CN105694104B - A kind of preparation method of rubber nano-calcium carbonate - Google Patents
A kind of preparation method of rubber nano-calcium carbonate Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of rubber nano-calcium carbonate, comprises the following steps：A, to Ca (OH)2Amino acid, amino acid and Ca (OH) are added in slurry2The weight ratio of slurry is 0.2~2：100, it is uniformly mixed；B, it is passed through CO2With Ca (OH)2Slurry carries out carburizing reagent so that slurry pH reaches 7~8, so as to obtain the ripe slurry of calcium carbonate；C, after the ripe slurry of calcium carbonate being heated into 60~75 DEG C, add surface conditioning agent and carry out activation process, then press filtration obtains filter cake；D, filter cake is further dried, crushed, and nano-calcium carbonate is made.When the nano-calcium carbonate being prepared of this method is used for rubber, with good processability and dispersiveness, the indexs such as intensity, elongation and the hardness of rubber can be improved, it can be widely used in the rubbers such as tire, sole, sebific duct, be used for instead of carbon black and white carbon as supporting material in rubber.
Description
Technical field
The present invention relates to technical field of nano material, is specifically related to a kind of preparation method of rubber nano-calcium carbonate.
Background technology
Currently used for the filler of rubber, mainly there are white carbon, carbon black, kaolin, talcum powder, coarse whiting, precipitated calcium carbonate etc.,
Only white carbon and carbon black can be used as reinforced filling, can improve wearability, have higher hardness, but white carbon and carbon black
Price is high, and oil factor is big, and viscosity is high during processing, and frictional heat, processing characteristics is poor, and loading is small, and mixing is difficult, processing electric current
It is excessive, and easily vulcanize in advance, user is unsatisfied with.
For rubber, calcium carbonate is the third-largest reinforcing filler for being only second to carbon black, white carbon, have small toxicity,
The advantages such as price is low, are widely used in the rubber processing industry such as tire, rubber overshoes, sebific duct and adhesive tape, electric wire, rubber roll.
Relative to ordinary calcium carbonate, the sharpest edges of nano-calcium carbonate are shown in the strengthening action to rubber elastomer,
Many studies have shown that nano-calcium carbonate is no matter in polar rubber or non-polar rubber, saturated rubber or unsaturation rubber
The effect to elastic reinforcement body is all shown to some extent, greatly improves the power for being filled sizing material.But work as
When the average grain diameter of nano-calcium carbonate is too big, after rubber mix, reinforcing property is bad.Particle is too small, is such as less than 30nm, easily group
It is poly-, poor dispersion.
Therefore compared to fillers such as carbon black, white carbons, it is small that nano-calcium carbonate in the market is used for intensity during rubber, firmly
Spend small, elongation is poor, it is difficult to obtains high-performance rubber product.
Chinese invention patent CN 1631789A disclose a kind of available for coating, plastics, the nano-calcium carbonate of rubber
The preparation method of particle, including following steps：Nucleus is formed into accelerator and adds calcium hydroxide suspension, then passes to two
Carbon oxide gas, add the aqueous solution of dispersant and covering.Described covering mainly includes aliphatic acid and its alkali metal
One or both of salt or titanate coupling agent.But nanometer calcium reinforcing deficiency, elongation in rubber prepared by this method
Rate is poor.
Chinese invention patent CN 1709960A provide a kind of preparation side of ternary ethylene-propylene rubber reinforced by nano calcium carbonate
Method, i.e., there is excellent physics with unsaturated carboxylic acid-modified nanon calcium carbonatefilled ethylene propylene diene rubber, gained rubber blend
Mechanical performance.However, the introducing of unsaturated carboxylic acid, inoxidizability and durability to rubber all bring some problems.
In summary, the nano-calcium carbonate that prepared by currently available technology can not solve the filling demand of high-performance rubber.
The content of the invention
The present invention provides a kind of preparation method of rubber nano-calcium carbonate, the nano-calcium carbonate being prepared of this method
During for rubber, there is good processability and dispersiveness, the finger such as intensity, elongation and hardness of rubber can be improved
Mark, can be widely used in the rubbers such as tire, sole, sebific duct, is used for rubber as supporting material instead of carbon black and white carbon
In.
