CN113088102B - Preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive - Google Patents
Preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive Download PDFInfo
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- CN113088102B CN113088102B CN202110349887.5A CN202110349887A CN113088102B CN 113088102 B CN113088102 B CN 113088102B CN 202110349887 A CN202110349887 A CN 202110349887A CN 113088102 B CN113088102 B CN 113088102B
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- calcium carbonate
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- coupling agent
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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 159
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 79
- 239000013464 silicone adhesive Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 125
- 230000004913 activation Effects 0.000 claims abstract description 46
- 238000010521 absorption reaction Methods 0.000 claims abstract description 34
- 238000007689 inspection Methods 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 238000003860 storage Methods 0.000 claims abstract description 11
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 51
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 51
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 51
- -1 sucrose ester Chemical class 0.000 claims description 43
- 229930006000 Sucrose Natural products 0.000 claims description 42
- 239000005720 sucrose Substances 0.000 claims description 42
- 239000003607 modifier Substances 0.000 claims description 40
- 239000007822 coupling agent Substances 0.000 claims description 38
- 239000002131 composite material Substances 0.000 claims description 36
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 31
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 24
- 239000011734 sodium Substances 0.000 claims description 24
- 229910052708 sodium Inorganic materials 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 150000004645 aluminates Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 6
- 238000010009 beating Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000011575 calcium Substances 0.000 description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004581 coalescence Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 125000005313 fatty acid group Chemical group 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 125000000185 sucrose group Chemical group 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
Classifications
-
- 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
- C09C3/003—Flushing
-
- 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
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- 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
-
- 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
- C09C3/045—Agglomeration, granulation, pelleting
-
- 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
-
- 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
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
-
- 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
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- 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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/65—Chroma (C*)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive, which sequentially comprises the steps of ore storage, cleaning, ore dressing, crushing and homogenizing, grinding, grading, powder collection, quality inspection I, activation, cooling and quality inspection II. The preparation method is simple and feasible, and the prepared calcium carbonate powder has good dispersibility, extremely high activation degree, higher whiteness and extremely low oil absorption value, and can effectively improve the thixotropy and tensile strength of the silicone adhesive.
Description
Technical Field
The invention belongs to the technical field of calcium carbonate preparation, and particularly relates to a preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive.
Background
Calcium carbonate belongs to inorganic powder, has many hydroxyl groups on the surface, is easy to absorb moisture, presents hydrophilic and oleophobic characteristics, is difficult to be uniformly dispersed in an organic medium, and cannot be subjected to cross-linking reaction with high polymer materials such as rubber, plastic and the like. Calcium carbonate with poor dispersion not only seriously affects the appearance of products, but also easily forms internal defects of materials due to aggregates with larger sizes, and cannot achieve ideal reinforcing effect on polymer materials. In order to solve the above problems, surface modification of calcium carbonate powder is required, and surface treatment can change the surface characteristics of calcium carbonate powder, reduce surface energy, reduce agglomeration force among particles, improve dispersibility in products, and increase compatibility with high polymer materials, so that the products have good mechanical properties. The surface modification effect is the main direction for distinguishing the grade of calcium carbonate products.
Heavy calcium carbonate, called heavy calcium for short, is prepared by grinding natural carbonate minerals such as calcite, marble and limestone, is a common powdery inorganic filler, and has the advantages of high chemical purity, high inertia, difficult chemical reaction, good thermal stability, no decomposition at the temperature of below 400 ℃, high whiteness, low oil absorption rate, low refractive index, soft quality, dryness, no crystal water, low hardness, low abrasion value, no toxicity, no odor, good dispersibility and the like. The heavy calcium carbonate is generally used as a filler, is widely used in daily chemical industries such as artificial floor tiles, rubber, plastics, papermaking, coatings, paints, printing ink, cables, building products, food, medicine, textile, feed, toothpaste and the like, and is used as a filler to increase the volume of products and reduce the production cost.
The ground limestone is the main filler for preparing the silicone adhesive, and the larger the filling amount is, the less the silicone oil is used, the lower the production cost is, and the more environment-friendly is the product. Because of the inorganic characteristic of calcium carbonate powder, the calcium carbonate powder has poor compatibility with silicone oil, and needs to be modified, however, the existing composite surface modifier has the problems of complex components, high preparation cost and the like, and the single-component modifier has the problems of single effect, poor modification effect and the like.
