CN107629487B - Modification method of superfine light calcium carbonate and application of superfine light calcium carbonate in plastics - Google Patents
Modification method of superfine light calcium carbonate and application of superfine light calcium carbonate in plastics Download PDFInfo
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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 165
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 83
- 238000002715 modification method Methods 0.000 title abstract description 9
- 239000004033 plastic Substances 0.000 title description 4
- 229920003023 plastic Polymers 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000003763 carbonization Methods 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 230000004913 activation Effects 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 19
- -1 butyl ether phthalate sodium salt Chemical compound 0.000 claims abstract description 18
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 11
- 238000004381 surface treatment Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000004310 lactic acid Substances 0.000 claims abstract description 8
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 8
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 8
- 239000001509 sodium citrate Substances 0.000 claims abstract description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 8
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims abstract description 7
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940035044 sorbitan monolaurate Drugs 0.000 claims abstract description 6
- GKHAMKUBNXPDAS-UHFFFAOYSA-N 1-butoxybutane;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.CCCCOCCCC GKHAMKUBNXPDAS-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 15
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 15
- 230000029087 digestion Effects 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- GQQZWJGHYIMFRS-UHFFFAOYSA-N 1-butoxybutane;phthalic acid Chemical compound CCCCOCCCC.OC(=O)C1=CC=CC=C1C(O)=O GQQZWJGHYIMFRS-UHFFFAOYSA-N 0.000 claims 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 description 16
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 4
- ODCMOZLVFHHLMY-UHFFFAOYSA-N 1-(2-hydroxyethoxy)hexan-2-ol Chemical compound CCCCC(O)COCCO ODCMOZLVFHHLMY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CMCJNODIWQEOAI-UHFFFAOYSA-N bis(2-butoxyethyl)phthalate Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1C(=O)OCCOCCCC CMCJNODIWQEOAI-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a modification method of superfine light calcium carbonate, belonging to the technical field of calcium carbonate manufacture, and the modification method comprises the following steps: pulping, surface treatment and preparing a finished product; wherein, the pulping comprises: preparation of Ca (OH)2Suspension, adding a crystal form control agent and carrying out carbonization reaction; the crystal form control agent is prepared from the following raw materials: 4-8 parts of sodium citrate, 5-10 parts of citric acid, 3-5 parts of glycolic acid, 1-3 parts of propionic acid and 1-3 parts of lactic acid; the surface activation coating agent is prepared from the following raw materials: 14-20 parts of butyl ether phthalate sodium salt, 2-6 parts of isopropanol, 3-7 parts of butyl ether diethylene glycol, 8-12 parts of octadecylamine, 4-8 parts of dodecylamine and 5-9 parts of sorbitan monolaurate; the invention can be applied to improving the toughness and strength of PVC, and solves the problems that the traditional nano calcium carbonate is difficult to uniformly disperse when being blended with PVC and has poor compatibility with PVC.
Description
Technical Field
The invention belongs to the technical field of calcium carbonate manufacturing, and particularly relates to a modification method of superfine light calcium carbonate and application of the superfine light calcium carbonate in plastics.
Background
PVC is one of thermoplastic resins which are most widely applied and used in daily life, has the advantages of flame retardance, wear resistance, corrosion resistance, low price and the like, and is widely applied to the aspects of pipelines, door and window profiles, electric wires and the like. However, PVC has low impact strength and poor thermal stability; among them, the disadvantage of lower impact strength severely limits the application of PVC, so we must toughen and modify PVC.
CaCO3Is an important inorganic chemical product. Because of low price, wide raw material sources and no toxicity, the filler is widely used as the filler of rubber, plastics, paper, paint, toothpaste and the like. Common CaCO3The nano calcium carbonate is used as a filler and only has the functions of increasing the volume and reducing the price of a finished product, and the nano calcium carbonate not only has the functions of increasing the volume and reducing the cost, but also has the function of reinforcing, and can be used for improving the mechanical properties such as the strength, the modulus and the like of a matrix to achieve the aim of increasing the volume and the strength; however, the traditional nano calcium carbonate has a large specific surface area and a high surface free energy, is very easy to agglomerate, is difficult to uniformly disperse when being blended with PVC, and has poor compatibility with PVC, so that the impact strength of the blended PVC cannot be improved.
