CN106277015A - The preparation method that a kind of polyurethane sealant is Nano calcium carbonate dedicated - Google Patents
The preparation method that a kind of polyurethane sealant is Nano calcium carbonate dedicated Download PDFInfo
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- CN106277015A CN106277015A CN201610699888.1A CN201610699888A CN106277015A CN 106277015 A CN106277015 A CN 106277015A CN 201610699888 A CN201610699888 A CN 201610699888A CN 106277015 A CN106277015 A CN 106277015A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/011—Nanostructured additives
Abstract
The present invention discloses the preparation method that a kind of polyurethane sealant is Nano calcium carbonate dedicated, comprises the steps: A, to Ca (OH)2Solution adds chemical additives, is uniformly mixed, is passed through CO2Gas carries out bubbling carbonizing reaction until pH value of solution is 7～8, obtains ripe slurry；B, ripe slurry are warmed up to 60～85 DEG C after sieving, add the mixture of satisfied fatty acid sodium and bismuth carboxylate salt as surfactant under stirring, and to regulate pH value be between 7 ~ 9, continue stirring 45～60min；In C, step B, the ripe slurry after stirring carries out filter pressing, obtains filter cake, and filter cake is dried and pulverized and be further dried, and to obtain final product.Nano-calcium carbonate prepared by the present invention and polyurethane system have preferable adhesion, and can significantly improve polyurethane sealant mechanical property, are applied to polyurethane sealant and can improve the hot strength of polyurethane sealant, elongation at break, tearing strength.
Description
Technical field
The present invention relates to technical field of nano material, be specifically related to a kind of polyurethane sealant Nano calcium carbonate dedicated
Preparation method.
Background technology
Nano-calcium carbonate (Na-CaCO3) it is the new type functional nano-sized filler of a kind of function admirable, it can not only be filled
Increase-volume, reduces cost, more can improve the surface color degree of goods, improves the comprehensive mechanical property of goods.At present, in flourishing state
Family, nano-calcium carbonate is commonly used in medium-to-high grade rubber, plastic, fluid sealant, coating, ink etc..And in state
In, the field of nano-calcium carbonate consumption maximum is silicone sealant, is secondly polyurethane sealant.The performance of polyurethane sealant
More excellent than the performance of silicone sealant, but be difficult to prepare, external polyurethane sealant consumption is with silicone sealant consumption difference not
Many, the technology of preparing low SI being mainly the most domestic fluid sealant and the filler not had；Technical merit along with China
Raising, polyurethane sealant all has application at daily life, the aspect such as military and industrial, it is contemplated that the five-year by with 7% speed
Rate increases.
The surface modification of nano-calcium carbonate, mainly rely on modifying agent calcium carbonate surface absorption, react, be coated with or become
Film realizes.Therefore, surface modifier processes have decisive role for surface modification and the surface of calcium carbonate.It is at carbon
" bridging " effect is played between substrate and other component in acid calcium particle and material.The surface of nano-calcium carbonate processes often to be had
Its specific application background or application.Therefore, surface modifier is selected to must take into the application processing material.Example
As, for pearl filler surface modifiers such as polymer composites materials, plastics and rubber, should be with calcium carbonate surface
Absorption or reaction, be covered in the surface of particle, have stronger chemical action again with organic polymer.Therefore, come from structure
Saying, surface modifier should be that a class has more than one functional group being combined with calcium carbonate surface and more than one can be with organic
The compound of the functional group that high polymer combines.Field should be had a lot of due to what calcium carbonate surface modifying agent related to, can be used as surface
The material of modifying agent is also a lot, and conventional surface modifier has following a few class: fatty acid, oils and fats, wax, non-ionic surfactant
Agent, silicone, titanate esters, amine, phosphoric acid lipid, aluminum based compound, zirconium----aluminum based compound.Use most common stearic acid
And the long-chain fatty acid such as salt, paraffin, DOP, Oleum Cocois, but due between fatty acid acid chain adhesion weak, after filled polymer
Mechanical strength is bad；Ideal surface modifier is various types of coupling agent such as silane, titanate esters, Aluminate etc..Silicon
Alkane coupling agent is expensive, and to nono calcium carbonate modified DeGrain；Titanate coupling agent is widely used, and price is fitted
In, but owing to the central atom of coupling agent is Titanium atom, its product has deeper color (from light brown to dark-brown),
Therefore range of application is subject to certain restrictions.Aluminate color and luster is pure white, but owing to product easily hydrolyzes, it is impossible to it is exposed to air
In, also limit it and cannot be used for the wet-process modified of nano-calcium carbonate.