Disclosure of Invention
The invention provides a preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive, which is combined with a unique using method, has good dispersibility, extremely high activation degree, higher whiteness and extremely low oil absorption value after being used for modifying the heavy calcium carbonate for the silicone adhesive, and can effectively improve the thixotropy and tensile strength of the silicone adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive sequentially comprises the steps of ore storage, cleaning, ore dressing, crushing and homogenizing, grinding, grading, powder collection, quality inspection I, activation, cooling and quality inspection II;
the ore storage step is as follows: storing the ore raw materials separately according to the types and grades of the ores;
the cleaning steps are as follows: cleaning the mud adhered on the surface of the ore with water;
the beneficiation steps are as follows: selecting out the unqualified ores carried in the ores;
the crushing and homogenizing steps are as follows: crushing qualified ore into ore material with the particle size of less than 20mm, and then sending the ore material into a ten-thousand-ton-level homogenizing tank for homogenizing;
the grinding step is as follows: feeding the mineral aggregate into grinding equipment for grinding;
the grading step comprises the following steps: products with different fineness are obtained by setting different rotating speeds;
the powder collecting step is as follows: collecting the classified powder particles;
the quality inspection I comprises the following steps: sampling and inspecting the collected powder product, and taking the qualified powder product as a raw material for surface treatment of the heavy calcium carbonate for the silicone adhesive; if the product is not qualified, carrying out degradation or back beating treatment;
the activation step is as follows: adding a composite modifier into the powder product which is qualified in inspection, so that the surface of the powder particles is wrapped by the composite modifier, and the surface characteristics of the powder particles are completely changed;
the cooling step is as follows: cooling the modified product to room temperature;
the quality inspection II comprises the following steps: and (4) inspecting the activation degree and the oil absorption value of the cooled product, packaging and warehousing the qualified product, and degrading or returning the unqualified product.
Further, in the beneficiation step, the unqualified ores are ores with low whiteness and skin and other impurities.
Further, in the step I of quality inspection, the qualified powder product is 1250-mesh product.
Further, in the quality inspection step II, the qualified product is a product with the activation degree of more than or equal to 90 percent and the oil absorption value of less than or equal to 11g/100 g.
Further, the composite modifier comprises a silane coupling agent, oleamide, a titanate coupling agent, an aluminate coupling agent, rosin sodium and sucrose ester.
Further, the adding amount of the silane coupling agent is 0.7-0.9% of the mass of the powder, the adding amount of the oleamide is 0.3-0.5% of the mass of the powder, the adding amount of the titanate coupling agent is 0.2-0.5% of the mass of the powder, the adding amount of the aluminate coupling agent is 0.3-0.5% of the mass of the powder, the adding amount of the stearic acid is 0.5-0.7% of the mass of the powder, and the adding amount of the rosin is 0.1-0.5% of the mass of the powder; the addition amount of the sucrose ester is 0.1-0.5% of the mass of the powder.
Further, the adding method of the composite modifier comprises the following steps: adding rosin sodium at the temperature of 30-40 ℃, reacting for 20-40 minutes, heating to 80-90 ℃, adding oleamide and sucrose ester into the powder, reacting for 1-5 minutes, adding a silane coupling agent, a titanate coupling agent and an aluminate coupling agent, reacting for 3-5 minutes, adding stearic acid, and continuing to react for 1-10 minutes.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method is simple and feasible, and the prepared calcium carbonate powder has good dispersibility, extremely high activation degree, higher whiteness and extremely low oil absorption value, and can effectively improve the thixotropy and tensile strength of the silicone adhesive.