Disclosure of Invention
The invention aims to provide a method for modifying superfine light calcium carbonate, which is used for solving the problems that the traditional nano calcium carbonate is difficult to uniformly disperse when being blended with PVC and has poor compatibility with PVC.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for modifying superfine light calcium carbonate comprises the following steps:
(1) pulping: which comprises the following steps:
A1. preparation of Ca (OH)2Suspension: placing CaO into a digestion tank, adding water for digestion to obtain Ca (OH)2A suspension;
A2. adding a crystal form control agent: ca (OH) prepared in step A12Adding a crystal form control agent into the suspension to obtain a mixed solution; the crystal form control agent is prepared from the following raw materials in parts by weight: 4-8 parts of sodium citrate, 5-10 parts of citric acid, 3-5 parts of glycolic acid, 1-3 parts of propionic acid and 1-3 parts of lactic acid;
A3. and (3) carbonization reaction: firstly, adding the mixed solution obtained in the step A2 into a carbonization reactor with a stirring device; then, adding a dispersant into the mixed solution; then, the volume concentration of the raw materials is input into the carbonization reactor to be 70 to 80 percentCO of2The gas is subjected to carbonization reaction and is stirred by the stirring device; finally, stopping the reaction when the pH value of the solution in the carbonization reactor is 6.8-7.2 to obtain nano calcium carbonate slurry;
(2) surface treatment: firstly, conveying the nano calcium carbonate slurry obtained in the step A3 to an activation treatment pool; then, heating the nano calcium carbonate slurry to 60-70 ℃, and continuously stirring; then, adding a surface activation coating agent into the nano calcium carbonate slurry for coating; the surface activation coating agent is prepared from the following raw materials in parts by weight: 14-20 parts of butyl ether phthalate sodium salt, 2-6 parts of isopropanol, 3-7 parts of butyl ether diethylene glycol, 8-12 parts of octadecylamine, 4-8 parts of dodecylamine and 5-9 parts of sorbitan monolaurate; finally, after surface treatment for 1-2 hours, modified slurry is obtained;
(3) preparing a finished product: and (3) carrying out filter pressing, drying and crushing on the modified slurry obtained in the step (2) to obtain a finished product of the nano calcium carbonate.
Preferably, in the step A1, when water is added for digestion, the mass ratio of the water to the CaO is 1:15-20, and the water temperature is 70-80 ℃.
Preferably, in the step A2, the mass ratio of the crystal form control agent to the CaO is 1: 20-50.
Preferably, in step A3, CO2The gas flow rate was: 0.8-1.5L/h gCa (OH)2。
Preferably, in step a3, the dispersant is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl methacrylate, triethanolamine, and phosphate ester salt.
Preferably, in step a3, the mass ratio of the dispersant to the CaO is: 1: 40-50.
Preferably, in the step (2), the method for preparing butyl cellosolve phthalate sodium salt comprises the following steps:
B1. the following raw materials were prepared: phthalic anhydride, butyl cellosolve, sodium hydroxide;
B2. adding phthalic anhydride in the step B1 into a reaction tank, and heating to 80-90 ℃;
B3. adding ethylene glycol monobutyl ether in the step B1 into the reaction tank in the step B2 gradually, after reacting for a period of time at constant temperature, starting timing when phthalic anhydride begins to dissolve, and measuring the esterification rate by adopting an alkali titration method;
B4. stopping the reaction when the esterification rate measured in the step B3 is not increased any more to obtain phthalic acid monoethylene glycol butyl ether ester;
B5. and (3) when the temperature of the butyl ether mono-glycol phthalate in the step B4 is reduced to 60-70 ℃, adding sodium hydroxide, and violently stirring to obtain the butyl ether mono-glycol phthalate sodium salt in the step (2).
Preferably, in the step (2), the mass ratio of the surface-activated coating agent to the nano calcium carbonate is as follows: 1:30-100.
The modification method of the superfine light calcium carbonate can be applied to improving the toughness and strength of PVC, and the finished product of the nanometer calcium carbonate is mixed with PVC to prepare the PVC composite material.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the crystal form control agent contains sodium citrate, citric acid, glycolic acid, propionic acid and lactic acid in a reasonable proportion; in the carbonization reaction process, the crystal form control agent can control the directional growth of the nano calcium carbonate, so that the nano calcium carbonate has the advantages of narrow particle size range and uniform distribution; the addition of the sodium citrate changes the appearance of the nano calcium carbonate, and reduces the crystallinity of the nano calcium carbonate, so that the crystal form of the nano calcium carbonate is more complete and the crystallinity is higher; the citric acid, the glycolic acid, the propionic acid and the lactic acid can ensure that the nano calcium carbonate has good dispersibility, uniform particle size distribution and stable chemical structure; the nano calcium carbonate obtained after the crystal form control agent is added has good dispersibility, so that the specific surface area and the surface free energy of the nano calcium carbonate are greatly reduced, and the agglomeration phenomenon is not easy to occur.