To achieve the above object, technical scheme is as follows：
The preparation method of the rubber nano-calcium carbonate of the present invention, comprises the following steps：
A, to Ca (OH)2Amino acid, amino acid and Ca (OH) are added in slurry2The weight ratio of slurry is 0.2~2：100, stir
Mix well mixed；
B, it is passed through CO2With Ca (OH)2Slurry carries out carburizing reagent so that slurry pH reaches 7~8, ripe so as to obtain calcium carbonate
Slurry；
C, after the ripe slurry of calcium carbonate being heated into 60~75 DEG C, add surface conditioning agent and carry out activation process, then press filtration obtains
To filter cake；
D, filter cake is further dried, crushed, and nano-calcium carbonate is made.
Amino acid is one or more kinds of combinations in alanine, glycine, glutamic acid in described step A.
Ca (OH) in described step A2Slurry temperature is controlled after 10 DEG C~30 DEG C, adds amino acid.
The carburizing reagent time in described step B is 30-90min, and the initial temperature control that is carbonized is between 10-30 DEG C.
The specific surface area of the ripe slurry of calcium carbonate is controlled in 30-60m in described step B2Between/g.
In described step C, the weight ratio of described surface conditioning agent and the ripe slurry of calcium carbonate is 3~6：100, activation process
Process is to mix surface conditioning agent with the ripe slurry of calcium carbonate, is stirred more than 1 hour.
Surface conditioning agent in described step C is the mixture of sodium resinate and cocoyl diethanolamine, described
The weight ratio of sodium resinate and cocoyl diethanolamine Shuangzi doped quaternary ammonium salt is 3-7：7-3.
When sodium resinate dosage is less than 30%, the difference of hardness of rubber, wearability and screen resilience are poor；When dosage is more than 70%, then
The tensile strength and elongation of rubber are poor；The dosage of resin acid enables to the hardness of rubber moderate in 30-70%, and stretching is strong
Degree and elongation are held at the level being fated.
Cocoyl diethanolamine gemini quaternary ammonium salt, when dosage is less than 30%, the intensity and tensile property of rubber are poor；Dosage
During more than 70%, then the difference of hardness of rubber, resilience are poor.
In described step C, first surfactant, the i.e. mixture of sodium resinate and cocoyl diethanolamine are heated
To 80~95 DEG C, then add in the ripe slurry of calcium carbonate.
Described resin acid is tricyclic diterpene class compound.
Described resin acid is more than one or both of rosin acid, newtrex, disproportionation rosin, hydrogenated rosin mixed
Close.
Beneficial effects of the present invention are：
The present invention uses amino acid to be added and Ca (OH) before carbonization as chemical additives2It is pre-mixed, due to ammonia
After base acid dissolves in water, amino acid molecular and Ca (OH)2Ca in slurry2+, complex compound is formed by coordinate bond, reaction can be improved
Speed, so as to easily form tiny nano-calcium carbonate crystal, with the increase of the addition of amino acid in carbodiimide solution, CaCO3
Particle diameter be suppressed and reduce rapidly due to growth, but when amino acid reaches a certain amount of, Ca2+When increasing unobvious, continue
Increase the amount of amino acid to Nano-meter CaCO33Particle diameter and form influence and unobvious, therefore, the most suitable addition of amino acid is
Ca(OH)20.2-3%, when dosage be less than 0.2% when, dosage very little, DeGrain；When dosage is more than 3%, specific surface area oneself
Stabilization is in certain level, cost of idleness.
And being smoothed out for carburizing reagent has also further been consolidated in the initial temperature control that is carbonized in the range of 10-30 DEG C, temperature
Degree is higher, and specific surface area is lower, and particle is thicker；Temperature is lower, and specific surface area is bigger, finer particles.By the calcium carbonate after carbonization
The specific surface area control of ripe slurry is 30-60m2/ g, when the specific surface area of nano-calcium carbonate is too small, particle is big, and reinforcing effect is poor；Than
Surface area is too big, and second particle is easily condensed into big particle, to be unable to fine dispersion in rubber matrix, reinforcing effect can also subtract
It is small.