Patent of invention CN 102702795A discloses the preparation method that a kind of polyurethane adhesive is Nano calcium carbonate dedicated: use
Secondary deep is crossed carbonization and squeezing type filter press filter pressing and is squeezed two steps dehydrations farthest reduction magnesium ion in the product
Residual, thus at utmost reduce the alkalescence of the nano-calcium carbonate of preparation, and with inorganic dehydroamino acid to nano-calcium carbonate
Grain carries out surface process, makes product meet the requirement to modified filler basicity of the polyurethane adhesive system；Use hot blast to nano-sized carbon
Acid calcium carries out secondary deep drying, with the silane based coupling agents that moisture absorption is the most weak, nano-calcium carbonate particles is carried out surface again simultaneously
Hydrophobic processes, and makes product moisture be reduced to less than 0.1%, and no longer moisture absorption bounce-back.But, the inorganic agent that this product is selected is nothing
Machine dehydroamino acid and silane based coupling agents, poor with the polyurethane system compatibility, adhesion is more weak, and mechanical strength is difficult to effectively obtain
Must promote.
Summary of the invention
Present invention aims to inorganic agent during the Nano calcium carbonate dedicated preparation of polyurethane adhesive in prior art is nothing
Machine dehydroamino acid and silane based coupling agents, poor with the polyurethane system compatibility, adhesion is more weak, and mechanical strength is difficult to effectively obtain
The technical problem that must promote, it is provided that a kind of have preferable adhesion with polyurethane system, and can significantly improve polyurethane sealant power
Learn the preparation method of the nano-calcium carbonate of performance, control temperature, concentration and crystal control agent by carbonization, process on surface and adopt
By fatty acid amine and bismuth carboxylate salt Combined Treatment, and add appropriate acid, through filter pressing, dry, pulverize and obtain nano-calcium carbonate
Product, the specific surface area controlling product is 20-40m2/ g, pH value 7-8.5, being applied to polyurethane sealant, can to improve polyurethane close
The hot strength of sealing, elongation at break, tearing strength.
For achieving the above object, technical scheme is as follows:
The preparation method that the polyurethane sealant of the present invention is Nano calcium carbonate dedicated, comprises the steps:
A, to Ca (OH)2Solution adds chemical additives, is uniformly mixed, is passed through CO2Gas carries out bubbling carbonizing reaction
Until pH value of solution is 7～8, obtain ripe slurry；Described chemical additives is sucrose, citric acid, sodium citrate, EDTA, three ethanol
One or more mixing in amine, aluminum sulfate, zinc sulfate, sulphuric acid, sodium sulfate, sodium hexameta phosphate, phosphoric acid, acetic acid, adds
Entering amount is Ca (OH)2The 0.1～2.0% of quality；
B, ripe slurry are warmed up to 60～85 DEG C after sieving, add the mixture conduct of fatty acid amine and bismuth carboxylate salt under stirring
Surfactant, and to regulate pH value be between 7 ~ 9, continues stirring 45～60min；
In C, step B, the ripe slurry after stirring carries out filter pressing, obtains filter cake, and filter cake is dried and pulverized and be further dried, and to obtain final product.
Ca (OH) in described step A2The preparation method of solution comprises the following steps:
Limestone is calcined in shaft kiln by 10:0.9～1.1 with anthracite in mass ratio, calcining heat be 900～
1200 DEG C, calcination time is 8～24h, obtains calcium oxide, and sieve removal coal ash and pulverized limestone, makes block Calx, adds water and disappear
Change, obtain essence serum after the removing impurity that sieves, be aged, to obtain final product.
Described block Calx add water digestion method comprise the following steps: the coolant-temperature gage used by control is 40～60 DEG C,
The consumption of water is 5～6 times of lime quality, is gradually added in block Calx, generates slip, controls calcium hydroxide quality in slurry
Concentration, between 10～15%, sequentially passes through 60 mesh sieves, cyclone hydraulic separators, 150 mesh sieves, 250 mesh sieves removing impurity, obtains smart breast
Slurry.