2. The composite modifier can quickly form a layer of extremely thin isolation oil film on the surface of calcium carbonate particles, hydrophilic groups of molecular layers in the isolation film face the calcium carbonate particles, and the molecular layers are in mutual contact with hydrophilic groups and hydrophobic groups between the molecular layers but not in close contact with each other and can slide mutually, so that the composite modifier not only has an isolation effect, but also has a better lubricating property, and generates an association type three-dimensional barrier through interaction force or hydrogen bonds and a solution to prevent the particles from being in contact with each other and gathering to play a role in inter-particle dispersion. In the raw materials, silane coupling agent and titanate coupling agent generate chemical bonds with calcium carbonate, the oxygen radical of the silane coupling agent and titanate coupling agent has reactivity to inorganic matters, and organic functional groups have reactivity or compatibility to organic matters of silicone adhesive, so that when the coupling agent is between inorganic and organic interfaces, a bonding layer of organic matrix-coupling agent-inorganic matrix can be formed, the surface of the bonding layer is modified, the dispersibility and adhesive force of calcium carbonate powder filler in the silicone adhesive can be improved, the compatibility between the calcium carbonate powder filler and the silicone adhesive is improved, the process performance is improved, and the mechanical, electrical and weather resistance and other performances of the filled silicone adhesive are improved; the titanate coupling agent also has the effect of improving the whiteness of the calcium carbonate powder and enabling the product to have bright color. The oleamide has lubricating, anti-sticking and anti-static properties, and when the oleamide is used for modifying calcium carbonate powder, the performance of the calcium carbonate powder can be improved, chemical bonds can be formed between the calcium carbonate powder and vulcanized silicone rubber, and finally the bonding property of the silicone rubber is obviously improved. The aluminate coupling agent can improve the activation degree of calcium carbonate particles and has good thermal stability and lubricity. One end of the molecular structure of stearic acid is long-chain alkyl which is a lipophilic group and has good compatibility with high polymer materials, and the other end is carboxyl which is a hydrophilic group, RCOO-Can be mixed with Ca in calcium carbonate solution2+、CaHCO3 +、CaOH+And the fatty acid calcium generated by the reaction is coated on the surface of the calcium carbonate, so that the surface of the calcium carbonate is changed from hydrophilicity to lipophilicity. The rosin sodium can be combined with calcium ions on the surface of calcium carbonate and can reactThe rosin calcium should be generated, firm chemical bonds can be formed between the rosin calcium and each component, the loss of the rosin calcium is reduced, the long-acting performance of the preservative is improved, the mechanical performance of the silicone adhesive is enhanced, and meanwhile, the rosin has good lubricating property and emulsifying property and can improve the dispersibility of calcium carbonate powder. The molecular structure of the sucrose ester contains strong hydrophilic sucrose groups and lipophilic fatty acid groups, so that the sucrose ester has strong surface activity, can have good dispersing and emulsifying effects on one hand, can improve the dispersibility of calcium carbonate powder, ensures the uniformity of the silicone adhesive in the solidification process, and further improves the solidification effect and the anti-aging effect; on the other hand, the softening point of the rosin calcium is high, the brittleness is high, the binding power is strong, the plasticity is good, the sucrose ester emulsifies the rosin calcium, the emulsification, dispersion and stabilization effects can be simultaneously realized, and the interfacial tension of a dispersed phase and a dispersion medium can be reduced, namely the interfacial specific surface free energy is reduced, so that the coalescence of an oil phase can be prevented, and the stability of the rosin calcium emulsion is improved; the sucrose ester can form an adsorption layer regularly arranged around dispersed phase droplets, and the sucrose ester stays on an interface of two phases, the nonpolar lipophilic group of the sucrose ester is contacted with the rosin calcium, the hydrophilic group is contacted with water molecules, and the formed adsorption layer can prevent the coalescence of the oil phase. The sucrose ester, the rosin sodium and the oleamide synergistically improve the activation degree of the calcium carbonate and reduce the oil absorption value.
3. The sucrose ester of the invention takes natural rosin as raw material, and the rosin-based modifier as environment-friendly modifier, has the advantages of being renewable, biodegradable and harmless to human body, on one hand, the rosin which is a renewable resource is fully utilized, the additional value of the rosin is greatly improved, the development of the rosin deep processing industry is promoted, and the sucrose ester has very important significance for the development of national and local economy, the reasonable development and utilization of forestry resources in China and the protection of ecological environment. Most importantly, the rosin-based modifier can improve the surface quality of the calcium carbonate powder, and the composite modifier disclosed by the invention is low in price, high in activity, non-toxic and environment-friendly.