2. The surface activation coating agent can modify the surface of the nano calcium carbonate particles, the modified nano calcium carbonate particles are uniformly dispersed, the agglomeration phenomenon in the use process of the nano calcium carbonate particles is prevented, and the problems that the nano calcium carbonate and PVC are difficult to uniformly disperse and poor in compatibility when being blended are further solved. The impact strength of the PVC composite material prepared by mixing the nano calcium carbonate modified by the surface activation coating agent and PVC is greatly improved by about 2 times compared with the PCV composite material prepared by mixing PVC and unmodified nano calcium carbonate. The surface activation coating agent of the invention is relative to the common coating agents: the sodium stearate and titanate coupling agent have better modification effect, and the impact strength is improved by about 1 time compared with the titanate coupling agent. Wherein, the butyl ether phthalate sodium monoethylene glycol in the surface activation coating agent has carboxylic acid groups and organic groups similar to dioctyl phthalate, and the carboxylic acid groups can form acting force with the nano calcium carbonate to coat on the surface; meanwhile, organic groups similar to dioctyl phthalate can be well dispersed in a PVC matrix; octadecylamine and dodecylamine can convert the hydrophilic oleophobic property of the surface of the nano calcium carbonate into oleophilic hydrophobic property, so that the dispersibility is greatly improved.
Detailed Description
The technical solution of the present invention will be further specifically described below with reference to specific embodiments.
Example 1
A method for modifying superfine light calcium carbonate comprises the following steps:
(1) pulping: which comprises the following steps:
A1. preparation of Ca (OH)2Suspension: placing CaO into a digestion tank, adding water for digestion to obtain Ca (OH)2A suspension; when water is added for digestion, the mass ratio of the water to the CaO is 1:20, and the water temperature is 70 ℃.
A2. Adding a crystal form control agent: ca (OH) prepared in step A12Adding a crystal form control agent into the suspension to obtain a mixed solution; the crystal form control agent is prepared from the following raw materials in parts by weight: 4 parts of sodium citrate, 5 parts of citric acid, 3 parts of glycolic acid, 1 part of propionic acid and 1 part of lactic acid; the mass ratio of the crystal form control agent to the CaO is 1: 50.
A3. And (3) carbonization reaction: first, the one obtained in step A2Adding the mixed solution into a carbonization reactor with a stirring device; then, adding a dispersant into the mixed solution; the dispersant is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl methacrylate, triethanolamine and phosphate; the mass ratio of the dispersing agent to the CaO is as follows: 1: 50; then, 70 vol% CO was supplied to the carbonization reactor2The gas is subjected to carbonization reaction and is stirred by the stirring device; CO 22The gas flow rate was: 0.8/h gCa (OH)2(ii) a And finally, stopping the reaction when the pH value of the solution in the carbonization reactor is 6.8 to obtain the nano calcium carbonate slurry.
(2) Surface treatment: firstly, conveying the nano calcium carbonate slurry obtained in the step A3 to an activation treatment pool; then, heating the nano calcium carbonate slurry to 60 ℃, and continuously stirring; then, adding a surface activation coating agent into the nano calcium carbonate slurry for coating; the surface activation coating agent is prepared from the following raw materials in parts by weight: 14 parts of butyl ether phthalate sodium salt, 2 parts of isopropanol, 3 parts of butyl diethylene glycol, 8 parts of octadecylamine, 4 parts of dodecylamine and 5 parts of sorbitan monolaurate; finally, after surface treatment for 1 hour, obtaining modified slurry; the mass ratio of the surface activation coating agent to the nano calcium carbonate is as follows: 1:100. The preparation method of the butyl ether phthalate sodium salt comprises the following steps:
B1. the following raw materials were prepared: phthalic anhydride, butyl cellosolve and sodium hydroxide.
B2. Phthalic anhydride from step B1 was added to the reaction tank and heated to 80 ℃.
B3. And B, gradually adding the ethylene glycol butyl ether in the step B1 into the reaction tank in the step B2, after the constant-temperature reaction is carried out for a period of time, timing when the phthalic anhydride begins to dissolve, and measuring the esterification rate by adopting an alkali titration method.
