CN117659505A - Modified calcium carbonate, preparation method thereof and application thereof in preparation of PBAT material - Google Patents
Modified calcium carbonate, preparation method thereof and application thereof in preparation of PBAT material Download PDFInfo
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- CN117659505A CN117659505A CN202311285071.6A CN202311285071A CN117659505A CN 117659505 A CN117659505 A CN 117659505A CN 202311285071 A CN202311285071 A CN 202311285071A CN 117659505 A CN117659505 A CN 117659505A
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- calcium carbonate
- mixed solution
- modified calcium
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 192
- 229920001896 polybutyrate Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title abstract description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 67
- 239000011259 mixed solution Substances 0.000 claims abstract description 49
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 41
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 239000004970 Chain extender Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 8
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 38
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 22
- 239000011575 calcium Substances 0.000 description 22
- 229910052791 calcium Inorganic materials 0.000 description 22
- 239000000243 solution Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 3
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000004301 calcium benzoate Substances 0.000 description 2
- 235000010237 calcium benzoate Nutrition 0.000 description 2
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 210000001072 colon Anatomy 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OTJDDUKPDMSZHT-UHFFFAOYSA-N 4-dodecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 OTJDDUKPDMSZHT-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- YMIFCOGYMQTQBP-UHFFFAOYSA-L calcium;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Ca+2] YMIFCOGYMQTQBP-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses modified calcium carbonate, a preparation method thereof and application thereof in preparing PBAT materials, belonging to the technical field of high polymer materials, wherein the preparation method of the modified calcium carbonate comprises the following steps: (1) Uniformly mixing calcium carbonate and water, adding sodium dodecyl benzene sulfonate, and uniformly mixing to obtain a mixed solution A; (2) Uniformly mixing benzoic acid and ethanol to obtain a mixed solution B; (3) And adding the mixed solution B into the mixed solution A, uniformly stirring, filtering and drying to obtain the modified calcium carbonate. The preparation method of the modified calcium carbonate has simple process, the modified calcium carbonate has loose and porous surface, large contact area with PBAT and high interface strength with PBAT, and the macromolecule of the resin can be wound or penetrated through the modified calcium carbonate, so that the bonding strength of the resin and the calcium carbonate is further improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to modified calcium carbonate, a preparation method thereof and application thereof in preparing PBAT materials.
Background
At present, the full-biodegradable film material mainly adopts PBAT/starch composite, PBAT/CaCO 3 Of composite material, wherein due to CaCO 3 Low cost and wide sources, so that the production enterprises use PBAT/CaCO 3 The composite material is mainly and the density of PBAT is 1.18-1.3g/cm 3 ，CaCO 3 Has a density of 2.6-2.8g/cm 3 Thus PBAT/CaCO 3 The density of the composite material is greater than that of the pure PBAT resin, so that the effective membrane area of the composite material is reduced and the material cost is indirectly increased under the same weight condition when the membrane product is prepared.
The patent CN102963919A discloses a production method of low-density active calcium carbonate, which is characterized in that the calcium carbonate and the surface treating agent are stirred and heated at a high speed by a high-speed stirrer, and the low-density active calcium carbonate is obtained by discharging after cooling. The invention only carries out surface treatment on the calcium carbonate, does not change the appearance of the calcium carbonate, and has limited density reduction range.
Patent CN103232051a discloses a preparation method of superfine porous calcium carbonate microsphere, which comprises dissolving tween-80 in water solution of n-hexane, stirring to obtain mixed solution a; PVP is added into Na2CO3 water solution, and mixed solution B is obtained through stirring and dissolution; adding the mixed solution A into the mixed solution B, and performing ultrasonic emulsification to obtain an emulsion; pouring the emulsion into CaCl2 water solution, and stirring for reaction to obtain suspension; and standing the suspension, performing suction filtration, washing and drying a filter cake to obtain the superfine porous calcium carbonate microspheres. The invention adopts a method for synthesizing calcium carbonate to prepare porous calcium carbonate, and the preparation is complicated.
The patent CN102874856A discloses a preparation method of porous calcium carbonate for PVC filling, which mainly utilizes the calcium carbonate surface to generate calcium sulfate dihydrate, then generates calcium carbonate on the calcium sulfate dihydrate surface, and finally utilizes the principle that the calcium sulfate dihydrate is dehydrated at high temperature to enable the calcium carbonate surface to form the porosity. The method is complicated.
Patent CN104016392a discloses a method for preparing low-density calcium carbonate, which comprises emulsifying a calcium source solution with an emulsifier to coat an oil core material with the calcium source solution to form a liquid bead with an oil-in-water structure, atomizing the emulsion by using an atomizing nozzle, carbonizing the emulsion in carbon dioxide gas to form calcium carbonate on the outer layer of the liquid bead, coating the central oil core material with the calcium carbonate to form particles, and finally drying to form the calcium carbonate particles with a hollow structure. The calcium carbonate has a hollow structure, and is easily sheared and damaged by a double-screw extruder, so that the effect cannot be achieved.
In view of this, the present application is presented.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide modified calcium carbonate, a preparation method and application thereof in preparing PBAT materials, wherein the modified calcium carbonate has loose and porous surface, large contact area with PBAT and high interface strength with PBAT, and macromolecules of resin can wind or penetrate through the modified calcium carbonate, so that the bonding strength of the resin and the calcium carbonate is further improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing modified calcium carbonate, comprising the following steps:
(1) Uniformly mixing calcium carbonate and water, adding sodium dodecyl benzene sulfonate, and uniformly mixing to obtain a mixed solution A;
(2) Uniformly mixing benzoic acid and ethanol to obtain a mixed solution B;
(3) And adding the mixed solution B into the mixed solution A, uniformly stirring, filtering and drying to obtain the modified calcium carbonate.
According to the invention, the modified calcium carbonate is obtained by firstly treating the calcium carbonate with sodium dodecyl benzene sulfonate and then mixing the sodium dodecyl benzene sulfonate with the benzoic acid and the ethanol, and the calcium carbonate is added into the PBAT composite material, so that the mechanical property of the composite material can be remarkably improved, the density of the composite material is reduced, the modified calcium carbonate has excellent dispersion property and stable performance, the filling amount of the modified calcium carbonate in the PBAT composite material can be effectively improved, and the modified calcium carbonate has good compatibility with the PBAT and cannot be sheared and damaged by a double-screw extruder when the PABT composite material is prepared.
The preparation method of the modified calcium carbonate has simple process, the modified calcium carbonate has loose and porous surface, large contact area with PBAT and high interface strength with PBAT, and the macromolecule of the resin can be wound or penetrated through the modified calcium carbonate, so that the bonding strength of the resin and the calcium carbonate is further improved.
According to the invention, sodium dodecyl benzene sulfonate is creatively adopted, calcium carbonate in the mixed solution A is dispersed on one hand, so that calcium carbonate and benzoic acid react uniformly, on the other hand, the sodium dodecyl benzene sulfonate can coat the calcium carbonate to achieve a surface treatment effect, and as the sodium dodecyl benzene sulfonate and the PBAT resin structure both contain benzene ring and polar bonds, the compatibility of the sodium dodecyl benzene sulfonate and the PBAT resin structure is good according to a similar compatibility principle, and the compatibility with PBAT is effectively improved.
As a preferred embodiment of the present invention, the calcium carbonate has a particle size of 2000 to 3000 mesh.
As a preferred embodiment of the present invention, the calcium carbonate has a particle size distribution width of 1.8 or less.
Wherein, the calculation formula of the particle size distribution width of the calcium carbonate is as follows: [ (D90-D10)/D50 ], namely the width of the particle size distribution of the calcium carbonate satisfies the following conditions: [ (D90-D10)/D50 ]. Ltoreq.1.8.
Wherein D10 is the particle size corresponding to the 10 percent of the accumulated volume of calcium carbonate, D50 is the particle size corresponding to the 50 percent of the accumulated volume of calcium carbonate, D90 is the particle size corresponding to the 90 percent of the accumulated volume of calcium carbonate, and the units of D10, D50 and D90 are mu m.
According to the invention, the mechanical property of the PBAT composite material is further improved and the density is further reduced by controlling the particle size distribution width of the calcium carbonate to be smaller than 1.8, wherein if the particle size distribution width is larger than 1.8, benzoic acid is reacted with coarse particles at first, fine particles are not reacted, and the performance is further reduced.
As a preferred embodiment of the present invention, the mass ratio of the calcium carbonate, water and sodium dodecyl benzene sulfonate is 1: (2-3): (0.01-0.02).
As a preferred embodiment of the present invention, the mass ratio of benzoic acid to ethanol is 1: (3-5).
As a preferred embodiment of the present invention, the mass ratio of the calcium carbonate to the benzoic acid is 1: (0.05-0.1). Wherein, the mass ratio of the calcium carbonate and the benzoic acid refers to the mass ratio of the calcium carbonate in the mixed solution A to the benzoic acid in the mixed solution B.
As a preferred embodiment of the present invention, the stirring rate in the step (3) is 500 to 800rpm.
As a preferred embodiment of the present invention, when the mixed solution B is added to the mixed solution A, the liquid adding speed of the mixed solution B is 10 to 30mL/min. Wherein, the liquid adding speed of the mixed liquid B is realized by controlling a liquid pump.
The inventor of the invention researches and discovers that the concentration of benzoic acid in the mixed solution B, the stirring speed and the liquid adding speed of the mixed solution B have certain influence on the effect, and the mechanical property of the PBAT composite material is further improved and the density is further reduced by controlling the concentration of benzoic acid, the stirring speed and the liquid adding speed of the mixed solution B within the range of the invention, if the concentration and the speed of benzoic acid dripping are high, the benzoic acid and calcium carbonate can react fully to become calcium benzoate; the stirring speed is too high, and the benzoic acid added in the last time is probably not reacted with the calcium carbonate, and the benzoic acid added in the second time is indirectly increased to cause the concentration of the benzoic acid, so that the performance is reduced.
The invention also provides modified calcium carbonate which is prepared by adopting the preparation method.
The invention also provides a low-density PBAT composite material, which comprises the following components in percentage by mass: 50-80% of PBAT, 20-40% of modified calcium carbonate, 0.1-0.3% of chain extender and 1-3% of lubricant;
the calcium carbonate is the modified calcium carbonate.
The low-density PBAT composite material with excellent mechanical property and low density is prepared by combining the raw materials according to a specific proportion.
As a preferred embodiment of the present invention, the PBAT has a melt index of 3 to 5g/10min.
As a preferred embodiment of the present invention, the chain extender includes at least one of a glycidyl methacrylate chain extender and a glycidyl acrylate chain extender.
As a preferred embodiment of the present invention, the lubricant includes at least one of polyester wax, polyamide wax, polyethylene oxide, ethylene bis-stearamide, ethylene bis-oleamide, polyethylene wax.
The invention also provides application of the PBAT composite material in preparing packaging bags, shopping bags and express bags.
The invention has the beneficial effects that: (1) According to the invention, the modified calcium carbonate is obtained by firstly treating the calcium carbonate with sodium dodecyl benzene sulfonate and then mixing the sodium dodecyl benzene sulfonate with the benzoic acid and the ethanol, and the calcium carbonate is added into the PBAT composite material, so that the mechanical property of the composite material can be remarkably improved, the density of the composite material is reduced, the modified calcium carbonate has excellent dispersion property and stable performance, the filling amount of the modified calcium carbonate in the PBAT composite material can be effectively improved, and the modified calcium carbonate has good compatibility with the PBAT and cannot be sheared and damaged by a double-screw extruder when the PABT composite material is prepared. (2) The preparation method of the modified calcium carbonate has simple process, the modified calcium carbonate has loose and porous surface, large contact area with PBAT and high interface strength with PBAT, and the macromolecule of the resin can be wound or penetrated through the modified calcium carbonate, so that the bonding strength of the resin and the calcium carbonate is further improved. (3) According to the invention, sodium dodecyl benzene sulfonate is creatively adopted, calcium carbonate in the mixed solution A is dispersed on one hand, so that calcium carbonate and benzoic acid react uniformly, on the other hand, the sodium dodecyl benzene sulfonate can coat the calcium carbonate to achieve a surface treatment effect, and as the sodium dodecyl benzene sulfonate and the PBAT resin structure both contain benzene ring and polar bonds, the compatibility of the sodium dodecyl benzene sulfonate and the PBAT resin structure is good according to a similar compatibility principle, and the compatibility with PBAT is effectively improved.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
In the present application, the technical features described in an open manner include a closed technical scheme composed of the listed features, and also include an open technical scheme including the listed features.
In the present application, reference is made to numerical intervals, where the numerical intervals are considered to be continuous unless specifically stated, and include the minimum and maximum values of the range, and each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The raw materials used in the examples and comparative examples of the present invention are described below:
PBAT: the melt index of the Lanshan Tunhe river, brand TH801T, is 4.5g/10min according to the ISO1133 method.
Calcium carbonate-1: the particle size distribution width of the powder of Colon powder limited company in Guangxi Hezhou is 1.4-1.6, and the particle size is 3000 meshes.
Calcium carbonate-2: the particle size distribution width of the powder of Colon powder limited company in Guangxi Hezhou is 1.9-2.0, and the particle size is 3000 meshes.
Benzoic acid, technical grade, commercially available;
sodium dodecyl benzene sulfonate, technical grade, commercially available;
ethanol, technical grade, commercially available;
chain extender: BTCE-9013, nanjing Baitong New Material Co., ltd;
and (3) a lubricant: polyester wax, commercially available from Guangzhou bany New Material technology Co., ltd;
aluminate, DL411, dongguan city Dinghai plastic chemical industry.
The raw materials of the components used in each of the examples and comparative examples of the present invention were all commercially available raw materials unless otherwise specified, and the raw materials of the components used in each of the parallel experiments were all the same.
Example 1
A low density PBAT composite material, comprising the following components in percentage by mass: 78.8% PBAT, 20% modified calcium carbonate, 0.2% BTCE-9013, 1% polyester wax;
weighing according to the proportion, uniformly mixing, and putting into a double-screw extruder to prepare the low-density PBAT composite material, wherein the processing temperature is 150-170 ℃, and the length-diameter ratio of the screw is 40:1.
the preparation method of the modified calcium carbonate comprises the following steps:
(1) Adding calcium carbonate-1 and water into a stirring kettle, stirring uniformly, adding sodium dodecyl benzene sulfonate, and mixing uniformly at 60 ℃ to obtain a mixed solution A;
wherein, the mass ratio of the calcium carbonate-1 to the water to the sodium dodecyl benzene sulfonate is 1:2:0.01.
(2) Uniformly mixing benzoic acid and ethanol to obtain a mixed solution B;
wherein, the mass ratio of the calcium carbonate-1 to the benzoic acid to the ethanol is 1:0.05:0.15.
(3) The mixed solution B is added into the mixed solution A by a liquid pump at a speed of 10 ml/min, stirred for 0.5h at a rotation speed of 500rpm, filtered and dried to obtain the modified calcium carbonate.
Example 2
A low density PBAT composite material, comprising the following components in percentage by mass: 68.8% PBAT, 30% modified calcium carbonate, 0.2% BTCE-9013, 1% polyester wax;
weighing according to the proportion, uniformly mixing, and putting into a double-screw extruder to prepare the low-density PBAT composite material, wherein the processing temperature is 150-170 ℃, and the length-diameter ratio of the screw is 40:1.
the preparation method of the modified calcium carbonate comprises the following steps:
(1) Adding calcium carbonate-1 and water into a stirring kettle, stirring uniformly, adding sodium dodecyl benzene sulfonate, and mixing uniformly at 60 ℃ to obtain a mixed solution A;
wherein, the mass ratio of the calcium carbonate-1 to the water to the sodium dodecyl benzene sulfonate is 1:2.5:0.015.
(2) Uniformly mixing benzoic acid and ethanol to obtain a mixed solution B;
wherein, the mass ratio of the calcium carbonate-1 to the benzoic acid to the ethanol is 1:0.075:0.3.
(3) And adding the mixed solution B into the mixed solution A at a speed of 20 ml/min by using a liquid pump, stirring at a speed of 650rpm for 0.7h, carrying out suction filtration and drying to obtain the modified calcium carbonate.
Example 3
A low density PBAT composite material, comprising the following components in percentage by mass: 57.7% pbat, 40% modified calcium carbonate-1, 0.3% BTCE-9013, 2% polyester wax;
weighing according to the proportion, uniformly mixing, and putting into a double-screw extruder to prepare the low-density PBAT composite material, wherein the processing temperature is 150-170 ℃, and the length-diameter ratio of the screw is 40:1.
the preparation method of the modified calcium carbonate comprises the following steps:
(1) Adding calcium carbonate-1 and water into a stirring kettle, stirring uniformly, adding sodium dodecyl benzene sulfonate, and mixing uniformly at 60 ℃ to obtain a mixed solution A;
wherein, the mass ratio of the calcium carbonate-1 to the water to the sodium dodecyl benzene sulfonate is 1:3:0.02.
(2) Uniformly mixing benzoic acid and ethanol to obtain a mixed solution B;
wherein, the mass ratio of the calcium carbonate-1 to the benzoic acid to the ethanol is 1:0.1:0.5.
(3) And adding the mixed solution B into the mixed solution A at a speed of 30ml/min by using a liquid pump, stirring at 800rpm for 1h, filtering, and drying to obtain the modified calcium carbonate.
Comparative example 1
Comparative example 1 differs from example 2 in that comparative example 1 uses calcium carbonate-1 instead of modified calcium carbonate, all other things being equal.
Comparative example 2
Comparative example 2 is different from example 2 in that the preparation method of the modified calcium carbonate of comparative example 2 is different from example 2, and the other are the same.
The preparation method of the modified calcium carbonate of the comparative example comprises the following steps: and (3) placing the calcium carbonate-1 into a high-speed mixer at 90 ℃ for 8 minutes to ensure that the moisture content of the calcium carbonate is less than or equal to 0.1 weight percent, and then adding an aluminate coupling agent with the mass of 1 percent of the calcium carbonate for 3 minutes to obtain the modified calcium carbonate.
Comparative example 3
Comparative example 3 is different from example 2 in that in the preparation method of the modified calcium carbonate of comparative example 3, calcium carbonate-2 is used instead of calcium carbonate-1, and the other are the same.
Comparative example 4
Comparative example 4 differs from example 2 in that the mass ratio of benzoic acid to ethanol of comparative example 4 is 1:2, all other things being equal.
That is, the concentration of benzoic acid in the mixed solution B in this comparative example was too high.
Comparative example 5
Comparative example 5 is different from example 2 in that the stirring rate of step (3) of comparative example 5 is 900rpm, and the other are the same.
Comparative example 6
Comparative example 6 was different from example 2 in that the liquid charging rate of the mixed liquid B of comparative example 6 was 40 ml/min, and the other was the same.
Comparative example 7
Comparative example 7 differs from example 2 in that comparative example 7 does not add sodium dodecylbenzenesulfonate, all other things being equal.
The preparation method of the modified calcium carbonate of the comparative example comprises the following steps:
(1) Adding calcium carbonate-1 and water into a stirring kettle, and uniformly stirring to obtain a mixed solution A;
wherein, the mass ratio of the calcium carbonate-1 to the water is 1:2.5.
(2) Uniformly mixing benzoic acid and ethanol to obtain a mixed solution B;
wherein, the mass ratio of the calcium carbonate-1 to the benzoic acid to the ethanol is 1:0.075:0.3.
(3) And adding the mixed solution B into the mixed solution A at a speed of 20 ml/min by using a liquid pump, stirring at a speed of 650rpm for 0.7h, carrying out suction filtration and drying to obtain the modified calcium carbonate.
Comparative example 8
Comparative example 8 is different from example 2 in that the mixed solution B is not added to comparative example 8, and the other are the same.
The preparation method of the modified calcium carbonate of the comparative example comprises the following steps:
(1) Adding calcium carbonate-1 and water into a stirring kettle, stirring uniformly, adding sodium dodecyl benzene sulfonate, and mixing uniformly at 60 ℃ to obtain a mixed solution A;
wherein, the mass ratio of the calcium carbonate-1 to the water to the sodium dodecyl benzene sulfonate is 1:2.5:0.015.
(2) And (3) carrying out suction filtration and drying on the mixed solution A to obtain the modified calcium carbonate.
Test case
1. The tensile strength, nominal strain at break, 50mm/min of the composites of examples and comparative examples were tested using GB/T1040.2 standard and the test results are shown in Table 1 below.
2. The test examples and comparative examples were tested for notched Izod impact strength using GB/T1843 standard, V notch, 5.5J, and P as part of the failure test results shown in Table 1 below.
3. The density of the composites of examples and comparative examples was measured using the GB/T1033 standard and the results are shown in Table 1 below.
TABLE 1
As can be seen from the results of the performance tests of examples 1-3 in Table 1, the tensile properties of the composite materials gradually decrease and the toughness and density gradually increase as the calcium carbonate increases.
