CN114804178A - 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 PDFInfo
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- CN114804178A CN114804178A CN202210557658.7A CN202210557658A CN114804178A CN 114804178 A CN114804178 A CN 114804178A CN 202210557658 A CN202210557658 A CN 202210557658A CN 114804178 A CN114804178 A CN 114804178A
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 285
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 137
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 45
- 229920000728 polyester Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000012065 filter cake Substances 0.000 claims abstract description 35
- 229920002635 polyurethane Polymers 0.000 claims abstract description 29
- 239000004814 polyurethane Substances 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002562 thickening agent Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- -1 zirconium alcohol compound Chemical class 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims description 87
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 52
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 45
- 239000000920 calcium hydroxide Substances 0.000 claims description 45
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 45
- 230000004048 modification Effects 0.000 claims description 40
- 238000012986 modification Methods 0.000 claims description 40
- 239000012528 membrane Substances 0.000 claims description 34
- 239000001569 carbon dioxide Substances 0.000 claims description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 26
- 238000003763 carbonization Methods 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 229920000647 polyepoxide Polymers 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 18
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 18
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 12
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 239000005639 Lauric acid Substances 0.000 claims description 9
- 235000019738 Limestone Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 230000029087 digestion Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- 239000006028 limestone Substances 0.000 claims description 9
- RQIHICWHMWNVSA-UHFFFAOYSA-N propan-1-ol;zirconium Chemical compound [Zr].CCCO RQIHICWHMWNVSA-UHFFFAOYSA-N 0.000 claims description 9
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 239000008399 tap water Substances 0.000 claims description 9
- 235000020679 tap water Nutrition 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 235000021314 Palmitic acid Nutrition 0.000 claims description 7
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 7
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- SKFIUGUKJUULEM-UHFFFAOYSA-N butan-1-ol;zirconium Chemical compound [Zr].CCCCO SKFIUGUKJUULEM-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 32
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 230000009974 thixotropic effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 22
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001896 polybutyrate Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical group CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Classifications
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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
- C01F11/182—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of special nano calcium carbonate for polyester family degradable plastics, which adopts a zirconium alcohol compound as a crystal form control agent and can effectively avoid the problem of high moisture absorption rate of the nano calcium carbonate caused by the residue of the crystal control agent; 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 agglomeration phenomenon generated by crystals can be effectively reduced, and the phenomenon of high water content of nano calcium carbonate caused by the agglomeration phenomenon is avoided; meanwhile, the filter cake is washed for multiple times by adopting the aprotic solvent in the filter pressing process, so that a hydrogen bond network system remained in the nano calcium carbonate filter cake can be removed as much as possible, the capillary effect caused in the filter cake drying process is reduced, the drying efficiency of the finished nano calcium carbonate product is further improved, and the technical effect of producing the nano calcium carbonate with the water content of less than 0.1% in conventional drying equipment and a preparation system is realized.
Description
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 degradable plastics.
Background
China, as the biggest world plastic product production and consumption country, must pay attention to the problem of white pollution, and the degradable plastic industry is expected to be put in quantity quickly under the condition of no plastic instruction. According to the execution time table and the execution strength of the plastic prohibition policy of each province and city and the development process of overseas degradable plastics, the demand change of the degradable plastics in the future 10 years of China is predicted. In 2025, the demand of degradable plastics in China is estimated to be 238 million tons, and the market scale can reach 477 hundred million yuan; by 2030, the demand of degradable plastics in China is estimated to be 428 ten thousand tons, and the market scale can reach 855 hundred million yuan. The market space of degradable plastics in China is huge.
With the contraction of plastic regulations in various places, the biodegradable environment-friendly materials of the polyester family mainly comprising PLA and PBAT are developed and met. Biodegradable plastics refer to a class of polymeric materials that can be broken down into carbon dioxide and water by the action of microorganisms in industrial or municipal composting facilities. According to different synthesis modes and raw material sources, biodegradable plastics can be divided into bio-based degradable plastics and petroleum-based degradable plastics. However, in the conventional techniques, it is difficult to popularize bulk materials such as PLA and PBAT in actual use because they lack sufficient toughness and stiffness. The application of the conventional nano materials such as silicon dioxide, aluminum oxide, titanium dioxide, barium sulfate and the like in the field of degradable 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, and when polymerization is stressed, the debonding of the nano particles and the polymer matrix material can initiate voiding 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 with the greatest application prospect in 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 undoubtedly causes the degradation of the polyester family degraded 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.