In the surface conditioning agent that the present invention uses, the resin acid such as newtrex, disproportionation rosin, hydrogenated rosin has preferable
Inoxidizability, resinate is added in surface treatment, the dispersiveness of nano-calcium carbonate can be improved and improve the hardness of rubber；
The dosage of resin acid will also control proper in surface conditioning agent, and very little, the difference of hardness of rubber, wearability and screen resilience are poor for dosage；
Dosage is too big, then the tensile strength of rubber and elongation are poor；The dosage of the resin acid of the present invention, enables to the hardness of rubber to fit
In, tensile strength and elongation are held at appropriate level.
Cocoyl diethanolamine gemini quaternary ammonium salt in the surface conditioning agent of the present invention, there are two hydrophobic groups in molecule
With two hydrophilic groups, hydrophilic group is coupled by spacer group by chemical bond, thereby results in two surfactant monomer phases
Combined when close, this structure, on the one hand enhance the hydrophobic effect of hydrocarbon chain；On the other hand, the repulsion between hydrophilic group is made
Effect weakens the long-chain surface-active both containing increase tensile property in gemini quaternary ammonium salt molecule because being limited by chemical bond significantly
Agent molecule, again containing the rigid ethoxy head base of increase, thus possesses more excellent physicochemical characteristics.It is being surface-treated
When, cocoyl diethanolamine gemini quaternary ammonium salt is added, the tensile strength and elongation of rubber can be improved, its dosage is also required to
Rationally control, dosage is very few, and the intensity and tensile property of rubber are poor；Dosage is excessive, then the difference of hardness of rubber, resilience are poor.
The present invention is by Ca (OH)2With CO2Carburizing reagent in, add amino acid be used as crystal control agent, rationally control
The specific surface area of nano-calcium carbonate, surface is carried out using resinate and oil base diethanolamine gemini quaternary ammonium salt during surface treatment
Processing, when the nano-calcium carbonate being prepared is used for rubber, has good processability and dispersiveness, can improve rubber
The indexs such as intensity, elongation and the hardness of product, instead of carbon black and white carbon as supporting material, be widely used in tire, sole,
In the rubbers such as sebific duct.
Embodiment
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
（1）The refined Ca (OH) of regulation2Proportion be 1.036, carburizing temperature initially degree be 10 DEG C, be incorporated as Ca (OH)2Weight
1.0% crystal control agent alanine（C3H7NO2）, glycine（NH2CH2COOH）Mixture, open stirring for carbonization reactor
Mix, be passed through the CO of volumetric concentration 30%2Reacted, when carbonization is to pH=7, stop carbonization, the reaction time is 30 minutes, detection
The BET specific surface area of the ripe slurry of nano-calcium carbonate is 56.9m2/g。
（2）10 cubic silicon carbides good ripe slurries is pumped into surface treatment pond, 1 cube is now determined and is received containing 95 kilograms
Rice calcium carbonate, slurry are heated to 60 DEG C, and 10 cubes of slurries contain 0.95 ton of nano-calcium carbonate altogether.
Added in saponification kettle in 80 DEG C of hot water, add 2.2% rosin acid for accounting for weight of calcium carbonate, 20.9 kilograms of pines
Fragrant acid, add 4.5 kilograms of NaOH and reacted, after saponification generation sodium abietate, addition accounts for the 48.7 of the 5.1% of weight of calcium carbonate
Kilogram cocoyl diethanolamine gemini quaternary ammonium salt, after mixing, surface treatment pond is added to, is stirred 1 hour.
（3）To the slurry being surface-treated, space press filtration, drying, drying temperature is 110 DEG C, using oven drying, obtains water
Divide≤0.3% product, packed, obtain the product of the present invention, BET specific surface area is 51.2m after testing2/ g, oil factor are
45ml/100g。
Embodiment 2
（1）The refined Ca (OH) of regulation2Proportion be 1.049, carbonization initial temperature be 15 DEG C, be incorporated as Ca (OH)2Amount
1.2% crystal control agent glutamic acid C5H9NO4, the stirring of carbonization reactor is opened, is passed through the CO that volumetric concentration is 30%2Carry out anti-
Should, when carbonization is to pH=7.2, stop carbonization, the reaction time is 50 minutes, detects the BET specific surface area of the ripe slurry of nano-calcium carbonate
For 55.4m2/g。
（2）10 cubic silicon carbides good ripe slurries is pumped into surface treatment pond, 1 cube is now determined and is received containing 99 kilograms
Rice calcium carbonate, slurry are heated to 65 DEG C, and 10 cubes of slurries contain 0.99 ton of nano-calcium carbonate altogether.