4. The use method of the composite modifier is reasonably designed, the modification effect of the composite modifier can be fully exerted, the components of the composite modifier can be well cooperated to modify the calcium carbonate powder, so that after the heavy calcium carbonate for the silicone adhesive is modified by the composite modifier produced by the invention, the modified heavy calcium carbonate has good dispersibility, extremely high activation degree, higher whiteness and extremely low oil absorption value, and the thixotropy and tensile strength of the silicone adhesive can be effectively improved. Meanwhile, the prepared rubber strip has lower specific gravity, more rubber materials with the same mass can be obtained by feeding materials, and the yield is improved; the oil absorption value is low, the investment of silicone oil can be reduced, and the cost is reduced.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
Example 1
A preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive sequentially comprises the steps of ore storage, cleaning, ore dressing, crushing and homogenizing, grinding, grading, powder collection, quality inspection I, activation, cooling and quality inspection II;
the ore storage step is as follows: storing the ore raw materials separately according to the types and grades of the ores;
the cleaning steps are as follows: cleaning the mud adhered on the surface of the ore with water;
the beneficiation steps are as follows: selecting out the unqualified ores carried in the ores; the unqualified ores are ores with low whiteness and skin and other impurities;
the crushing and homogenizing steps are as follows: crushing the qualified ore into 18mm ore material, and then sending the ore material into a ten-thousand-ton-level homogenizing tank for homogenizing;
the grinding step is as follows: feeding the mineral aggregate into grinding equipment for grinding;
the grading step comprises the following steps: products with different fineness are obtained by setting different rotating speeds;
the powder collecting step is as follows: collecting the classified powder particles;
the quality inspection I comprises the following steps: sampling and inspecting the collected powder product, detecting that the fineness and distribution of the powder product are 1250 meshes, and using the powder product as a raw material for surface treatment of the heavy calcium carbonate for the silicone adhesive, wherein the powder product is qualified;
the activation step is as follows: adding a composite modifier into the powder product which is qualified in inspection, so that the surface of the powder particles is wrapped by the composite modifier, and the surface characteristics of the powder particles are completely changed; the composite modifier comprises a silane coupling agent, oleamide, a titanate coupling agent, an aluminate coupling agent, rosin sodium and sucrose ester; the additive amount of the silane coupling agent is 0.7 percent of the mass of the powder, the additive amount of the oleamide is 0.3 percent of the mass of the powder, the additive amount of the titanate coupling agent is 0.2 percent of the mass of the powder, the additive amount of the aluminate coupling agent is 0.5 percent of the mass of the powder, the additive amount of the stearic acid is 0.5 percent of the mass of the powder, and the additive amount of the rosin is 0.3 percent of the mass of the powder; the addition amount of the sucrose ester is 0.1 percent of the mass of the powder; the adding method of the composite modifier comprises the following steps: adding rosin sodium at 35 ℃, reacting for 20 minutes, heating to 80 ℃, adding oleamide and sucrose ester into the powder, reacting for 1 minute, adding a silane coupling agent, a titanate coupling agent and an aluminate coupling agent, reacting for 4 minutes, adding stearic acid, and continuing to react for 5 minutes;
the cooling step is as follows: cooling the modified product to room temperature;
the quality inspection II comprises the following steps: the activation degree and the oil absorption value of the cooled product are tested, and the activation degree is 95.8 percent and the oil absorption value is 9.98g/100 g; and (5) packaging and warehousing the qualified product.
Example 2
A preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive sequentially comprises the steps of ore storage, cleaning, ore dressing, crushing and homogenizing, grinding, grading, powder collection, quality inspection I, activation, cooling and quality inspection II;
the ore storage step is as follows: storing the ore raw materials separately according to the types and grades of the ores;
the cleaning steps are as follows: cleaning the mud adhered on the surface of the ore with water;
the beneficiation steps are as follows: selecting out the unqualified ores carried in the ores; the unqualified ores are ores with low whiteness and skin and other impurities;
the crushing and homogenizing steps are as follows: crushing qualified ores into ore materials with the particle size of 15mm, and then sending the ore materials into a ten-thousand-ton-level homogenizing tank for homogenizing;
the grinding step is as follows: feeding the mineral aggregate into grinding equipment for grinding;
the grading step comprises the following steps: products with different fineness are obtained by setting different rotating speeds;
the powder collecting step is as follows: collecting the classified powder particles;
the quality inspection I comprises the following steps: sampling and inspecting the collected powder product, detecting that the fineness and distribution of the powder product are 1250 meshes, and using the powder product as a raw material for surface treatment of the heavy calcium carbonate for the silicone adhesive, wherein the powder product is qualified;
the activation step is as follows: adding a composite modifier into the powder product which is qualified in inspection, so that the surface of the powder particles is wrapped by the composite modifier, and the surface characteristics of the powder particles are completely changed; the composite modifier comprises a silane coupling agent, oleamide, a titanate coupling agent, an aluminate coupling agent, rosin sodium and sucrose ester; the additive amount of the silane coupling agent is 0.8 percent of the mass of the powder, the additive amount of the titanate coupling agent is 0.3 percent of the mass of the powder, the additive amount of the aluminate coupling agent is 0.3 percent of the mass of the powder, the additive amount of the stearic acid is 0.7 percent of the mass of the powder, and the additive amount of the rosin is 0.5 percent of the mass of the powder; the addition amount of the sucrose ester is 0.3 percent of the mass of the powder; the adding method of the composite modifier comprises the following steps: adding rosin sodium at 30 ℃, reacting for 30 minutes, heating to 85 ℃, adding oleamide and sucrose ester into the powder, reacting for 3 minutes, adding a silane coupling agent, a titanate coupling agent and an aluminate coupling agent, reacting for 5 minutes, adding stearic acid, and continuing to react for 10 minutes;
the cooling step is as follows: cooling the modified product to room temperature;
the quality inspection II comprises the following steps: the activation degree and the oil absorption value of the cooled product are tested, and the activation degree is 96.4 percent and the oil absorption value is 8.63g/100 g; and (5) packaging and warehousing the qualified product.
Example 3
A preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive sequentially comprises the steps of ore storage, cleaning, ore dressing, crushing and homogenizing, grinding, grading, powder collection, quality inspection I, activation, cooling and quality inspection II;
the ore storage step is as follows: storing the ore raw materials separately according to the types and grades of the ores;
the cleaning steps are as follows: cleaning the mud adhered on the surface of the ore with water;
the beneficiation steps are as follows: selecting out the unqualified ores carried in the ores; the unqualified ores are ores with low whiteness and skin and other impurities;
the crushing and homogenizing steps are as follows: crushing qualified ores into ore materials with the size of 10mm, and then sending the ore materials into a ten-thousand-ton-level homogenizing tank for homogenizing;
the grinding step is as follows: feeding the mineral aggregate into grinding equipment for grinding;
the grading step comprises the following steps: products with different fineness are obtained by setting different rotating speeds;
the powder collecting step is as follows: collecting the classified powder particles;
the quality inspection I comprises the following steps: sampling and inspecting the collected powder product, detecting that the fineness and distribution of the powder product are 1250 meshes, and using the powder product as a raw material for surface treatment of the heavy calcium carbonate for the silicone adhesive, wherein the powder product is qualified;
the activation step is as follows: adding a composite modifier into the powder product which is qualified in inspection, so that the surface of the powder particles is wrapped by the composite modifier, and the surface characteristics of the powder particles are completely changed; the composite modifier comprises a silane coupling agent, oleamide, a titanate coupling agent, an aluminate coupling agent, rosin sodium and sucrose ester; the additive amount of the silane coupling agent is 0.9 percent of the mass of the powder, the additive amount of the oleamide is 0.5 percent of the mass of the powder, the additive amount of the titanate coupling agent is 0.5 percent of the mass of the powder, the additive amount of the aluminate coupling agent is 0.4 percent of the mass of the powder, the additive amount of the stearic acid is 0.6 percent of the mass of the powder, and the additive amount of the rosin is 0.1 percent of the mass of the powder; the addition amount of the sucrose ester is 0.5 percent of the mass of the powder; the adding method of the composite modifier comprises the following steps: adding rosin sodium at 40 ℃, heating to 90 ℃ after reacting for 40 minutes, adding oleamide and sucrose ester into the powder, adding a silane coupling agent, a titanate coupling agent and an aluminate coupling agent after reacting for 5 minutes, adding fatty alcohol-polyoxyethylene ether ammonium sulfate after reacting for 3 minutes, and continuing to react for 1 minute;
the cooling step is as follows: cooling the modified product to room temperature;
the quality inspection II comprises the following steps: the activation degree and the oil absorption value of the cooled product are tested, and the activation degree is 96.0 percent and the oil absorption value is 9.49g/100 g; and (5) packaging and warehousing the qualified product.