Chinese patent CN112646235 discloses a novel nano calcium carbonate for degradable plastic film and a preparation method thereof, which 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, 2-6 parts of coupling agent, 8-14 parts of activating agent, 1-5 parts of ionic liquid, 3-8 parts of polyethylene wax calcium carbonate master batch and a proper amount of water. The technology disclosed in the patent is not acceptable and accepted by people, more than the technology is like splicing and mixing of messy auxiliary agents, and as should be clear to chemical technicians, calcium oxide can have violent chemical reaction with water, ethylene propylene diene monomer and polyethylene wax calcium carbonate master batches both have higher melting points, and the forms in which the calcium carbonate is mixed with the calcium oxide cannot be known.
Chinese invention patent CN211575752 discloses a low moisture content nano calcium carbonate drying device, which mainly realizes drying in a physical mode, has better energy-saving and consumption-reducing functions, but cannot reduce the real moisture of the nano calcium carbonate fundamentally. Because the nano calcium carbonate is in a drying process due to capillary effect, when the moisture content is reduced to be below 0.3%, the conventional physical mode cannot realize dehydration.
In summary, in order to successfully apply the nano calcium carbonate to the field of degradable plastics, the control of low moisture and low moisture absorption rate is a prerequisite technical means.
Disclosure of Invention
The invention aims to solve the technical problem that the moisture content of the nano calcium carbonate cannot be reduced to below 0.3 percent due to high moisture content and high moisture absorption rate in the prior art; provides a preparation method of special nano calcium carbonate for polyester family degradable plastics, which aims to realize the technical effects of effectively reducing the water content and the moisture absorption rate of the nano calcium carbonate and ensuring that the final water content of the product is lower than 0.1 percent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of special nano calcium carbonate for polyester family degradable plastics comprises the following steps:
1) calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 6-8%, controlling the temperature to be 25-30 ℃, and then adding a zirconium alcohol compound serving as a crystal form control agent, and uniformly stirring and mixing;
3) conveying 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 aperture of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8 mm; when the conductivity in the reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, adding the associative polyurethane thickener, and then continuing introducing the carbon dioxide gas to carry out carbonation reaction until the pH of the slurry is less than or equal to 7.0 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) performing filter pressing and dehydration on the modified calcium carbonate slurry obtained in the step 4) to obtain a filter cake, and then performing pressure washing on the filter cake for 3-5 times by adopting an aprotic solvent; the washed solvent enters a distillation system and is recycled after water is evaporated;
6) and (3) crushing, drying, crushing and grading the filter cake washed in the step 5).
According to the invention, the zirconium alcohol compound is used as the crystal form control agent, so that the regrowth of the crystal face {104} of the calcium carbonate crystal can be promoted, and the zirconium alcohol compound can not remain on the surface of the nano calcium carbonate finished product after the 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; according to the method, the associative polyurethane thickener is added at the later stage of the 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 agglomeration phenomenon generated by crystals can be effectively reduced, and the phenomenon that the water content of nano calcium carbonate is high due to the agglomeration phenomenon is avoided; meanwhile, the filter cake is washed for many times by adopting the aprotic solvent in the filter pressing process, so that a hydrogen bond network system remained in the nano calcium carbonate filter cake can be removed as much as possible, the capillary effect caused in the filter cake drying process is reduced, the drying efficiency of the finished nano calcium carbonate product is further improved, and the nano calcium carbonate with the moisture content of less than 0.1 percent can be produced in conventional drying equipment and a preparation system.
On the basis of the technical scheme, the invention can be further 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 basis amount of the calcium hydroxide.
In a preferred embodiment of the present invention, the zirconium alcohol compound in step 2) is one of zirconium propanol and zirconium butanol, or a mixture of two of them mixed in any ratio.