The time of described ageing is 16～32h.
CO in described step A2The volumetric concentration of gas is 20～50%, and the time of carburizing reagent is 30～90min.
In described step B, total consumption of surface conditioning agent is Ca (OH)2The 2～8% of quality, wherein sodium soap and carboxylic
The mass ratio of acid bismuth salt is 3 ~ 5:1.
Described fatty acid amine uses fatty acid and triethanolamine to carry out saponification acquisition, and triethanolamine consumption is fat
The 10-15% of acid consumption, wherein fatty acid is lauric acid, stearic acid, Palmic acid, oleic acid, linoleic acid etc..One or both with
On mixing；
Described bismuth carboxylate salt is one or more the mixture in isooctyl acid bismuth, bismuth naphthenate, new certain herbaceous plants with big flowers acid bismuth.
The regulation of the pH in described step B uses zinc sulfate, aluminum sulfate or acetic acid as regulator, and addition is Ca
(OH)2Quality 0.1 ~ 3%.
The invention have the benefit that
The surface conditioning agent of the present invention uses fatty acid amine and bismuth carboxylate salt Combined Treatment, can regulate consolidating of polyurethane sealant
Change speed, control the cross-linked network structure of polyurethane sealant, increase mechanical property；Wherein, bismuth carboxylate salt can not only be effective
It is coated on carbonic acid surface, forms chemistry clad, and in polyurethane system is applied, remaining bismuth salt can play catalyst
Effect, promotes that polyurethane forms cross-linked network structure, and mechanical strength effectively promotes.The introducing of amino, can be raw with polyurethane system
Polarity bigger urea groups, gives the higher intensity of elastomer to a great extent.
And in the composition of surface conditioning agent, if fatty acid amine ratio is excessive, the intensity of polyurethane system is poor；If it is fatty
Acid amide ratio is too small, and polyurethane reaction short-term training is spent soon, and bin stability is poor；If bismuth carboxylate salt ratio is excessive, remaining bismuth
Salt can play catalyst action, and reaction short-term training is spent soon, causes bin stability poor；If bismuth carboxylate salt ratio is too small, poly-ammonia
Ester forms cross-linked network structure, and inconspicuous, mechanical strength is poor.Present invention applicant passes through lot of experiments, it is thus achieved that science
The addition of rational surface conditioning agent and proportioning, it is possible to ensure stability and the quality of product of reaction.
CO in carbonation reaction2The suitable of carburizing reagent has been consolidated in the control of gas concentration and carbonization time the most further
Profit is carried out, CO2Gas concentration is the biggest, and the carburizing reagent time is the shortest, and the calcium carbonate particle of generation is the least；CO2Gas concentration is the least,
Carbonization time is the longest, and the calcium carbonate particle of generation is the biggest.When the specific surface area of nano-calcium carbonate is too small, particle is big, reinforcing effect
Difference；Specific surface area is too big, and second particle is easily condensed into big particle, in rubber matrix can not fine dispersion, reinforcing effect
Also can reduce.The specific surface area controlling product of the ripe slurry of calcium carbonate after carbonization of the present invention is 20-40m2/ g, adds appropriate acid
With control ph between 7-9, to improve the bin stability of polyurethane sealant.
The present invention processes the nano-calcium carbonate of preparation through in-stiu coating, during especially for polyurethane sealant, has
Good storage-stable, intensity, tensile property, i.e. have good mechanical property.The nano-calcium carbonate of this project also can be answered
For other fields such as plastics, rubber, fluid sealants, the hot strength of goods, elongation at break, elastic modelling quantity can be improved, have
Good mechanical performance；The nano-calcium carbonate produced by the inventive method has broad application prospects.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
The preparation method that the polyurethane sealant of the present invention is Nano calcium carbonate dedicated, comprises the steps:
A, to 10kgCa (OH)2Solution adds chemical additives, is uniformly mixed, is passed through CO2Gas carries out bubbling carbonizing
Reaction, until pH value of solution is 7, obtains ripe slurry；Described chemical additives is the mixing of sucrose, citric acid, and addition is
0.01kg；
B, ripe slurry are warmed up to 60 DEG C after sieving, add the fatty acid amine mixture with bismuth carboxylate salt as surface under stirring
Activating agent, and to regulate pH value be 7, continues stirring 45min；
In C, step B, the ripe slurry after stirring carries out filter pressing, obtains filter cake, and filter cake is dried and pulverized and be further dried, and to obtain final product.
Ca (OH) in described step A2The preparation method of solution comprises the following steps:
Being calcined in shaft kiln with 0.9kg anthracite by 10kg limestone, calcining heat is 900 DEG C, and calcination time is 8h,
To calcium oxide, sieve removal coal ash and pulverized limestone, makes block Calx, and add water digestion, obtains essence serum after the removing impurity that sieves,
It is aged, to obtain final product.
Described block Calx add water digestion method comprise the following steps: the coolant-temperature gage used by control is 40 DEG C, water
Consumption is 50kg, is gradually added in block Calx, generates slip, and controlling calcium hydroxide mass concentration in slurry is between 10%, depends on
Secondary through 60 mesh sieves, cyclone hydraulic separators, 150 mesh sieves, 250 mesh sieves removing impurity, obtain smart serum.
The time of described ageing is 16h.
CO in described step A2The volumetric concentration of gas is 20%, and the time of carburizing reagent is 30min.
In described step C, total consumption of surface conditioning agent is Ca (OH)2The 0.2kg of quality, the wherein matter of fatty acid amine
Amount is for 0.15kg, and the quality of bismuth carboxylate salt is that ratio is for 0.05kg.
Described fatty acid amine is saponified with triethanolamine after lauric acid, stearic acid mass ratio 1:1 mixing, three ethanol
The 5% of amine consumption fatty acid quality；Bismuth carboxylate salt is isooctyl acid bismuth.
The regulation of the pH in described step B uses zinc sulfate as regulator, and addition is 0.01kg.
Embodiment 2
The preparation method that the polyurethane sealant of the present invention is Nano calcium carbonate dedicated, comprises the steps:
A, to 10kgCa (OH)2Solution adds chemical additives, is uniformly mixed, is passed through CO2Gas carries out bubbling carbonizing
Reaction, until pH value of solution is 7.3, obtains ripe slurry；Described chemical additives is the mixing of sodium citrate, EDTA, and addition is
0.05kg；
B, ripe slurry are warmed up to 65 DEG C after sieving, add the fatty acid amine mixture with bismuth carboxylate salt as surface under stirring
Activating agent, and to regulate pH value be between 7.5, continues stirring 50min；
In C, step B, the ripe slurry after stirring carries out filter pressing, obtains filter cake, and filter cake is dried and pulverized and be further dried, and to obtain final product.
Ca (OH) in described step A2The preparation method of solution comprises the following steps:
Being calcined in shaft kiln with 1kg anthracite by 10kg limestone, calcining heat is 1000 DEG C, and calcination time is 12h,
To calcium oxide, sieve removal coal ash and pulverized limestone, makes block Calx, and add water digestion, obtains essence serum after the removing impurity that sieves,
It is aged, to obtain final product.
Described block Calx add water digestion method comprise the following steps: the coolant-temperature gage used by control is 45 DEG C, water
Consumption is 52kg, is gradually added in block Calx, generates slip, and controlling the mass concentration of calcium hydroxide in slurry is 12%, successively
Remove impurity through 60 mesh sieves, cyclone hydraulic separators, 150 mesh sieves, 250 mesh sieves, obtain smart serum.
The time of described ageing is 20h.
CO in described step A2The volumetric concentration of gas is 25%, and the time of carburizing reagent is 50min.
In described step C, total consumption of surface conditioning agent is 0.4kg, and wherein the quality of fatty acid amine is 0.24kg, carboxylic
The quality of acid bismuth salt is 0.06kg.
Described fatty acid amine be after oleic acid, Oleum Cocois, palm-kernel oil mass ratio 1:2:3 mixing with the saponification of triethanolamine
Thing, the 8% of triethanolamine consumption fatty acid quality；Bismuth carboxylate salt is bismuth naphthenate.
The regulation of the pH in described step B uses aluminum sulfate as regulator, and addition is 0.05kg.
Embodiment 3
The preparation method that the polyurethane sealant of the present invention is Nano calcium carbonate dedicated, comprises the steps:
A, to 10kgCa (OH)2Solution adds chemical additives, is uniformly mixed, is passed through CO2Gas carries out bubbling carbonizing
Reaction, until pH value of solution is 7.5, obtains ripe slurry；Described chemical additives is the mixing of sucrose, aluminum sulfate, and addition is Ca
(OH)2The 0.1kg of quality；
B, ripe slurry are warmed up to 70 DEG C after sieving, add the fatty acid amine mixture with bismuth carboxylate salt as surface under stirring
Activating agent, and to regulate pH value be 8, continues stirring 55min；
In C, step B, the ripe slurry after stirring carries out filter pressing, obtains filter cake, and filter cake is dried and pulverized and be further dried, and to obtain final product.
Ca (OH) in described step A2The preparation method of solution comprises the following steps:
Being calcined in shaft kiln with 1.1kg anthracite by 10kg limestone, calcining heat is 1100 DEG C, and calcination time is 16h,
Obtaining calcium oxide, sieve removal coal ash and pulverized limestone, makes block Calx, and add water digestion, obtains essence breast after the removing impurity that sieves
Slurry, is aged, to obtain final product.
Described block Calx add water digestion method comprise the following steps: the coolant-temperature gage used by control is 50 DEG C, water
Consumption is 55kg, is gradually added in block Calx, generates slip, and controlling calcium hydroxide mass concentration in slurry is 13%, warp successively
Cross 60 mesh sieves, cyclone hydraulic separators, 150 mesh sieves, 250 mesh sieves removing impurity, obtain smart serum.
The time of described ageing is 24h.
CO in described step A2The volumetric concentration of gas is 30%, and the time of carburizing reagent is 50min.
In described step C, total consumption of surface conditioning agent is 0.6kg, and wherein the quality of fatty acid amine is 0.5kg, carboxylic acid
The quality of bismuth salt is 0.1kg.
Described fatty acid amine be after oleic acid, Oleum Cocois, palm-kernel oil mass ratio 1:2:4 mixing with the saponification of triethanolamine
Thing, the 10% of triethanolamine consumption fatty acid quality；Bismuth carboxylate salt is new certain herbaceous plants with big flowers acid bismuth.
The regulation of the pH in described step B uses acetic acid as regulator, and addition is Ca (OH)2Quality 0.1kg.
Embodiment 4
The preparation method that the polyurethane sealant of the present invention is Nano calcium carbonate dedicated, comprises the steps:
A, to 10kgCa (OH)2Solution adds chemical additives, is uniformly mixed, is passed through CO2Gas carries out bubbling carbonizing
Reaction, until pH value of solution is 7.8, obtains ripe slurry；Described chemical additives is the mixing of sodium hexameta phosphate, phosphoric acid, acetic acid, adds
Entering amount is 0.15kg；
B, ripe slurry are warmed up to 80 DEG C after sieving, add the fatty acid amine mixture with bismuth carboxylate salt as surface under stirring
Activating agent, and to regulate pH value be 8.5, continues stirring 55min；
In C, step B, the ripe slurry after stirring carries out filter pressing, obtains filter cake, and filter cake is dried and pulverized and be further dried, and to obtain final product.
Ca (OH) in described step A2The preparation method of solution comprises the following steps:
Being calcined in shaft kiln with 0.95kg anthracite by 10kg limestone, calcining heat is 1150 DEG C, and calcination time is
20h, obtains calcium oxide, and sieve removal coal ash and pulverized limestone, makes block Calx, and add water digestion, obtains after the removing impurity that sieves
Essence serum, is aged, to obtain final product.
Described block Calx add water digestion method comprise the following steps: the coolant-temperature gage used by control is 55 DEG C, water
Consumption is the 58kg of lime quality, is gradually added in block Calx, generates slip, controls the mass concentration of calcium hydroxide in slurry
It is between 14%, sequentially passes through 60 mesh sieves, cyclone hydraulic separators, 150 mesh sieves, 250 mesh sieves removing impurity, obtain smart serum.
The time of described ageing is 28h.
CO in described step A2The volumetric concentration of gas is 40%, and the time of carburizing reagent is 70min.
In described step C, total consumption of surface conditioning agent is 0.7kg, and wherein the quality of fatty acid amine is 0.56kg, carboxylic
The quality of acid bismuth salt is 0.14kg.
Described fatty acid amine is saponified with triethanolamine after lauric acid, palm-kernel oil mass ratio 2:3 mixing, three second
Hydramine consumption is the 8% of fatty acid consumption；Bismuth carboxylate salt is the mixture of isooctyl acid bismuth, bismuth naphthenate.
The regulation of the pH in described step B uses zinc sulfate as regulator, and addition is Ca (OH)2Quality
0.2kg。
Embodiment 5
The preparation method that the polyurethane sealant of the present invention is Nano calcium carbonate dedicated, comprises the steps:
A, to 10kgCa (OH)2Solution adds chemical additives, is uniformly mixed, is passed through CO2Gas carries out bubbling carbonizing
Reaction, until pH value of solution is 8, obtains ripe slurry；Described chemical additives is sodium hexameta phosphate, and addition is 0.2kg；
B, ripe slurry are warmed up to 85 DEG C after sieving, add the fatty acid amine mixture with bismuth carboxylate salt as surface under stirring
Activating agent, and to regulate pH value be between 9, continues stirring 60min；
In C, step B, the ripe slurry after stirring carries out filter pressing, obtains filter cake, and filter cake is dried and pulverized and be further dried, and to obtain final product.
Ca (OH) in described step A2The preparation method of solution comprises the following steps:
10kg limestone and 1.1 anthracites being calcined in shaft kiln, calcining heat is 1200 DEG C, calcination time be 8～
24h, obtains calcium oxide, and sieve removal coal ash and pulverized limestone, makes block Calx, and add water digestion, obtains after the removing impurity that sieves
Essence serum, is aged, to obtain final product.
Described block Calx add water digestion method comprise the following steps: the coolant-temperature gage used by control is 60 DEG C, water
Consumption is 60kg, is gradually added in block Calx, generates slip, and controlling the mass concentration of calcium hydroxide in slurry is 15%, successively
Remove impurity through 60 mesh sieves, cyclone hydraulic separators, 150 mesh sieves, 250 mesh sieves, obtain smart serum.
The time of described ageing is 32h.
CO in described step A2The volumetric concentration of gas is 50%, and the time of carburizing reagent is 90min.
In described step C, total consumption of surface conditioning agent is 0.8kg, wherein fatty acid amine 0.6kg, the matter of bismuth carboxylate salt
Amount is 0.2kg.
What described fatty acid amine was stearic acid with triethanolamine is saponified, and triethanolamine consumption is fatty acid consumption
10%；Bismuth carboxylate salt is the mixture in bismuth naphthenate, new certain herbaceous plants with big flowers acid bismuth.
The regulation of the pH in described step B uses acetic acid as regulator, and addition is 0.3kg.
Embodiment 6
Contrast test
1, nano-calcium carbonate is prepared by the method for the embodiment of the present invention 2 ~ 4
2, prepared by matched group nano-calcium carbonate
(1) being that 10:1 calcines in shaft kiln by limestone and anthracite mass ratio, calcining heat controls at 1000 ± 50 DEG C
In the range of, calcination time is 12h, obtains block Calx.Bulk Calx is delivered to ashing melting machine add water ashing, obtain unscreened stock；Ashing
It is 50 DEG C that the coolant-temperature gage of Shi Suoyong controls, and the consumption of water is 5 times of lime quality.Unscreened stock sequentially passes through 60 mesh sieves, rotary filter press
Device, 150 mesh and 250 mesh sieves remove impurity, obtain essence serum, are aged 24h, prepare Ca (OH)2Raw slurry is standby.
(2) regulation raw slurry Ca (OH)2Concentration be 10%, carbonization initial temperature is 17 DEG C, add 0.5%(with calcium hydroxide
Solid content calculates) crystal control agent sodium hexameta phosphate, open the stirring of carbonization reactor, be passed through CO2Concentration be 33% kiln gas enter
Row reaction, when carbonization to pH=7.5, stops carbonization, and the BET specific surface area of the detection ripe slurry of nano-calcium carbonate is 35.8m2/g。
(3) by ripe for nano-calcium carbonate slurry after 350 mesh vibrosieves, entering process pond, surface, ripe slurry is warmed up to 70 DEG C, with
Time add and account for the sodium stearate of weight of calcium carbonate 4.2%.
(4) slurry handling surface well, carries out filter pressing, is dried, obtain the product of moisture≤0.5%, then carry out pulverizing,
Classification, packaging, obtain the product of the present invention.The specific surface area of detection product is 32.4m2/ g, pH are 9.6.
2, the preparation of fluid sealant
Before preparing fluid sealant, first nano-calcium carbonate filler is dried 3 hours at 120 DEG C；When preparing fluid sealant, first will be poly-
Ether dihydroxylic alcohols-220, polyether-tribasic alcohol-330, DOP add in 500ml there-necked flask in the following proportions, and 110-120 DEG C of vacuum takes off
Water 2h；System is cooled to 80 DEG C, adds the MDI measured and react 3 hours, obtain base polyurethane prepolymer for use as.By polyurethane prepolymer
Body, pearl filler and remaining auxiliary agent are sequentially added into planetary double-shaft blender, evacuation, mixing dispersion 2 hours, discharging at 60 DEG C
Obtain polyurethane sealant, fill this blend in vinyon bottle and save backup.
Various embodiments above is filled with according to the following formulation polyurethane sealant:
The formula of polyurethane sealant such as table 1:
Table 1 polyurethane sealant formula
| Raw material | Mass fraction |
| Polyether Glycols-220 | 50 parts |
| Polyether-tribasic alcohol-330 | 50 parts |
| MDI | 25 parts |
| DOP | 32 parts |
| Coupling agent (KH550) | 2.5 part |
| Coupling agent (KH560) | 1 part |
| Chain extender | 3 parts |
| Dibutyl tin laurate | 1 part |
| Nano-calcium carbonate | 100 parts |
After nano-calcium carbonate prepared by the embodiment of the present invention 2 ~ 4 and matched group filled polyurethane fluid sealant respectively, test,
First fluid sealant is made the thin film of 1.8-2.2mm, solidify 7 days under the conditions of standard cure, with GB/T 528 standard A type cutting knife
Prepare standard dog bone sample, measure hot strength, elongation at break, tearing strength.
The performance test results is as shown in table 2:
The each the performance test results of table 2 polyurethane sealant
| Project | Embodiment 2 | Embodiment 3 | Embodiment 4 | Matched group |
| BET specific surface area (m2/ g) | 24.9 | 33.1 | 36.8 | 32.4 |
| pH | 8.3 | 8.0 | 7.8 | 9.6 |
| Hot strength/Mpa | 2.34 | 2.65 | 2.93 | 2.02 |
| Elongation at break % | 679 | 623 | 610 | 575 |
| Tearing strength/N/mm | 8.4 | 10.1 | 12.9 | 7.9 |
From above comparative example it can be seen that the present invention nano-calcium carbonate calcium product, use soap and bismuth carboxylate salt to join
Conjunction processes, and pH value controls the nano-calcium carbonate between 7-9 when being applied to polyurethane sealant, have more preferable hot strength,
Elongation at break, tearing strength.
Claims (8)
1. the preparation method that a polyurethane sealant is Nano calcium carbonate dedicated, it is characterised in that comprise the steps:
A, to Ca (OH)2Solution adds chemical additives, is uniformly mixed, is passed through CO2It is straight that gas carries out bubbling carbonizing reaction
It is 7～8 to pH value of solution, obtains ripe slurry；Described chemical additives be sucrose, citric acid, sodium citrate, EDTA, triethanolamine,
One or more mixing in aluminum sulfate, zinc sulfate, sulphuric acid, sodium sulfate, sodium hexameta phosphate, phosphoric acid, acetic acid, addition
For Ca (OH)2The 0.1～2.0% of quality；
B, ripe slurry are warmed up to 60～85 DEG C after sieving, add the mixture conduct of fatty acid amine and bismuth carboxylate salt under stirring
Surfactant, and to regulate pH value be between 7-9, continues stirring 45～60min；
C, filter pressing, obtain filter cake, and filter cake is dried and pulverized and be further dried, and to obtain final product.
The preparation method that polyurethane sealant the most according to claim 1 is Nano calcium carbonate dedicated, it is characterised in that described
Step A in Ca (OH)2The preparation method of solution comprises the following steps:
Limestone is calcined in shaft kiln by 10:0.9～1.1 with anthracite in mass ratio, calcining heat be 900～
1200 DEG C, calcination time is 8～24h, obtains calcium oxide, and sieve removal coal ash and pulverized limestone, makes block Calx, adds water and disappear
Change, obtain essence serum after the removing impurity that sieves, be aged, to obtain final product.
The preparation method that polyurethane sealant the most according to claim 2 is Nano calcium carbonate dedicated, it is characterised in that described
Block Calx add water digestion method comprise the following steps: the coolant-temperature gage used by control is 40～60 DEG C, and the consumption of water is stone
Ash 5～6 times of quality, is gradually added in block Calx, generates slip, control in slurry calcium hydroxide mass concentration 10～
Between 15%, sequentially pass through 60 mesh sieves, cyclone hydraulic separators, 150 mesh sieves, 250 mesh sieves removing impurity, obtain smart serum.
The preparation method that polyurethane sealant the most according to claim 2 is Nano calcium carbonate dedicated, it is characterised in that: described
Time of ageing be 16～32h.
The preparation method that polyurethane sealant the most according to claim 1 is Nano calcium carbonate dedicated, it is characterised in that: described
Step A in CO2The volumetric concentration of gas is 20～50%, and the time of carburizing reagent is 30～90min.
The preparation method that polyurethane sealant the most according to claim 1 is Nano calcium carbonate dedicated, it is characterised in that: described
Step B in total consumption of surface conditioning agent be Ca (OH)2The 2～8% of quality, wherein fatty acid amine and the quality of bismuth carboxylate salt
Ratio is 3 ~ 5:1.
The preparation method that polyurethane sealant the most according to claim 6 is Nano calcium carbonate dedicated, it is characterised in that: described
Fatty acid amine use fatty acid and triethanolamine to carry out saponification acquisition, wherein fatty acid is lauric acid, stearic acid, Petiolus Trachycarpi
One or more mixing in acid, oleic acid, Oleum Cocois, palm-kernel oil；Bismuth carboxylate salt be isooctyl acid bismuth, bismuth naphthenate,
One or more mixture in new certain herbaceous plants with big flowers acid bismuth.
The preparation method that polyurethane sealant the most according to claim 1 is Nano calcium carbonate dedicated, it is characterised in that: described
The regulation of the pH in step B uses zinc sulfate, aluminum sulfate or acetic acid as regulator, and addition is Ca (OH)2Quality 0.1
~3%。
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| CN108546342A (en) * | 2018-04-04 | 2018-09-18 | 中国科学院宁波材料技术与工程研究所 | A kind of calcium carbonate dispersion treating agent, preparation method and a kind of composite material |
| CN109879304A (en) * | 2019-03-29 | 2019-06-14 | 桂林理工大学 | A kind of nano/submicron efficient calcium carbonate carbonization technique |
| CN109970088A (en) * | 2019-03-06 | 2019-07-05 | 江西华明纳米碳酸钙有限公司 | The Nano calcium carbonate dedicated preparation method of high-end PE blown film |
| CN111422894A (en) * | 2019-12-23 | 2020-07-17 | 广西大学 | Calcium carbonate coated calcium carbonate (CaCO)3@CaCO3) Powder and preparation method thereof |
| CN112457690A (en) * | 2020-12-07 | 2021-03-09 | 江西华明纳米碳酸钙有限公司 | Preparation method of nano calcium carbonate for polyurethane adhesive |
| CN113416430A (en) * | 2021-06-29 | 2021-09-21 | 常州碳酸钙有限公司 | Preparation method and application of special nano calcium carbonate for polyurethane sealant |
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| CN113416430A (en) * | 2021-06-29 | 2021-09-21 | 常州碳酸钙有限公司 | Preparation method and application of special nano calcium carbonate for polyurethane sealant |
| CN114212812A (en) * | 2021-11-01 | 2022-03-22 | 山东宇信纳米科技有限公司 | Preparation method of nano calcium carbonate for PVC edge sealing strip |
| CN114212812B (en) * | 2021-11-01 | 2023-11-21 | 山东宇信纳米科技有限公司 | Preparation method of nano calcium carbonate for PVC edge banding |
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