85 DEG C of hot water is added in saponification kettle, adds 3% newtrex for accounting for weight of calcium carbonate, 29.7 kilograms of polymerizations
Rosin, add 4.8 kilograms of NaOH and reacted, after saponification generation disproportionation rosin sodium, addition accounts for the 4.5% of weight of calcium carbonate
44.6 kilograms of cocoyl diethanolamine gemini quaternary ammonium salts, after mixing, surface treatment pond is added to, is stirred 1.5 hours.
（3）To the slurry being surface-treated, space press filtration, drying, drying temperature is 110 DEG C, using oven drying, obtains water
Divide≤0.3% product, packed, obtain the product of the present invention, BET specific surface area is 50.8m after testing2/ g, oil factor are
46ml/100g。
Embodiment 3
（1）The refined Ca (OH) of regulation2Proportion be 1.055, carbonization initial temperature be 20 DEG C, be incorporated as Ca (OH)2Amount
1.5% crystal control agent glycine（NH2CH2COOH）, the stirring of carbonization reactor is opened, is passed through the CO that volumetric concentration is 30%2Enter
Row reaction, when carbonization is to pH=7.5, stop carbonization, the reaction time is 60 minutes, and the BET of the detection ripe slurry of nano-calcium carbonate compares table
Area is 47.2m2/g。
（2）The good ripe slurry of 10 cubic silicon carbides is pumped into surface treatment pond, now determining 1 cube contains 106 kilograms
Nano-calcium carbonate, slurry are heated to 70 DEG C, and 10 cubes of slurries contain 1.06 tons of nano-calcium carbonates altogether.
95 DEG C of hot water is added in saponification kettle, adds 3% disproportionation rosin for accounting for weight of calcium carbonate, 31.8 kilograms of disproportionations
Rosin is added in 90 DEG C of hot water, is added 5.09 kilograms of NaOH and is reacted, and after saponification generation disproportionation rosin sodium, addition accounts for carbonic acid
37.1 kilograms of cocoyl diethanolamine gemini quaternary ammonium salts of the 3.5% of calcium weight, after mixing, it is added to surface treatment pond, stirring
2 hours.
（3）To the slurry being surface-treated, space press filtration, drying, drying temperature is 110 DEG C, using oven drying, obtains water
Divide≤0.3% product, packed, obtain the product of the present invention, BET specific surface area is 43.5m after testing2/ g, oil factor are
48ml/100g。
Embodiment 4
（1）The refined Ca (OH) of regulation2Proportion be 1.059, carbonization initial temperature be 25 DEG C, be incorporated as Ca (OH)2Amount
1.8% crystal control agent glutamic acid C5H9NO4, the stirring of carbonization reactor is opened, is passed through the CO that volumetric concentration is 30%2Carry out anti-
Should, when carbonization is to pH=7.8, stop carbonization, the reaction time is 80 minutes, detects the BET specific surface area of the ripe slurry of nano-calcium carbonate
For 55.2m2/g。
（2）The good ripe slurry of 10 cubic silicon carbides is pumped into surface treatment pond, now determining 1 cube contains 110 kilograms
Nano-calcium carbonate, slurry are heated to 75 DEG C, and 10 cubes of slurries contain 1.1 tons of nano-calcium carbonates altogether.
95 DEG C of hot water is added in saponification kettle, adds 3.2% newtrex for accounting for weight of calcium carbonate, 35.2 kilograms poly-
Rosin is closed, 5.12 kilograms of NaOH is added and is reacted, after saponification generation disproportionation rosin sodium, addition accounts for the 3.2% of weight of calcium carbonate
35.2 kilograms of cocoyl diethanolamine gemini quaternary ammonium salts, after mixing, surface treatment pond is added to, is stirred 2.5 hours.