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 basis amount of the 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 percent, and the viscosity is less than or equal to 14000 cp.
As a preferred technical solution of the present invention, the method for secondary surface modification in step 4) comprises: conveying 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, wherein the modification time is 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 amount of the calcium carbonate slurry, and the addition amount of the epoxy resin is 2.0-3.5% of the dry basis amount of the calcium carbonate slurry.
As a preferable technical scheme of the invention, the lower carbon chain saturated fatty acid is a saturated fatty acid with 10-14 carbon atoms, the epoxy resin is glycidyl amine epoxy resin, the epoxy value is 0.8-1.0, and the epoxy equivalent is 100-.
In a preferred embodiment of the present invention, the low-carbon-chain saturated fatty acid is a mixture of any one or more of capric acid, lauric acid and palmitic acid mixed at any ratio.
As a preferred embodiment of the present invention, the aprotic solvent in step 5) is any one of carbon tetrachloride and N, N-dimethylformamide.
The invention has the beneficial effects that:
1. the nano calcium carbonate product prepared by the method has the moisture content lower than 0.1 percent and low moisture absorption rate, and can not be degraded due to high moisture content or high moisture absorption rate in a degradable plastic system when used in the 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 property of the composite material of the nano calcium carbonate product and the degradable plastic system;
3. the preparation method 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 special nano calcium carbonate for polyester family degradable plastics, which aims to solve the technical problem that the moisture content of the nano calcium carbonate cannot be reduced to be below 0.3% due to high moisture content and high moisture absorption rate in the prior art, so that the technical effects of effectively reducing the moisture content and the moisture absorption rate of the nano calcium carbonate and enabling the final moisture content of a product to be lower than 0.1% are achieved.
The general idea adopted by the invention is as follows:
in the prior art, a plurality of factors causing the high moisture content of the finished product of the nano calcium carbonate are not related to each other, and any one of the factors can directly cause the high horizontal content of the finished product of the nano calcium carbonate, so that each factor in the preparation method needs to be eliminated one by one to obtain the technical effect that the final moisture content of the finished product is lower than 0.1 percent, specifically as follows:
1. because the traditional nano calcium carbonate preparation industry mostly adopts substances such as sucrose, citric acid, sulfate and the like as crystal control agents, the crystal control agents are remained on the surface of the nano calcium carbonate product in the subsequent process, so that the nano calcium carbonate product has high moisture absorption rate; the zirconium alcohol compound is used as the crystal form control agent, so that the regrowth of the crystal face of the {104} calcium carbonate crystal can be promoted, and the zirconium alcohol compound can not remain on the surface of the finished product of the nano calcium carbonate after the carbonation reaction is finished, 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 begin to form initial agglomeration, thereby influencing the subsequent drying effect of nano calcium carbonate; according to the invention, the associative polyurethane thickener is added at the later stage of the 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 agglomeration 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 no matter the nano calcium carbonate is fatty acid or fatty acid salt, the calcium salt finally coated on the surface of the calcium carbonate is generally a fatty acid-form calcium salt (provided that the surface treatment temperature is higher than the melting point of the fatty acid), the fatty acid-form calcium salt is an amphiphile, the metal ions are hydrophilic, and the fatty chain segment is hydrophobic, and under the condition of excessive treatment agent, the fatty acid-form calcium salt can form double-layer or even multi-layer coating on the surface of the calcium carbonate, so that the fatty chain of the hydrophobic chain segment can not be completely exposed outside the surface of the calcium carbonate, and when more hydrophilic ions are exposed outside the surface of the calcium carbonate, the later-stage moisture absorption risk can be caused; and the fatty acid salt system does not form good compatibility in degraded plastics. Therefore, the invention adopts two surface treatment processes, wherein the first process adds low-carbon chain fatty acid as little as possible, and the addition amount is 0.5-1.0% of nano calcium carbonate; in the second treatment procedure, epoxy resin is used as a modifier to coat the nano calcium carbonate, so that the hydrophobic effect of the surface of the nano calcium carbonate is ensured, and the compatibility of the nano calcium carbonate in a degradable plastic system is improved;
4. the filter cake is washed for multiple times by adopting the aprotic solvent in the filter pressing process, so that a hydrogen bond network system remained in the nano calcium carbonate filter cake can be removed as much as possible, and a capillary effect caused in the filter cake drying process is reduced, so that the drying efficiency of the finished nano calcium carbonate 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 degradable plastics comprises the following steps:
1) calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 6-8%, controlling the temperature to be 25-30 ℃, and then adding a zirconium alcohol compound serving as a crystal form control agent, and uniformly stirring and mixing;
3) conveying 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 aperture of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8 mm; when the conductivity in the reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, adding the associative polyurethane thickener, and then continuing introducing the carbon dioxide gas to carry out carbonation reaction until the pH of the slurry is less than or equal to 7.0 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 and 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 be evaporated to dryness and then recycled;
6) and (3) 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 basis amount of the calcium hydroxide; the zirconium alcohol compound in the step 2) is any one of zirconium propanol or zirconium butanol or a mixture of the two in any proportion.