B4. And (4) stopping the reaction when the esterification rate measured in the step B3 is not increased any more, so as to obtain the phthalic acid monoethylene glycol butyl ether ester.
B5. And (3) when the temperature of the butyl ether mono-glycol phthalate in the step B4 is reduced to 60 ℃, adding sodium hydroxide, and violently stirring to obtain the butyl ether mono-glycol phthalate sodium salt in the step (2).
(3) Preparing a finished product: and (3) carrying out filter pressing, drying and crushing on the modified slurry obtained in the step (2) to obtain a finished product of the nano calcium carbonate.
The modification method of the superfine light calcium carbonate can be applied to improving the toughness and strength of PVC, and the finished product of the nanometer calcium carbonate is mixed with PVC to prepare the PVC composite material. The impact strength, tensile strength and bending strength of the PVC composite were measured, and the measurement data are shown in table 1.
Example 2
A method for modifying superfine light calcium carbonate comprises the following steps:
(1) pulping: which comprises the following steps:
A1. preparation of Ca (OH)2Suspension: placing CaO into a digestion tank, adding water for digestion to obtain Ca (OH)2A suspension; when water is added for digestion, the mass ratio of the water to the CaO is 1:15, and the water temperature is 80 ℃.
A2. Adding a crystal form control agent: ca (OH) prepared in step A12Adding a crystal form control agent into the suspension to obtain a mixed solution; the crystal form control agent is prepared from the following raw materials in parts by weight: 8 parts of sodium citrate, 10 parts of citric acid, 5 parts of glycolic acid, 3 parts of propionic acid and 3 parts of lactic acid; the mass ratio of the crystal form control agent to the CaO is 1: 20.
A3. And (3) carbonization reaction: firstly, adding the mixed solution obtained in the step A2 into a carbonization reactor with a stirring device; then, adding a dispersant into the mixed solution; the dispersant is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl methacrylate, triethanolamine and phosphate; the mass ratio of the dispersing agent to the CaO is as follows: 1: 40; then, CO with a volume concentration of 80% was supplied to the carbonization reactor2The gas is subjected to carbonization reaction and is stirred by the stirring device; CO 22The gas flow rate was: 1.5L/h gCa (OH)2(ii) a And finally, stopping the reaction when the pH value of the solution in the carbonization reactor is 7.2 to obtain the nano calcium carbonate slurry.
(2) Surface treatment: firstly, conveying the nano calcium carbonate slurry obtained in the step A3 to an activation treatment pool; then, heating the nano calcium carbonate slurry to 70 ℃, and continuously stirring; then, adding a surface activation coating agent into the nano calcium carbonate slurry for coating; the surface activation coating agent is prepared from the following raw materials in parts by weight: 20 parts of butyl ether phthalate sodium salt, 6 parts of isopropanol, 7 parts of butyl diethylene glycol, 12 parts of octadecylamine, 8 parts of dodecylamine and 9 parts of sorbitan monolaurate; finally, after surface treatment for 2 hours, modified slurry is obtained; the mass ratio of the surface activation coating agent to the nano calcium carbonate is as follows: 1:30. The preparation method of the butyl ether phthalate sodium salt comprises the following steps:
B1. the following raw materials were prepared: phthalic anhydride, butyl cellosolve and sodium hydroxide.
B2. Phthalic anhydride from step B1 was added to the reaction tank and heated to 90 ℃.
B3. And B, gradually adding the ethylene glycol butyl ether in the step B1 into the reaction tank in the step B2, after the constant-temperature reaction is carried out for a period of time, timing when the phthalic anhydride begins to dissolve, and measuring the esterification rate by adopting an alkali titration method.
B4. And (4) stopping the reaction when the esterification rate measured in the step B3 is not increased any more, so as to obtain the phthalic acid monoethylene glycol butyl ether ester.
B5. And (3) when the temperature of the butyl ether mono-glycol phthalate in the step B4 is reduced to 70 ℃, adding sodium hydroxide, and violently stirring to obtain the butyl ether mono-glycol phthalate sodium salt in the step (2).
(3) Preparing a finished product: and (3) carrying out filter pressing, drying and crushing on the modified slurry obtained in the step (2) to obtain a finished product of the nano calcium carbonate.
The modification method of the superfine light calcium carbonate can be applied to improving the toughness and strength of PVC, and the finished product of the nanometer calcium carbonate is mixed with PVC to prepare the PVC composite material. The impact strength, tensile strength and bending strength of the PVC composite were measured, and the measurement data are shown in table 1.
Example 3
A method for modifying superfine light calcium carbonate comprises the following steps:
(1) pulping: which comprises the following steps:
A1. preparation of Ca (OH)2Suspension: placing CaO into a digestion tank, adding water for digestion to obtain Ca (OH)2A suspension; when water is added for digestion, the mass ratio of the water to the CaO is 1:18, and the water temperature is 75 ℃.
A2. Adding a crystal form control agent: ca (OH) prepared in step A12Adding a crystal form control agent into the suspension to obtain a mixed solution; the crystal form control agent is prepared from the following raw materials in parts by weight: 6 parts of sodium citrate, 8 parts of citric acid, 4 parts of glycolic acid, 2 parts of propionic acid and 2 parts of lactic acid; the mass ratio of the crystal form control agent to the CaO is 1: 35.
A3. And (3) carbonization reaction: firstly, adding the mixed solution obtained in the step A2 into a carbonization reactor with a stirring device; then, adding a dispersant into the mixed solution; the dispersant is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl methacrylate, triethanolamine and phosphate; the mass ratio of the dispersing agent to the CaO is as follows: 1: 45, a first step of; then, CO with a volume concentration of 75% was supplied to the carbonization reactor2The gas is subjected to carbonization reaction and is stirred by the stirring device; CO 22The gas flow rate was: 1.1L/h gCa (OH)2(ii) a And finally, stopping the reaction when the pH value of the solution in the carbonization reactor is 7, and obtaining the nano calcium carbonate slurry.
(2) Surface treatment: firstly, conveying the nano calcium carbonate slurry obtained in the step A3 to an activation treatment pool; then, heating the nano calcium carbonate slurry to 65 ℃, and continuously stirring; then, adding a surface activation coating agent into the nano calcium carbonate slurry for coating; the surface activation coating agent is prepared from the following raw materials in parts by weight: 17 parts of butyl ether phthalate sodium salt, 4 parts of isopropanol, 5 parts of butyl diethylene glycol, 10 parts of octadecylamine, 6 parts of dodecylamine and 7 parts of sorbitan monolaurate; finally, after surface treatment for 1.5 hours, modified slurry is obtained; the mass ratio of the surface activation coating agent to the nano calcium carbonate is as follows: 1:65. The preparation method of the butyl ether phthalate sodium salt comprises the following steps:
B1. the following raw materials were prepared: phthalic anhydride, butyl cellosolve and sodium hydroxide.
B2. Phthalic anhydride from step B1 was added to the reaction tank and heated to 85 ℃.
B3. And B, gradually adding the ethylene glycol butyl ether in the step B1 into the reaction tank in the step B2, after the constant-temperature reaction is carried out for a period of time, timing when the phthalic anhydride begins to dissolve, and measuring the esterification rate by adopting an alkali titration method.
B4. And (4) stopping the reaction when the esterification rate measured in the step B3 is not increased any more, so as to obtain the phthalic acid monoethylene glycol butyl ether ester.
B5. And (3) when the temperature of the butyl ether mono-glycol phthalate in the step B4 is reduced to 65 ℃, adding sodium hydroxide, and violently stirring to obtain the butyl ether mono-glycol phthalate sodium salt in the step (2).
(3) Preparing a finished product: and (3) carrying out filter pressing, drying and crushing on the modified slurry obtained in the step (2) to obtain a finished product of the nano calcium carbonate.
The modification method of the superfine light calcium carbonate can be applied to improving the toughness and strength of PVC, and the finished product of the nanometer calcium carbonate is mixed with PVC to prepare the PVC composite material. The impact strength, tensile strength and bending strength of the PVC composite were measured, and the measurement data are shown in table 1.
In this regard, the applicant has also devised a comparative example of the present invention, specifically as follows:
comparative example 1
PVC is not added with nano calcium carbonate, and the impact strength, tensile strength and bending strength of the PVC are measured, and the measurement data are shown in Table 1.
Comparative example 2
When step (2) is performed, the surface-activated coating agent is replaced by a conventional activator titanate coupling agent, and other treatment is the same as that of example 3; the modified nano calcium carbonate prepared after the surface activation coating agent is replaced is mixed with PVC to prepare a PVC composite material, and the impact strength, the tensile strength and the bending strength of the PVC composite material are measured, wherein the measurement data are shown in Table 1.
TABLE 1
As can be seen from Table 1, the impact strength, tensile strength and bending strength of the PVC composite material prepared by mixing the nano calcium carbonate prepared by the method of the invention with PVC are greatly improved, and are improved by about 2 times compared with the PCV composite material prepared by mixing PVC with unmodified nano calcium carbonate. Compared with the common modified coating agent, the surface activated coating agent has better modification effect, and the impact strength is improved by about 1 time compared with the titanate coupling agent. In addition, after the calcium carbonate prepared by the common modified coating agent is compounded with PVC, the tensile strength and the bending strength of the PVC composite material are generally reduced, but the PVC composite material formed by compounding the nano calcium carbonate prepared by the method and the PVC cannot be subjected to the condition, and the tensile strength and the bending strength of the PVC composite material are also improved. The invention has simple manufacturing process, low equipment investment and good industrial popularization value.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (3)
1. A method for modifying superfine light calcium carbonate is characterized by comprising the following steps:
(1) pulping: which comprises the following steps:
A1. preparation of Ca (OH)2Suspension: placing CaO into a digestion tank, adding water for digestion to obtain Ca (OH)2A suspension;
A2. adding a crystal form control agent: ca (OH) prepared in step A12Adding a crystal form control agent into the suspension to obtain a mixed solution; the crystal form control agent is prepared from the following raw materials in parts by weight: 4-8 parts of sodium citrate, 5-10 parts of citric acid, 3-5 parts of glycolic acid, 1-3 parts of propionic acid and 1-3 parts of lactic acid;
A3. and (3) carbonization reaction: firstly, adding the mixed solution obtained in the step A2 into a carbonization reactor with a stirring device; then, adding a dispersant into the mixed solution; then, feeding CO with the volume concentration of 70-80% into the carbonization reactor2The gas is subjected to carbonization reaction and is stirred by the stirring device; finally, stopping the reaction when the pH of the solution in the carbonization reactor is =6.8-7.2, and obtaining nano calcium carbonate slurry;
(2) surface treatment: firstly, conveying the nano calcium carbonate slurry obtained in the step A3 to an activation treatment pool; then, heating the nano calcium carbonate slurry to 60-70 ℃, and continuously stirring; then, adding a surface activation coating agent into the nano calcium carbonate slurry for coating; the surface activation coating agent is prepared from the following raw materials in parts by weight: 14-20 parts of butyl ether phthalate sodium salt, 2-6 parts of isopropanol, 3-7 parts of butyl ether diethylene glycol, 8-12 parts of octadecylamine, 4-8 parts of dodecylamine and 5-9 parts of sorbitan monolaurate; finally, after surface treatment for 1-2 hours, modified slurry is obtained;
(3) preparing a finished product: carrying out filter pressing, drying and crushing on the modified slurry obtained in the step (2) to obtain a finished product of nano calcium carbonate;
in the step A1, when water is added for digestion, the mass ratio of the water to the CaO is 1:15-20, and the water temperature is 70-80 ℃; in the step A2, the mass ratio of the crystal form control agent to the CaO is 1: 20-50; in step A3, CO2The gas flow rate was: 0.8-1.5L/h gCa (OH)2；
In the step (2), the method for preparing the butyl ether phthalate sodium salt comprises the following steps:
B1. the following raw materials were prepared: phthalic anhydride, butyl cellosolve, sodium hydroxide;
B2. adding phthalic anhydride in the step B1 into a reaction tank, and heating to 80-90 ℃;
B3. adding ethylene glycol monobutyl ether in the step B1 into the reaction tank in the step B2 gradually, after reacting for a period of time at constant temperature, starting timing when phthalic anhydride begins to dissolve, and measuring the esterification rate by adopting an alkali titration method;
B4. stopping the reaction when the esterification rate measured in the step B3 is not increased any more to obtain phthalic acid monoethylene glycol butyl ether ester;
B5. when the temperature of the butyl ether phthalate in the step B4 is reduced to 60-70 ℃, adding sodium hydroxide, and violently stirring to obtain the butyl ether phthalate sodium salt in the step (2);
in the step (2), the mass ratio of the surface activation coating agent to the nano calcium carbonate is as follows: 1:30-100.
2. The method for modifying ultra-fine light calcium carbonate according to claim 1, wherein in step A3, the mass ratio of the dispersing agent to the CaO is: 1: 40-50.
3. The use of the precipitated calcium carbonate prepared by the method of claim 1 for improving the toughness and strength of PVC.
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