（3）To the slurry being surface-treated, space press filtration, drying, drying temperature is 110 DEG C, using oven drying, obtains water
Divide≤0.3% product, packed, obtain the product of the present invention, BET specific surface area is 34.8m after testing2/ g, oil factor are
50ml/100g。
Embodiment 5
（1）The refined Ca (OH) of regulation2Proportion be 1.063, carbonization initial temperature be 30 DEG C, be incorporated as Ca (OH)2The 2% of amount
Crystal control agent glutamic acid C5H9NO4, the stirring of carbonization reactor is opened, is passed through the CO that volumetric concentration is 30%2Reacted, when
When being carbonized to pH=8, stop carbonization, the reaction time is 90 minutes, and the BET specific surface area of the detection ripe slurry of nano-calcium carbonate is
55.8m2/g。
（2）The good ripe slurry of 10 cubic silicon carbides is pumped into surface treatment pond, now determining 1 cube contains 120 kg
Nano-calcium carbonate, slurry are heated to 75 DEG C, and 10 cubes of slurries contain 1.2 tons of nano-calcium carbonates altogether.
95 DEG C of hot water is added in saponification kettle, adds 4% newtrex for accounting for weight of calcium carbonate, 48 kilograms of polymerization pines
The fragrant mixture with disproportionation rosin, add 5.54 kilograms of NaOH and reacted, saponification generation newtrex sodium, disproportionation rosin sodium
After mixture, the 1.7% 2.04 kilograms of cocoyl diethanolamine gemini quaternary ammonium salts for accounting for weight of calcium carbonate are added, after mixing, are added
Enter to surface treatment pond, stir 3 hours.
（3）To the slurry being surface-treated, space press filtration, drying, drying temperature is 110 DEG C, using oven drying, obtains water
Divide≤0.3% product, packed, obtain the product of the present invention, BET specific surface area is 40.2m after testing2/ g, oil factor are
51ml/100g。
The contrast test of embodiment 6
Comparative example 1
Other conditions are same as Example 1, add 5% stearic acid for accounting for weight of calcium carbonate, 56.2 kilograms of stearic acid, add 8.5
Kilogram NaOH reacted, saponification generation odium stearate after, be added to surface treatment pond.The BET of finished product compares surface after testing
Product is 50.5m2/ g, oil factor 35ml/100g.
Comparative example 2
Other conditions are same as Example 2, are not added with crystal control agent glycine（NH2CH2COOH）, by detection, nano-calcium carbonate
The BET specific surface area of the ripe slurry of calcium is 27.3m2/g；The BET specific surface area of finished product is 24.8m after testing2/ g, oil factor 32ml/
100g。
Comparative example 3
Other conditions are same as Example 3, and surface treatment processing accounts for calcium carbonate using the hot water that 95 DEG C are added in kettle is changed, addition
7.5% newtrex of weight, 74.3 kilograms of newtrexes, add 11.5 kilograms of NaOH and reacted, saponification generation disproportionation pine
After fragrant sodium, surface treatment pond is added to, is stirred 2 hours.
Obtained nano-calcium carbonate finished product, BET specific surface area is 43.2m after testing2/ g, oil factor 54ml/100g.
The powder of the nano-calcium carbonate example of the above is obtained, respectively by formula as below, carries out detection performance：
（1）Formula（By weight）
CR neoprenes 100；Zinc oxide 5；Stearic acid 1；Altax 1.2；TM monex TM (TS) 0.5；Sulfur 2；
Filler nanometer calcium carbonate 100.
The mill produced by being formulated in Fujian Yongchun machinery plant is to be kneaded about 30min, and sulphur is carried out with 25T vulcanizing presses
Change, curing temperature is 160 degree, and cure time is determined by sulfurizing time.
（2）Physical and mechanical properties
Think carefully the electronic tensile machine that company produces in length and breadth with Shenzhen；Stretching property is blocked by GB/T 528-1998 test vulcanizates
Can, by the LX-A type durometers produced with Jiangyin, the shore a hardness of vulcanizate is tested according to GB/T531-1999.
