDO in OH-And obtaining laminate stripping magnesium-iron hydrotalcite slurry in the anion solution.
And taking out 500g of magnesium-iron laminate stripped hydrotalcite slurry, mixing the magnesium-iron laminate stripped hydrotalcite slurry with 10g of aluminate coupling agent, and performing ultrasonic dispersion for 10min at 30kHz and 40 ℃. And (3) fully contacting the hydrotalcite with the coupling agent, and then drying the mixed slurry in a 60-DEG C drying oven for 10h to obtain the coupling agent grafted modified laminate stripped magnesium-iron hydrotalcite powder.
b. A preparation method of a high-performance hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material comprises the following steps:
the formula is as follows: the following raw material components by mass
The preparation method comprises the following steps: adding 90:10 epoxy natural rubber (75% epoxy degree) and styrene-butadiene rubber into an open mill, adding 1.5g of stearic acid and 1g of zinc oxide, mixing for a period of time, then adding 3g of antioxidant 4010NA, adding 100g of modified laminate stripped magnesium-iron hydrotalcite powder and 1g of carbon fiber filler, finally adding 2g of peroxide DCP to prepare hydrotalcite/epoxy natural rubber/styrene-butadiene rubber compound, and rolling and orienting for 10 times on the open mill. Under a vulcanization pressure of 50 MPa; the vulcanization temperature is 170 ℃; preparing the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material under the condition of vulcanizing time of 40min, and finally carrying out performance test.
The test results of the examples and comparative examples are shown in table 1:
mechanical properties: GB/T528-2009; air permeability coefficient: ISO 2782; flex fatigue: GB/T13943-2006
TABLE 1
Note: number of flexional cycles with flexural fatigue of first order crack
According to the data of 6 examples and 1 comparative example in the table. The tensile strength and flex fatigue increased and then decreased with increasing hydrotalcite loading, and the performance was best in both examples 2 and 3. This is because the addition of a certain amount of hydrotalcite can effectively improve the mechanical properties and the flex resistance of the composite material, but the introduction of a large amount of hydrotalcite can lead to poor dispersion in the rubber matrix, resulting in interfacial defects. The smaller the permeability coefficient, the better the airtightness. The data in the table show that the air tightness is reduced along with the increase of the using amount of the styrene butadiene rubber, but the air permeability coefficient is increased after being reduced by adding the hydrotalcite, which shows that the air tightness of the material can be improved by a small amount of LDH, and the air tightness is reduced by introducing excessive LDH due to excessive interface defects. The improved gas tightness may also be the orientation of the LDH sheets by the strong shear of the mill.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material is characterized by being prepared from the following raw materials:
epoxy natural rubber and styrene butadiene rubber, modified hydrotalcite powder, an anti-aging agent, an accelerator, a vulcanizing agent, stearic acid, zinc oxide and a filler;
the components are calculated according to the parts by weight,
the modified hydrotalcite powder is prepared by a method comprising the following steps:
(1) drying the hydrotalcite slurry in an oven at 60-100 ℃ to powder, placing the hydrotalcite powder in a muffle furnace at 500-600 ℃ to calcine for 1-5 h to obtain a metal composite oxide, and finally placing the metal composite in an anion solution to obtain laminate-stripped hydrotalcite slurry; the anion is NO3 -、F-、Cl-、Br-、I-、CO3 2-、SO4 2-Or OH-；
(2) Mixing the laminate stripping hydrotalcite slurry with a coupling agent, and ultrasonically dispersing for 10min to 3h at 30kHz to 120kHz and 40 ℃ to 60 ℃; drying the mixed slurry in an oven at 60-100 ℃ for 10-50 h to obtain modified hydrotalcite powder;
the coupling agent is a silane coupling agent, a phosphate coupling agent or an aluminate coupling agent;
the usage range ratio of the hydrotalcite to the coupling agent is (0.5-500): 1.
2. the hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material according to claim 1, wherein:
the components are calculated according to the parts by weight,
3. the hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material according to claim 1, wherein:
the usage range ratio of the hydrotalcite to the coupling agent (10-50) is 1.
4. The hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material according to claim 1, wherein:
the dosage ratio of the epoxy natural rubber to the styrene butadiene rubber is 10: 90-90: 10.
5. the hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material according to claim 1, wherein:
the epoxy degree of the epoxy natural rubber is 5-75%.
6. The hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material according to claim 1, wherein:
the filler is one or a combination of carbon black, white carbon black, organic resin, argil, calcium carbonate, fly ash, fibers, silicates and metal powder;
the accelerator is one or a combination of thiazole accelerators, sulfenamide accelerators, thiurams accelerators, thiourea accelerators, aldehyde ammonia accelerators, dithiocarbamates, guanidines or xanthate accelerators;
the anti-aging agent is quinoline, p-phenylenediamine or naphthylamine;
the vulcanizing agent is sulfur or peroxide vulcanizing agent.
7. A method for preparing the hydrotalcite/epoxy natural rubber/styrene-butadiene rubber composite material according to any one of claims 1 to 6, wherein the method comprises:
the components are mixed and vulcanized according to the using amount to prepare the hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material.