The addition amount of the associative polyurethane thickener in the step 3) is 2.0 to 3.0 percent of the dry basis amount of the calcium hydroxide; 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 percent, and the viscosity is less than or equal to 14000cp, such as German Wokkel VOK-WT 105 associative polyurethane thickener.
The method for secondary surface modification in the step 4) comprises the following steps: conveying 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, wherein the modification time is 30-45 minutes.
The addition amount of the low-carbon chain saturated fatty acid is 0.5-1.0% of the dry basis amount of the calcium carbonate slurry, and the addition amount of the epoxy resin is 2.0-3.5% of the dry basis amount of the calcium carbonate slurry; the low-carbon-chain saturated fatty acid is a saturated fatty acid with 10-14 carbon atoms, when the carbon atoms are 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 atoms are less than 10, the hydrophobic effect of the fatty acid is poor, and the later hygroscopic property of a finished product is influenced, so that the low-carbon-chain saturated fatty acid is a mixture formed by mixing any one or more than any two of capric acid, lauric acid and palmitic acid according to any proportion; the epoxy resin is glycidyl 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.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of nano calcium carbonate special for polyester family degradable plastics comprises the following steps:
1) calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 6%, controlling the temperature to be 30 ℃, and then adding zirconium propanol as a crystal form control agent, and uniformly stirring and mixing; wherein the addition amount of zirconium propanol is 1.5 percent of the dry basis amount of calcium hydroxide;
3) conveying 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 aperture of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8 mm; when the conductivity in the reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding the associative polyurethane thickener, wherein the addition amount of the associative polyurethane thickener is 2.5 percent of the dry basis amount of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH 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, heating to 90 ℃, and then adding lauric acid to perform primary surface modification, wherein the addition amount of the lauric acid is 0.5 percent of the dry basis amount of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the adding amount of the epoxy resin is 2.5 percent of the dry basis amount 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 be evaporated to dryness and then recycled;
6) and (3) 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 degradable plastics comprises the following steps:
1) calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 7%, controlling the temperature to be 28 ℃, and then adding zirconium butoxide serving as a crystal form control agent to be uniformly stirred and mixed; wherein the addition amount of zirconium butoxide is 1.0 percent of the dry basis amount of calcium hydroxide;
3) conveying 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 aperture of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8 mm; when the conductivity in the reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding the associative polyurethane thickener, wherein the addition amount of the associative polyurethane thickener is 2.0 percent of the dry basis amount of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH 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, heating to 90 ℃, and then adding palmitic acid to perform primary surface modification, wherein the addition amount of the palmitic acid is 0.5 percent of the dry basis amount of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the adding amount of the epoxy resin is 2.5 percent of the dry basis amount 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 3 times by adopting a carbon tetrachloride solvent; the washed solvent enters a distillation system to be evaporated to dryness and then recycled;
6) and (3) 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 degradable plastics comprises the following steps:
1) calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 8%, controlling the temperature to be 25 ℃, and then adding zirconium propanol as a crystal form control agent, and uniformly stirring and mixing; wherein the addition amount of zirconium propanol is 2.0 percent of the dry basis amount of calcium hydroxide;
3) conveying 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 aperture of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8 mm; when the conductivity in the reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding the associative polyurethane thickener, wherein the addition amount of the associative polyurethane thickener is 3.0 percent of the dry basis amount of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH 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, heating to 90 ℃, and then adding capric acid to carry out primary surface modification, wherein the addition amount of the capric acid is 1.0 percent of the dry basis amount of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the adding amount of the epoxy resin is 3.0 percent of the dry basis amount of the calcium carbonate slurry, and the modification time is 35 minutes;