Test result is as follows：
1 each the performance test results of table
The contrast test of table 2 is tested
| Performance | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| BET specific surface area m2/g | 50.5 | 24.8 | 43.2 |
| Oil factor ml/100g | 35 | 32 | 54 |
| Outward appearance dispersiveness | It is good | It is good | It is good |
| Hardness (Shao Er A) | 50 | 52 | 77 |
| Tensile strength（300%）（MPa） | 2.6 | 3.3 | 8.5 |
| Ultimate tensile strength（MPa） | 13.2 | 14.8 | 21.4 |
| Maximum elongation rate（%） | 640 | 580 | 500 |
It can be seen that from table 1,2：Comparative example 1 is handled using stearic acid surface, and tensile strength is poor；Comparative example 2 is not added with crystalline substance
Shape controlling agent, specific surface area is low, and intensity and elongation are all poor；Comparative example 3, it is not added with cocoyl diethanolamine Shuangzi quaternary ammonium
Salt, elongation are poor.
From contrast test as can be seen that the nano-calcium carbonate of the present invention, regulation Ca (OH)2Temperature and concentration after, add
Amino acid is carbonized as crystal control agent, and the specific surface area that product is controlled after carbonization is 30-60m2/ g, using sodium resinate
With cocoyl diethanolamine Shuangzi quaternary ammonium compound carry out activation process, for rubber can improve rubber elongation at break,
Hardness, intensity and processing characteristics are good, and dispersiveness is excellent.
Claims (9)
1. a kind of preparation method of rubber nano-calcium carbonate, it is characterised in that comprise the following steps：
A, amino acid is added into the slurries of Ca (OH) 2, the weight ratio of amino acid and the slurries of Ca (OH) 2 is 0.2~2：100, stirring
It is well mixed；
B, it is passed through CO2 and carries out carburizing reagent with the slurries of Ca (OH) 2 so that slurry pH reaches 7~8, so as to obtain the ripe slurry of calcium carbonate；
C, after the ripe slurry of calcium carbonate being heated into 60~75 DEG C, add surface conditioning agent and carry out activation process, then press filtration is filtered
Cake；
D, filter cake is further dried, crushed, and nano-calcium carbonate is made；
Surface conditioning agent in described step C is the mixture of sodium resinate and cocoyl diethanolamine gemini quaternary ammonium salt,
The weight ratio of described sodium resinate and cocoyl diethanolamine gemini quaternary ammonium salt is 3-7：7-3.
2. the preparation method of rubber nano-calcium carbonate according to claim 1, it is characterised in that：In described step A
Amino acid is one or more kinds of combinations in alanine, glycine, glutamic acid.
3. the preparation method of rubber nano-calcium carbonate according to claim 1, it is characterised in that：In described step A
The slurry temperatures of Ca (OH) 2 are controlled after 10 DEG C~30 DEG C, add amino acid.
4. the preparation method of rubber nano-calcium carbonate according to claim 1, it is characterised in that：In described step B
The carburizing reagent time be 30-90min, the initial temperature control that is carbonized is between 10-30 DEG C.
5. the preparation method of rubber nano-calcium carbonate according to claim 1, it is characterised in that：In described step B
The specific surface area of the ripe slurry of calcium carbonate is controlled between 30-60m2/g.
6. the preparation method of rubber nano-calcium carbonate according to claim 1, it is characterised in that：In described step C,
The weight ratio of described surface conditioning agent and the ripe slurry of calcium carbonate is 3~6：100, activated process is by surface conditioning agent and carbon
The sour ripe slurry mixing of calcium, is stirred more than 1 hour.
7. the preparation method of rubber nano-calcium carbonate according to claim 1, it is characterised in that：In described step C,
Surface conditioning agent, the i.e. mixture of sodium resinate and cocoyl diethanolamine gemini quaternary ammonium salt are first heated to 80~95 DEG C,
Then add in the ripe slurry of calcium carbonate.
8. the preparation method of rubber nano-calcium carbonate according to claim 1, it is characterised in that：Described resin acid is
Tricyclic diterpene class compound.
9. the preparation method of rubber nano-calcium carbonate according to claim 1, it is characterised in that：Described resin acid is
Mixing more than one or both of rosin acid, newtrex, disproportionation rosin, hydrogenated rosin.
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| CN108359274A (en) * | 2018-02-07 | 2018-08-03 | 广西大学 | Rosin derivative chelates calcium modified Nano or lightweight CaCO3Powder preparation method |
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