Comparative example 2 and comparative example 1 show that the invention significantly improves the mechanical properties of the composite material and reduces the density by modifying the calcium carbonate.
As can be seen from the results of performance tests of example 2 and comparative example 2 in table 1, the calcium carbonate treated with benzoic acid and sodium dodecylbenzenesulfonate of the present application has significantly improved mechanical properties to aluminate treatment ratio and significantly reduced density. This phenomenon may occur because the treated calcium carbonate becomes a loose porous structure, increasing the contact area with the resin, while the surface is attached with sodium dodecylbenzenesulfonate active agent, further enhancing the interfacial strength, and the macromolecules of the resin intertwine or pass through the voids, further enhancing the bonding strength of the resin with the calcium carbonate.
As can be seen from the results of performance tests of example 2 and comparative examples 3 to 6 in Table 1, the use of calcium carbonate with too wide a particle size width, too high a concentration of benzoic acid to be added dropwise, too high a dropping speed and too high a stirring speed resulted in the formation of calcium carbonate voids, which affected the performance and did not significantly reduce the density. Too wide a particle size may result in benzoic acid first reacting off the coarse particles, while the fine particles do not react; the concentration of the benzoic acid is high and the speed is high, and the benzoic acid and calcium carbonate can react fully to become calcium benzoate; the stirring speed is too high, and the benzoic acid added in the last time is probably not reacted with the calcium carbonate, and the benzoic acid added in the second time is indirectly increased to cause the concentration of the benzoic acid.
As can be seen from the results of the performance tests of example 2 and comparative example 7 in Table 1, the composite material was significantly reduced in performance without adding sodium dodecylbenzenesulfonate, and the density was maintained substantially unchanged. The reason for this may be that the pure water is mixed with the calcium carbonate, the dispersion is not uniform, the reaction is not uniform after the benzoic acid is added dropwise, the density change is not obvious, and the performance is reduced due to agglomeration.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the modified calcium carbonate is characterized by comprising the following steps of:
(1) Uniformly mixing calcium carbonate and water, adding sodium dodecyl benzene sulfonate, and uniformly mixing to obtain a mixed solution A;
(2) Uniformly mixing benzoic acid and ethanol to obtain a mixed solution B;
(3) And adding the mixed solution B into the mixed solution A, uniformly stirring, filtering and drying to obtain the modified calcium carbonate.
2. The method for producing a modified calcium carbonate according to claim 1, wherein the calcium carbonate has a particle size of 2000 to 3000 mesh; and/or
The particle size distribution width of the calcium carbonate is less than or equal to 1.8.
3. The preparation method of the modified calcium carbonate according to claim 1, wherein the mass ratio of the calcium carbonate to the water to the sodium dodecyl benzene sulfonate is 1: (2-3): (0.01-0.02).
4. The preparation method of the modified calcium carbonate according to claim 1, wherein the mass ratio of the benzoic acid to the ethanol is 1: (3-5).
5. The preparation method of the modified calcium carbonate according to claim 1, wherein the mass ratio of the calcium carbonate to the benzoic acid is 1: (0.05-0.1).
6. The method for producing modified calcium carbonate according to claim 1, wherein the stirring rate in the step (3) is 500 to 800rpm; and
when the mixed solution B is added into the mixed solution A, the liquid adding speed of the mixed solution B is 10-30 mL/min.
7. A modified calcium carbonate characterized by being prepared by the preparation method according to any one of claims 1 to 6.
8. The low-density PBAT composite material is characterized by comprising the following components in percentage by mass: 50-80% of PBAT, 20-40% of modified calcium carbonate, 0.1-0.3% of chain extender and 1-3% of lubricant;
the calcium carbonate is the modified calcium carbonate of claim 7.
9. The low density PBAT composite material of claim 8, wherein the PBAT has a melt index of 3 to 5g/10min; and/or
The chain extender comprises at least one of glycidyl methacrylate chain extender and glycidyl acrylate chain extender; and/or
The lubricant comprises at least one of polyester wax, polyamide wax, polyethylene oxide, ethylene bis-stearamide, ethylene bis-oleamide and polyethylene wax.
10. Use of the low density PBAT composite material according to any one of claims 8 to 9 in the preparation of packaging bags, shopping bags, express bags.
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