8. The method of claim 7, wherein:
the vulcanization pressure is 15MPa to 50MPa, the vulcanization temperature is 145 ℃ to 170 ℃, and the vulcanization time is 5min to 40 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810755221.8A CN110713638B (en) | 2018-07-11 | 2018-07-11 | Hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810755221.8A CN110713638B (en) | 2018-07-11 | 2018-07-11 | Hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110713638A CN110713638A (en) | 2020-01-21 |
| CN110713638B true CN110713638B (en) | 2020-12-11 |
Family
ID=69208898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810755221.8A Active CN110713638B (en) | 2018-07-11 | 2018-07-11 | Hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110713638B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955977B (en) * | 2021-11-05 | 2022-08-16 | 禹智环保科技（深圳）有限公司 | Water-permeable colored rubber pavement material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241752A (en) * | 2013-05-29 | 2013-08-14 | 肇庆学院 | Preparation method of surface-modified hydrotalcite |
| CN103374153A (en) * | 2013-06-30 | 2013-10-30 | 北京化工大学 | Preparation method of supermolecule/rubber airtight materials |
| CN104194109A (en) * | 2014-08-12 | 2014-12-10 | 中国热带农业科学院农产品加工研究所 | Thermo-oxidative ageing resistant epoxidized natural rubber composite material and preparation method thereof |
| CN104292549A (en) * | 2014-09-26 | 2015-01-21 | 北京化工大学 | Method for preparing high-filling hydrotalcite/rubber nanometer composite material |
| CN104558724A (en) * | 2015-01-26 | 2015-04-29 | 北京化工大学 | Preparation method of high-performance hydrotalcite/silicon dioxide/rubber nano composite material |
| CN108239306A (en) * | 2017-12-11 | 2018-07-03 | 山东玲珑轮胎股份有限公司 | Tire sidewall rubber composite material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2332678B (en) * | 1997-12-23 | 2000-09-27 | Ciba Sc Holding Ag | Stabilizer mixtures containing a sterically hindered amine |
-
2018
- 2018-07-11 CN CN201810755221.8A patent/CN110713638B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241752A (en) * | 2013-05-29 | 2013-08-14 | 肇庆学院 | Preparation method of surface-modified hydrotalcite |
| CN103374153A (en) * | 2013-06-30 | 2013-10-30 | 北京化工大学 | Preparation method of supermolecule/rubber airtight materials |
| CN104194109A (en) * | 2014-08-12 | 2014-12-10 | 中国热带农业科学院农产品加工研究所 | Thermo-oxidative ageing resistant epoxidized natural rubber composite material and preparation method thereof |
| CN104292549A (en) * | 2014-09-26 | 2015-01-21 | 北京化工大学 | Method for preparing high-filling hydrotalcite/rubber nanometer composite material |
| CN104558724A (en) * | 2015-01-26 | 2015-04-29 | 北京化工大学 | Preparation method of high-performance hydrotalcite/silicon dioxide/rubber nano composite material |
| CN108239306A (en) * | 2017-12-11 | 2018-07-03 | 山东玲珑轮胎股份有限公司 | Tire sidewall rubber composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110713638A (en) | 2020-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102532629B (en) | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material | |
| KR100939818B1 (en) | Modified calcium carbonate, polymer composition containing the same and process for producing them | |
| US5872176A (en) | Addition of salts to improve the interaction of silica with rubber | |
| CN101230248B (en) | Sealing strip using EPDM rubber as host material and production method thereof | |
| Laskowska et al. | Ionic elastomers based on carboxylated nitrile rubber (XNBR) and magnesium aluminum layered double hydroxide (hydrotalcite). | |
| CN110713665B (en) | Hydrotalcite/epoxy natural rubber/brominated butyl rubber composite material and preparation method thereof | |
| CN103571064A (en) | Ethylene propylene diene monomer/polyvinyl chloride plastic composite sheath material for cables and preparation method thereof | |
| JP2009518487A (en) | Nanocomposite material containing rubber and modified layered double hydroxide, method for its production and use thereof | |
| CN110121410B (en) | Pneumatic tire with sealant layer and air-tight layer | |
| CN102417668A (en) | Cable sheath material for wind power generation and production method thereof | |
| CN102977428B (en) | Method for preparing blend composite material by virtue of performing blending modification on kaolin/white carbon black | |
| CN107603112B (en) | High-performance high-speed rail outer windshield rubber material and compression molding preparation method thereof | |
| CN104558873A (en) | Preparation method for high-performance composite material based on simultaneous use of hydrotalcite masterbatch and halogenated butyl rubber | |
| CN110713638B (en) | Hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and preparation method thereof | |
| CN110628163A (en) | Low-compression permanent deformation ethylene propylene diene monomer sealing material and preparation method thereof | |
| CN104212084A (en) | Rubber for covering layer of fabric core flame-retarded conveyor belt with CPE as main body and preparation method and application of rubber | |
| EP1837368B1 (en) | Composition containing zinc hydroxide, blend containing the composition and article made thereof | |
| TWI424959B (en) | Calcium carbonate treated with sulfurized active ingredients | |
| WO2005000957A1 (en) | Rubber composition containing silica and method for production thereof | |
| CN1295255C (en) | Process for preparing in-situ graft modified rubber by using general rubber preparing device and its modifier | |
| CN105881925B (en) | A kind of colored chlorinated polyethylene rubber dam bag and its production technology | |
| CN105754236A (en) | High-strength and anti-aging computer cable | |
| WO2009043861A1 (en) | Composite material, process for preparing the composite material, and use thereof | |
| CN101173063A (en) | Multifunctional rubber chemicals and method for producing the same | |
| EP3452543A1 (en) | Tire with component comprising cured rubber composition having high dielectric constant and related methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |