CN114804178B - Preparation method of special nano calcium carbonate for polyester family degradable plastics - Google Patents

Preparation method of special nano calcium carbonate for polyester family degradable plastics Download PDF

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CN114804178B
CN114804178B CN202210557658.7A CN202210557658A CN114804178B CN 114804178 B CN114804178 B CN 114804178B CN 202210557658 A CN202210557658 A CN 202210557658A CN 114804178 B CN114804178 B CN 114804178B
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calcium carbonate
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CN114804178A (en
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颜干才
吴明
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Guangxi Mintai Nano Technology Co ltd
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    • 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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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

Abstract

The invention discloses a preparation method of nano calcium carbonate special for polyester family degradable plastics, which adopts a zirconium alcohol compound as a crystal form control agent, so that the problem of high moisture absorption rate of the nano calcium carbonate caused by residual crystal control agent can be effectively avoided; the associative polyurethane thickener is added in the later stage of carbonation reaction, and the water-based thixotropic network constructed by polyurethane is used for replacing a hydrogen bond network on the surface of calcium carbonate, so that the aggregation phenomenon generated by crystals can be effectively reduced, and the phenomenon of high water content of nano calcium carbonate caused by the aggregation phenomenon is avoided; meanwhile, the invention adopts aprotic solvent to wash the filter cake for multiple times in the filter pressing process, so that a residual hydrogen bond network system of the nano calcium carbonate filter cake can be removed as much as possible, capillary pore effect caused by the filter cake drying process is reduced, the drying efficiency of the nano calcium carbonate finished product is further improved, and the technical effect that the nano calcium carbonate with the moisture content less than 0.1% can be produced in conventional drying equipment and preparation systems is realized.

Description

Preparation method of special nano calcium carbonate for polyester family degradable plastics
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of special nano calcium carbonate for polyester family degradable plastics.
Background
China is the largest plastic product production and consumption country in the world, and must pay attention to the problem of white pollution, and under the forbidden plastic, the degradable plastic industry is expected to rapidly discharge. According to the execution schedule and execution strength of the plastic forbidden policies in each province and overseas degradable plastic development process, the demand change of the degradable plastic in the future 10 years in China is predicted. By 2025, the demand of degradable plastics in China is estimated to be 238 ten thousand tons, and the market scale is estimated to be 477 hundred million yuan; by 2030, the demand of degradable plastics in China is expected to be up to 428 ten thousand tons, and the market scale can be up to 855 hundred million yuan. The market space of the degradable plastics in China is huge.
With the tightening of plastic limiting command in various places, polyester biodegradable environment-friendly materials mainly comprising PLA and PBAT are newly developed and subjected to opportunity. Biodegradable plastics are a class of polymeric materials which can be decomposed into carbon dioxide and water by microbial action in industrial or urban composting facilities. Depending on the manner of synthesis and the source of the raw materials, biodegradable plastics can be classified into bio-based degradable plastics and petroleum-based degradable plastics. However, in the prior art, the main materials such as PLA and PBAT have insufficient toughness and stiffness, which makes it difficult to widely popularize them in practical use. The application of conventional nano materials such as silicon dioxide, aluminum oxide, titanium dioxide, barium sulfate and the like in the field of degradation plastics is questioned due to the lack of degradability and environmental protection.
The nano calcium carbonate is a nontoxic and environment-friendly degradable inorganic material, when the polymerization is stressed, the debonding of the nano particles and the polymer matrix material can induce cavitation to absorb energy, so that the mechanical property of the composite material can be effectively improved, and the nano calcium carbonate is a reinforcing and toughening modifier which has the most application prospect in the degradable plastics. However, the common nano calcium carbonate can only be controlled to be between 0.2 and 0.6 percent due to the limitation of the preparation technology, which can certainly lead to degradation of polyester family degradation plastics due to the existence of trace moisture in the processing process, and further optimization and improvement on the nano calcium carbonate preparation technology are required.
The Chinese patent No. 112646235 discloses a novel nano calcium carbonate for degradable plastic films and a preparation method thereof, wherein the novel nano calcium carbonate comprises the following raw materials in parts by weight: 7-10 parts of calcium carbonate, 3-5 parts of calcium oxide, 3-9 parts of graphene, 3-7 parts of ethylene propylene diene monomer rubber, 2-6 parts of a coupling agent, 8-14 parts of an activating agent, 1-5 parts of an ionic liquid, 3-8 parts of a polyethylene wax calcium carbonate master batch and a proper amount of water. The technology disclosed in the patent is difficult to accept and recognize, more of the auxiliary agents are mixed like a splicing mess, and as a chemical technical person should be clear, calcium oxide can undergo a severe chemical reaction with water, and ethylene propylene diene monomer rubber and polyethylene wax calcium carbonate master batches have higher melting points, and the mode of mixing the calcium oxide and the calcium carbonate is unknown.
Chinese patent No. 211575752 discloses a low water content nano calcium carbonate drying device, which is mainly realized by a physical mode and has better energy-saving and consumption-reducing functions, but the real water content of the nano calcium carbonate cannot be reduced fundamentally. Because nano calcium carbonate is dehydrated in a conventional physical manner when the moisture is reduced below 0.3% due to capillary pore effect during drying.
In summary, in order to successfully apply the nano calcium carbonate to the field of degradation plastics, the control of low moisture and low moisture absorption rate is a precondition technical means.
Disclosure of Invention
The invention aims to solve the technical problem that the water content of nano calcium carbonate cannot be reduced below 0.3 percent due to high water content and high moisture absorption rate in the prior art; the preparation method of the nano calcium carbonate special for the polyester degradation plastic is provided to realize the technical effects that the water content and the moisture absorption rate of the nano calcium carbonate are effectively reduced, and the final water content of the product is lower than 0.1 percent.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of special nano calcium carbonate for polyester family degradation plastic comprises the following steps:
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 6-8%, controlling the temperature to 25-30 ℃, and then adding a zirconium alcohol compound as a crystal form control agent, and uniformly stirring and mixing;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction, wherein the pore diameter of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8mm; when the conductivity of a reaction system in the film dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, adding an associated polyurethane thickener, and then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, so as to obtain calcium carbonate slurry;
4) Conveying the calcium carbonate slurry obtained in the step 3) to an activation kettle for secondary surface modification to obtain modified calcium carbonate slurry;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then carrying out pressurized washing on the filter cake for 3-5 times by adopting an aprotic solvent; the washed solvent enters a distillation system to evaporate water for recycling;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5).
According to the invention, the zirconium alkoxide compound is used as a crystal form control agent, so that the regrowth of {104} crystal faces of calcium carbonate crystals can be promoted, and meanwhile, the zirconium alkoxide compound cannot remain on the surface of a finished product of nano calcium carbonate after carbonation reaction is completed, so that the problem of high moisture absorption rate of the nano calcium carbonate caused by the residue of the crystal control agent can be effectively avoided; the invention adds the association polyurethane thickener in the later stage of carbonation reaction (namely when the conductivity begins to drop to 5 ms/cm), utilizes the aqueous thixotropic network constructed by polyurethane to replace the hydrogen bond network on the surface of calcium carbonate, can effectively reduce the aggregation phenomenon generated by crystals, thereby avoiding the phenomenon of high water content of nano calcium carbonate caused by the aggregation phenomenon; meanwhile, the invention adopts aprotic solvent to wash the filter cake for multiple times in the filter pressing process, so that a residual hydrogen bond network system of the nano calcium carbonate filter cake can be removed as much as possible, capillary pore effect caused by the filter cake drying process is reduced, the drying efficiency of the nano calcium carbonate finished product is further improved, and the nano calcium carbonate with the moisture content less than 0.1% can be produced in conventional drying equipment and preparation systems.
On the basis of the technical scheme, the invention can be improved as follows.
As a preferable technical scheme of the invention, the adding amount of the zirconium alcohol compound in the step 2) is 1.0-2.0% of the dry weight of the calcium hydroxide.
As a preferable technical scheme of the invention, the zirconium alkoxide compound in the step 2) is any one of zirconium propoxide and zirconium butoxide or a mixture formed by mixing the two compounds in any proportion.
As a preferable technical scheme of the invention, the addition amount of the associative polyurethane thickener in the step 3) is 2.0-3.0% of the dry weight of calcium hydroxide.
As a preferable technical scheme of the invention, the associative polyurethane thickener in the step 3) is a nonionic associative polyurethane thickener, the concentration of the effective component is more than or equal to 40%, and the viscosity is less than or equal to 14000cp.