5) carrying out filter pressing and 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 5 times by adopting an N, N-dimethylformamide solvent; the washed solvent enters a distillation system to be evaporated to dryness and then recycled;
6) and (3) 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 degradable plastics comprises the following steps:
1) calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 7%, controlling the temperature to be 28 ℃, and then adding zirconium propanol and zirconium butanol according to a mass ratio of 1: 1 as a crystal form control agent, and stirring and mixing uniformly; wherein the addition amount of the crystal form control agent is 1.8 percent of the dry basis amount of the calcium hydroxide;
3) conveying 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 aperture of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8 mm; when the conductivity in the reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding the associative polyurethane thickener, wherein the addition amount of the associative polyurethane thickener is 2.6 percent of the dry basis amount of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH 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, heating to 90 ℃, and adding lauric acid and palmitic acid in a 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 percent of the dry basis amount of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the adding amount of the epoxy resin is 3.5 percent of the dry basis amount of the calcium carbonate slurry, and the modification time is 35 minutes;
5) carrying out filter pressing and 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 an N, N-dimethylformamide solvent; the washed solvent enters a distillation system to be evaporated to dryness and then recycled;
6) and (3) 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 degradable plastics comprises the following steps:
1) calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 6.5%, controlling the temperature to be 25.5 ℃, and then adding zirconium propanol and zirconium butanol according to the mass ratio of 3: 2 as a crystal form control agent, and stirring and mixing uniformly; wherein the addition amount of the crystal form control agent is 1.2 percent of the dry basis amount of the calcium hydroxide;
3) conveying 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 aperture of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8 mm; when the conductivity in the reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, and adding the associative polyurethane thickener, wherein the addition amount of the associative polyurethane thickener is 2.8 percent of the dry basis amount of calcium hydroxide; then continuously introducing carbon dioxide gas to carry out carbonation reaction until the pH 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, heating to 90 ℃, and adding lauric acid, palmitic acid and capric acid according to a 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 percent of the dry basis amount of the calcium carbonate slurry, and the modification time is 30 minutes; then adding epoxy resin for secondary surface modification, wherein the adding amount of the epoxy resin is 3.5 percent of the dry basis amount of the calcium carbonate slurry, and the modification time is 35 minutes;
5) carrying out filter pressing and 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 5 times by adopting an N, N-dimethylformamide solvent; the washed solvent enters a distillation system to be evaporated to dryness and then recycled;
6) and (3) crushing, drying, crushing and grading the filter cake washed in the step 5) to obtain the nano calcium carbonate product.
Comparative example 1
1) Calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 6.5%, controlling the temperature to be 25.5 ℃, and then adding sucrose serving as a crystal form control agent, and uniformly stirring and mixing; wherein the addition amount of the sucrose is 0.8 percent of the dry basis amount of the calcium hydroxide;
3) conveying the calcium hydroxide slurry obtained in the step 2) to a film dispersion carbonization device, and introducing carbon dioxide gas to carry out carbonation reaction until the pH of the slurry is less than or equal to 7.0 to obtain calcium carbonate slurry; wherein the aperture of the membrane pores of the membrane dispersion carbonization device is 0.3-0.8 mm;
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 addition amount of the lauric acid is 3.7 percent of the dry basis amount of the calcium carbonate slurry, and the modification 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) and (3) crushing, drying, crushing and grading the filter cake washed in the step 5) to obtain the nano calcium carbonate product.
Nano calcium carbonate product moisture absorption stability test
The nano calcium carbonate products obtained in examples 1 to 5 and comparative example 1 of the present invention were subjected to a comparative moisture absorption stability test (test method is referred to the test method of GB/T19591 water content and a coulometry method water content measuring instrument), and the results are shown in the following table:
as can be seen from the above table, the moisture content of the nano calcium carbonate product prepared by the invention is lower than 0.1%, and the moisture 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 to 5 and comparative example 1 of the present invention were respectively left for 30 days and then the degradable plastics were prepared according to the following formulation and process:
the application formula of the degradable plastic comprises the following steps:
| composition of | Mass ratio of |
| PLA | 40％ |
| PBAT | 25％ |
| Thermoplastic starch | 20％ |
| Nano 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 temperature of each process zone is respectively set to be 155, 165, 170, 180, 185 and 180 ℃;
after granulation, standard sample bars are prepared by an injection molding machine for testing the tensile strength and the 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 can be seen from the above table, the nano calcium carbonate product prepared by the method 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 illustrative of the present invention and do not limit the scope of the present invention. In addition, other variations and modifications will be apparent to persons skilled in the art based on the foregoing description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A preparation method of special nano calcium carbonate for polyester family degradable plastics comprises the following steps:
1) calcining limestone in a vertical kiln at the temperature of 950-1150 ℃; after calcination, mixing lime and tap water according to a mass ratio of 1: 5, carrying out mixed digestion reaction, and sieving by a hydrocyclone to remove impurities to obtain calcium hydroxide slurry;
2) adjusting the concentration of the calcium hydroxide slurry obtained in the step 1) to 6-8%, controlling the temperature to be 25-30 ℃, and then adding a zirconium alcohol compound serving as a crystal form control agent, and uniformly stirring and mixing;
3) conveying 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 aperture of a membrane hole of the membrane dispersion carbonization device is 0.3-0.8 mm; when the conductivity in the reaction system in the membrane dispersion carbonization device is reduced to 5ms/cm, stopping introducing carbon dioxide gas, adding the associative polyurethane thickener, and then continuing introducing the carbon dioxide gas to carry out carbonation reaction until the pH of the slurry is less than or equal to 7.0 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 and 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 be evaporated to dryness and then recycled;
6) and (3) crushing, drying, crushing and grading the filter cake washed in the step 5).
2. The method for preparing the nano calcium carbonate special for the polyester family degradable plastics according to claim 1, which is characterized in that: the adding amount of the zirconium alcohol compound in the step 2) is 1.0-2.0% of the dry basis amount of the calcium hydroxide.
3. The method for preparing the nano calcium carbonate special for the polyester family degradable plastics according to claim 1, which is characterized in that: the zirconium alcohol compound in the step 2) is any one of zirconium propanol or zirconium butanol or a mixture of the two in any proportion.
4. The method for preparing the nano calcium carbonate special for the polyester family degradable plastics according to claim 1, which is characterized in that: the addition amount of the associative polyurethane thickener in the step 3) is 2.0-3.0% of the dry basis amount of the calcium hydroxide.
5. The method for preparing the nano calcium carbonate special for the polyester family degradable plastics according to claim 1, which is characterized by comprising the following steps: 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 percent, and the viscosity is less than or equal to 14000 cp.
6. The method for preparing the nano calcium carbonate special for the polyester family degradable plastics according to claim 1, which is characterized in that: the secondary surface modification in the step 4) comprises the following steps: conveying 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, wherein the modification time is 30-45 minutes.
7. The method for preparing the nano calcium carbonate special for the polyester family degradable plastics according to 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 amount of the calcium carbonate slurry, and the addition amount of the epoxy resin is 2.0-3.5% of the dry basis amount of the calcium carbonate slurry.
8. The method for preparing the nano calcium carbonate special for the polyester family degradable plastics according to claim 6 is characterized in that: the low-carbon chain saturated fatty acid is a saturated fatty acid with 10-14 carbon atoms, the epoxy resin is glycidyl 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 plastics according to claim 8 is characterized in that: the low-carbon chain saturated fatty acid is a mixture formed by mixing any one or 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 the polyester family degradable plastics according to claim 1, which 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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| CN116004035A (en) * | 2022-12-20 | 2023-04-25 | 烟台大学 | Inorganic calcium carbonate surface modification method and application thereof |
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