As a preferable technical scheme of the invention, the method for secondary surface modification in the step 4) comprises the following steps: delivering the calcium carbonate slurry to an activation kettle, heating to 90 ℃, and then adding low carbon chain saturated fatty acid to perform primary surface modification for 20-40 minutes; then adding epoxy resin to carry out secondary surface modification for 30-45 minutes.
As a preferable technical scheme of the invention, the addition amount of the low carbon chain saturated fatty acid is 0.5-1.0% of the dry basis of the calcium carbonate slurry, and the addition amount of the epoxy resin is 2.0-3.5% of the dry basis of the calcium carbonate slurry.
As a preferable technical scheme of the invention, the low carbon chain saturated fatty acid is saturated fatty acid with 10-14 carbon atoms, the epoxy resin is glycidol amine epoxy resin, the epoxy value is 0.8-1.0, and the epoxy equivalent is 100-130.
As a preferable technical scheme of the invention, the low carbon chain saturated fatty acid is any one or a mixture of more than two of capric acid, lauric acid and palmitic acid according to any proportion.
As a preferable technical scheme of the invention, the aprotic solvent in the step 5) is any one of carbon tetrachloride and N, N-dimethylformamide.
The beneficial effects of the invention are as follows:
1. the water content of the nano calcium carbonate product prepared by the invention is lower than 0.1%, the product has low moisture absorption rate, and the degradation phenomenon caused by high water content or high moisture absorption rate in the system can not be caused when the nano calcium carbonate product is used in a degradable plastic system;
2. the nano calcium carbonate product prepared by the invention has good compatibility with a degradable plastic system, and can effectively improve the mechanical properties of the composite material of the nano calcium carbonate product and the degradable plastic system;
3. the preparation method of the invention is simple, low in production cost and high in industrialization degree.
Drawings
FIG. 1 is a scanning electron microscope analysis chart of the nano calcium carbonate obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope analysis chart of the nano calcium carbonate obtained in example 2 of the present invention;
FIG. 3 is a scanning electron microscope analysis chart of the nano calcium carbonate obtained in comparative example 1;
Detailed Description
The embodiment of the invention provides a preparation method of nano calcium carbonate special for polyester degradation plastic, which aims to solve the technical problem that the water content of the nano calcium carbonate cannot be reduced below 0.3% due to high water content and moisture absorption rate in the prior art, so as to realize the technical effects of effectively reducing the water content and the moisture absorption rate of the nano calcium carbonate, and the final water content of a product is lower than 0.1%.
The invention adopts the following general ideas:
in the prior art, the factors causing the higher moisture content of the nano calcium carbonate finished product are many, and all the influencing factors are not related to each other, and any one of the factors can directly cause the higher level content of the nano calcium carbonate finished product, so that each influencing factor in the preparation method needs to be removed one by one to obtain the technical effect that the final moisture content of the finished product is lower than 0.1%, and the method comprises the following steps of:
1. as sucrose, citric acid, sulfate and other substances are mostly adopted as crystal control agents in the traditional nano calcium carbonate preparation industry, the crystal control agents remain on the surface of the nano calcium carbonate product in the subsequent process, so that the moisture absorption rate of the nano calcium carbonate product is high; the zirconium alkoxide compound is used as the crystal form control agent, so that the regrowth of {104} crystal faces of calcium carbonate crystals can be promoted, and meanwhile, the zirconium alkoxide compound cannot remain on the surface of a finished product of nano calcium carbonate after carbonation reaction is completed, so that the problem of high moisture absorption rate of the nano calcium carbonate caused by the residue of the crystal control agent can be effectively avoided;
2. in the prior art, in the later stage of calcium hydroxide carbonation, the pH of slurry is rapidly reduced, so that the surface potential of calcium carbonate obtained by carbonation is reduced, and calcium carbonate particles start to form primary agglomeration, thereby influencing the subsequent drying effect of nano calcium carbonate; in the invention, the associative polyurethane thickener is added in the later stage of carbonation reaction (namely, when the conductivity begins to drop to 5 ms/cm), and the water-based thixotropic network constructed by polyurethane is used for replacing a hydrogen bond network on the surface of calcium carbonate, so that the aggregation phenomenon generated by crystals can be effectively reduced;
3. in the prior art, the nano calcium carbonate generally adopts fatty acid or fatty acid salt for surface modification, but the calcium salt which is finally coated on the surface of the calcium carbonate and is generally in a fatty acid form (provided that the surface treatment temperature is higher than the melting point of the fatty acid) is a amphiphile, the metal ions are hydrophilic, the fatty chain segments are hydrophobic, and under the condition of excessive treatment agent, the calcium salt in the fatty acid form can form double layers or even multiple layers of coatings on the surface of the calcium carbonate, so that the fatty chain of the hydrophobic chain segments cannot be completely exposed outside the surface of the calcium carbonate, and the later moisture absorption risk can be caused when more hydrophilic ions are exposed outside the surface of the calcium carbonate; and fatty acid salt systems do not provide good compatibility in degrading plastics. Therefore, the invention adopts two surface treatment procedures, and the first step is to add as little low carbon chain fatty acid as possible, and the addition amount is 0.5-1.0% of nano calcium carbonate; the second treatment process uses epoxy resin as a modifier to coat the nano calcium carbonate, so that on one hand, the hydrophobic effect of the surface of the nano calcium carbonate is ensured, and on the other hand, the compatibility of the nano calcium carbonate in a degradable plastic system is improved;
4. according to the invention, the aprotic solvent is adopted to wash the filter cake for multiple times in the filter pressing process, so that a residual hydrogen bond network system of the nano calcium carbonate filter cake can be removed as much as possible, and capillary pore effect caused by the filter cake drying process is reduced, so that the drying efficiency of the nano calcium carbonate finished product is further improved.
The preparation method adopted by the invention is as follows:
a preparation method of special nano calcium carbonate for polyester family degradation plastic comprises the following steps:
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 6-8%, controlling the temperature to 25-30 ℃, and then adding a zirconium alcohol compound as a crystal form control agent, and uniformly stirring and mixing;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction, wherein the pore diameter of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8mm; when the conductivity of a reaction system in the film dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, adding an associated polyurethane thickener, and then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, so as to obtain calcium carbonate slurry;
4) Conveying the calcium carbonate slurry obtained in the step 3) to an activation kettle for secondary surface modification to obtain modified calcium carbonate slurry;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then carrying out pressurized washing on the filter cake for 3-5 times by adopting an aprotic solvent; the washed solvent enters a distillation system to evaporate water for recycling;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5).
Wherein the adding amount of the zirconium alcohol compound in the step 2) is 1.0-2.0% of the dry weight of the calcium hydroxide; the zirconium alcohol compound in the step 2) is any one or a mixture of two of zirconium propoxide and zirconium butoxide in any proportion.
The addition amount of the associative polyurethane thickener in the step 3) is 2.0-3.0% of the dry weight of calcium hydroxide; the associative polyurethane thickener in the step 3) is a nonionic associative polyurethane thickener, the concentration of the active ingredient is more than or equal to 40%, the viscosity is less than or equal to 14000cp, such as the Walker VOK-WT 105 associative polyurethane thickener in Germany.
The method for secondary surface modification in the step 4) comprises the following steps: delivering the calcium carbonate slurry to an activation kettle, heating to 90 ℃, and then adding low carbon chain saturated fatty acid to perform primary surface modification for 20-40 minutes; then adding epoxy resin to carry out secondary surface modification for 30-45 minutes.
The addition amount of the low carbon chain saturated fatty acid is 0.5-1.0% of the dry basis of the calcium carbonate slurry, and the addition amount of the epoxy resin is 2.0-3.5% of the dry basis of the calcium carbonate slurry; the low-carbon-chain saturated fatty acid is saturated fatty acid with the carbon number of 10-14, when the carbon number is more than 14, the water-soluble effect is poor, effective coating is difficult to form on the surface of calcium carbonate, and when the carbon number is less than 10, the hydrophobic effect of the fatty acid is poor, and the moisture absorption performance of the finished product in the later stage is influenced, so that the low-carbon-chain saturated fatty acid is any one or a mixture of more than two of capric acid, lauric acid and palmitic acid according to any proportion; the epoxy resin is glycidol amine epoxy resin, the epoxy value is 0.8-1.0, and the epoxy equivalent is 100-130.
The aprotic solvent in the step 5) is any one of carbon tetrachloride and N, N-dimethylformamide.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of special nano calcium carbonate for polyester family degradation plastic comprises the following steps:
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 6%, controlling the temperature to 30 ℃, and then adding zirconium propoxide as a crystal form control agent, and uniformly stirring and mixing; wherein the adding amount of zirconium propoxide is 1.5% of the dry weight of calcium hydroxide;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction, wherein the pore diameter of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8mm; when the conductivity of a reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding an associated polyurethane thickener, wherein the addition amount of the associated polyurethane thickener is 2.5% of the dry basis of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, thus obtaining calcium carbonate slurry;
4) Conveying the calcium carbonate slurry obtained in the step 3) to an activation kettle, heating to 90 ℃, and then adding lauric acid for primary surface modification, wherein the adding amount of the lauric acid is 0.5% of the dry basis of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the addition amount of the epoxy resin is 2.5% of the dry basis of the calcium carbonate slurry, and the modification time is 35 minutes;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then carrying out pressurized washing on the filter cake for 4 times by adopting a carbon tetrachloride solvent; the washed solvent enters a distillation system to evaporate water for recycling;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5) to obtain the nano calcium carbonate product.
Example 2
A preparation method of special nano calcium carbonate for polyester family degradation plastic comprises the following steps:
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 7%, controlling the temperature to 28 ℃, and then adding zirconium butoxide as a crystal form control agent, and uniformly stirring and mixing; wherein the adding amount of zirconium butoxide is 1.0% of the dry weight of calcium hydroxide;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction, wherein the pore diameter of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8mm; when the conductivity of a reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding an associated polyurethane thickener, wherein the addition amount of the associated polyurethane thickener is 2.0% of the dry basis of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, thus obtaining calcium carbonate slurry;
4) Conveying the calcium carbonate slurry obtained in the step 3) to an activation kettle, heating to 90 ℃, and then adding palmitic acid for carrying out primary surface modification, wherein the addition amount of the palmitic acid is 0.5% of the dry basis of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the addition amount of the epoxy resin is 2.5% of the dry basis of the calcium carbonate slurry, and the modification time is 35 minutes;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then adopting a carbon tetrachloride solvent to carry out pressurized washing on the filter cake for 3 times; the washed solvent enters a distillation system to evaporate water for recycling;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5) to obtain the nano calcium carbonate product.
Example 3
A preparation method of special nano calcium carbonate for polyester family degradation plastic comprises the following steps:
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 8%, controlling the temperature to 25 ℃, and then adding zirconium propoxide as a crystal form control agent, and uniformly stirring and mixing; wherein the adding amount of zirconium propoxide is 2.0% of the dry weight of calcium hydroxide;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction, wherein the pore diameter of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8mm; when the conductivity of a reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding an associated polyurethane thickener, wherein the addition amount of the associated polyurethane thickener is 3.0% of the dry basis of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, thus obtaining calcium carbonate slurry;
4) Conveying the calcium carbonate slurry obtained in the step 3) to an activation kettle, heating to 90 ℃, and then adding decanoic acid for primary surface modification, wherein the adding amount of the decanoic acid is 1.0% of the dry weight of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the addition amount of the epoxy resin is 3.0% of the dry basis of the calcium carbonate slurry, and the modification time is 35 minutes;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then adopting an N, N-dimethylformamide solvent to carry out pressurized washing on the filter cake for 5 times; the washed solvent enters a distillation system to evaporate water for recycling;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5) to obtain the nano calcium carbonate product.
Example 4
A preparation method of special nano calcium carbonate for polyester family degradation plastic comprises the following steps:
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 7%, controlling the temperature to 28 ℃, and then adding zirconium propoxide and zirconium butoxide according to the mass ratio of 1:1 as a crystal form control agent; wherein the addition amount of the crystal form control agent is 1.8% of the dry weight of calcium hydroxide;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction, wherein the pore diameter of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8mm; when the conductivity of a reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding an associated polyurethane thickener, wherein the addition amount of the associated polyurethane thickener is 2.6% of the dry basis of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, thus obtaining calcium carbonate slurry;
4) Delivering the calcium carbonate slurry obtained in the step 3) to an activation kettle, heating to 90 ℃, and then adding lauric acid and palmitic acid according to the mass ratio of 1:3, carrying out primary surface modification on the mixture, wherein the addition amount of the primary surface modifier is 1.0% of the dry basis of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the addition amount of the epoxy resin is 3.5% of the dry basis of the calcium carbonate slurry, and the modification time is 35 minutes;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then adopting an N, N-dimethylformamide solvent to carry out pressurized washing on the filter cake for 4 times; the washed solvent enters a distillation system to evaporate water for recycling;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5) to obtain the nano calcium carbonate product.
Example 5
A preparation method of special nano calcium carbonate for polyester family degradation plastic comprises the following steps:
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 6.5%, controlling the temperature to 25.5 ℃, and then adding zirconium propoxide and zirconium butoxide according to a mass ratio of 3:2 as a crystal form control agent; wherein the addition amount of the crystal form control agent is 1.2% of the dry weight of calcium hydroxide;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction, wherein the pore diameter of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8mm; when the conductivity of a reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding an associated polyurethane thickener, wherein the addition amount of the associated polyurethane thickener is 2.8% of the dry basis of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, thus obtaining calcium carbonate slurry;
4) Delivering the calcium carbonate slurry obtained in the step 3) to an activation kettle, heating to 90 ℃, and then adding lauric acid, palmitic acid and capric acid according to the mass ratio of 1:1:2, carrying out primary surface modification on the mixture, wherein the addition amount of the primary surface modifier is 1.0% of the dry basis of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the addition amount of the epoxy resin is 3.5% of the dry basis of the calcium carbonate slurry, and the modification time is 35 minutes;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then adopting an N, N-dimethylformamide solvent to carry out pressurized washing on the filter cake for 5 times; the washed solvent enters a distillation system to evaporate water for recycling;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5) to obtain the nano calcium carbonate product.
Comparative example 1
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 6.5%, controlling the temperature to 25.5 ℃, and then adding sucrose as a crystal form control agent, and stirring and mixing uniformly; wherein the adding amount of the sucrose is 0.8% of the dry weight of the calcium hydroxide;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, so as to obtain calcium carbonate slurry; wherein the pore diameter of the membrane pores of the membrane dispersion carbonization device is 0.3-0.8mm;
4) Conveying the calcium carbonate slurry obtained in the step 3) to an activation kettle, heating to 90 ℃, and then adding lauric acid for surface modification, wherein the adding amount of lauric acid is 3.7% of the dry basis of the calcium carbonate slurry, and the modifying time is 65 minutes;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5) to obtain the nano calcium carbonate product.
Moisture absorption stability test for nano calcium carbonate product
The nano calcium carbonate products obtained in examples 1 to 5 and comparative example 1 of the present invention were subjected to comparative test for moisture absorption stability (the test method referred to the test method of GB/T19591 moisture content using coulomb method moisture meter), and the results are shown in the following table:
as shown in the table above, the water content of the nano calcium carbonate product prepared by the invention is lower than 0.1%, and the water content of the product can still be kept lower than 0.2% after the product is placed for 30 days.
Application test of nano calcium carbonate product
The nano calcium carbonate products obtained in examples 1-5 and comparative example 1 of the present invention were left for 30 days respectively, and then degraded plastics were prepared according to the following formulation and process:
the application formula of the degradable plastic comprises the following steps:
the components Mass ratio
PLA 40％
PBAT 25％
Thermoplastic starch 20％
Nanometer calcium carbonate 15％
The preparation process of the degradable plastic comprises the following steps:
extruding and granulating the formula by using a screw machine, wherein the screw rotating speed of the screw machine is 75r/min, and the temperatures of all process areas are respectively set to 155, 165, 170, 180, 185 and 180 ℃;
after granulation, standard sample bars are prepared by an injection molding machine to test the tensile strength and impact strength of the sample (wherein the tensile strength test standard is GB/T1402-2006, the impact strength test standard is GB/T1843-2008), and the test results are shown in the following table:
sample name Tensile strength Mpa Elongation at break% Impact strength J/m
Example 1 32.6 73 17.5
Example 2 31.4 78 16.4
Example 3 30.8 71 18.1
Example 4 33.6 74 18.3
Example 5 31.7 79 17.8
Comparative example 1 15.3 4.6 7.2
As shown in the table above, the nano calcium carbonate product prepared by the invention has good compatibility with a degradable plastic system, and can effectively improve the mechanical properties of the composite material of the nano calcium carbonate product and the degradable plastic system.
Finally, it should be noted that: these embodiments are merely for illustrating the present invention and do not limit the scope of the present invention. Further, various other changes and modifications will be apparent to those skilled in the art from the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (10)

1. A preparation method of special nano calcium carbonate for polyester family degradation plastic comprises the following steps:
1) Placing limestone in a vertical kiln for calcination, wherein the calcination temperature is 950-1150 ℃; after the calcination is finished, lime and tap water are mixed according to the mass ratio of 1:5, carrying out mixed digestion reaction, and sieving and removing impurities through a hydrocyclone to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 6-8%, controlling the temperature to 25-30 ℃, and then adding a zirconium alcohol compound as a crystal form control agent, and uniformly stirring and mixing;
3) Delivering the calcium hydroxide slurry obtained in the step 2) to a membrane dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction, wherein the pore diameter of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8mm; when the conductivity of a reaction system in the film dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, adding an associated polyurethane thickener, and then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH value of the slurry is less than or equal to 7.0, so as to obtain calcium carbonate slurry;
4) Conveying the calcium carbonate slurry obtained in the step 3) to an activation kettle for secondary surface modification to obtain modified calcium carbonate slurry;
5) Carrying out filter pressing dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then carrying out pressurized washing on the filter cake for 3-5 times by adopting an aprotic solvent; the washed solvent enters a distillation system to evaporate water for recycling;
6) Crushing, drying, crushing and grading the filter cake washed in the step 5).
2. The method for preparing the nano calcium carbonate special for polyester degradation plastic, which is disclosed in claim 1, is characterized in that: the adding amount of the zirconium alcohol compound in the step 2) is 1.0-2.0% of the dry weight of the calcium hydroxide.
3. The method for preparing the nano calcium carbonate special for polyester degradation plastic, which is disclosed in claim 1, is characterized in that: the zirconium alcohol compound in the step 2) is any one or a mixture of two of zirconium propoxide and zirconium butoxide in any proportion.
4. The method for preparing the nano calcium carbonate special for polyester degradation plastic, which is disclosed in claim 1, is characterized in that: the addition amount of the associative polyurethane thickener in the step 3) is 2.0-3.0% of the dry weight of calcium hydroxide.
5. The method for preparing the nano calcium carbonate special for polyester degradation plastic, which is disclosed in claim 1, is characterized in that: the associative polyurethane thickener in the step 3) is a nonionic associative polyurethane thickener, the concentration of the active ingredients is more than or equal to 40%, and the viscosity is less than or equal to 14000cp.
6. The method for preparing the nano calcium carbonate special for polyester degradation plastic, which is disclosed in claim 1, is characterized in that: the step of secondary surface modification in the step 4) is as follows: delivering the calcium carbonate slurry to an activation kettle, heating to 90 ℃, and then adding low carbon chain saturated fatty acid to perform primary surface modification for 20-40 minutes; then adding epoxy resin to carry out secondary surface modification for 30-45 minutes.
7. The method for preparing the nano calcium carbonate special for polyester degradation plastic, which is disclosed in claim 6, is characterized in that: the addition amount of the low carbon chain saturated fatty acid is 0.5-1.0% of the dry basis of the calcium carbonate slurry, and the addition amount of the epoxy resin is 2.0-3.5% of the dry basis of the calcium carbonate slurry.
8. The method for preparing the nano calcium carbonate special for polyester degradation plastic, which is disclosed in claim 6, is characterized in that: the low carbon chain saturated fatty acid is saturated fatty acid with the carbon number of 10-14, the epoxy resin is glycidol amine epoxy resin, the epoxy value is 0.8-1.0, and the epoxy equivalent is 100-130.
9. The method for preparing the nano calcium carbonate special for the polyester family degradable plastic, which is disclosed in claim 8, is characterized in that: the low carbon chain saturated fatty acid is any one or a mixture formed by mixing more than two of capric acid, lauric acid and palmitic acid according to any proportion.
10. The method for preparing the nano calcium carbonate special for polyester degradation plastic, which is disclosed in claim 1, is characterized in that: the aprotic solvent in the step 5) is any one of carbon tetrachloride and N, N-dimethylformamide.
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