Comparative example 1
The same as example 2 except that sucrose ester was not added to the raw material of the composite modifier; in the step II of quality inspection, the measured activation degree is 94.5 percent, and the oil absorption value is 11.99g/100 g; and (5) unqualified products are treated by back beating.
Comparative example 2
The raw materials are basically the same as those of the example 2, except that the raw materials of the composite modifier are not added with rosin sodium; in the step II of quality inspection, the measured activation degree is 94.1 percent, and the oil absorption value is 12.93g/100 g; and (5) unqualified products are treated by back beating.
Comparative example 3
The raw materials are basically the same as those of the example 2, except that the composite modifier raw material is not added with oleamide; in the step II of quality inspection, the measured activation degree is 94.1 percent, and the oil absorption value is 12.93g/100 g; and (5) unqualified products are treated by back beating.
Comparative example 4
The modified polyester resin is basically the same as the raw material of the example 2, except that the raw material of the composite modifier is not added with oleamide, rosin sodium and sucrose ester; in the step II of quality inspection, the measured activation degree is 90.1 percent, and the oil absorption value is 20.32g/100 g; and (5) the product is unqualified and is degraded.
Comparative experiment
Firstly, preparing calcium carbonate powder:
calcium carbonate powder was prepared by the preparation methods of examples 1 to 3 and comparative examples 1 to 4.
The main performance indexes of the corresponding calcium carbonate powder products are shown in table 1.
TABLE 1 Main Performance index of calcium carbonate powder product
As can be seen from Table 1, the calcium carbonate powder products prepared by the invention have an activation degree of more than 90%; particularly, the calcium carbonate powder products prepared in the embodiments 1 to 3 have the activation degree of more than 95%, the oil absorption of less than 10g/100g, the whiteness of more than 97%, and excellent performance; the calcium carbonate powder products modified by the composite modifier prepared in the comparative examples 1-4 are qualified in activation degree, unqualified in oil absorption amount and required to be degraded or beaten back;
compared with the data of the comparative example 1, the sucrose ester is not added in the raw materials, the oil absorption is increased by 3.36g/100g, the activation degree is reduced by 1.9 percent, and the whiteness is reduced by 2.3 percent;
compared with the data of the example 2 and the comparative example 2, the oil absorption is increased by 4.30g/100g, the activation is reduced by 2.3 percent, and the whiteness is reduced by 2.4 percent without adding the aluminate coupling agent in the raw materials;
compared with the data of the comparative example 3, the oleic acid amide is not added in the raw materials, the oil absorption is increased by 2.92g/100g, the activation is reduced by 1.5%, and the whiteness is reduced by 1.8%;
compared with the data of the comparative example 4, when the sucrose ester, the rosin sodium and the oleamide are added simultaneously, the oil absorption is increased by 11.69g/100g, and the activation is reduced by 6.3%; the whiteness is reduced by 7.2 percent;
it can be seen that the sucrose ester acts independently, the oil absorption can be reduced by 3.36g/100g, the activation degree is improved by 1.4%, and the whiteness is improved by 2.3%; the rosin sodium acts independently, the oil absorption can be reduced by 4.30g/100g, and the activation degree is improved by 2.8%; the whiteness is improved by 2.4 percent; the oleamide acts independently, so that the oil absorption can be reduced by 2.92g/100g, the activation degree is improved by 1%, and the whiteness is improved by 1.8%; the combined action of sucrose ester, rosin sodium and oleamide can reduce the oil absorption by 11.69g/100g, improve the activation degree by 6.3 percent and improve the whiteness by 7.2 percent; therefore, the oil absorption reducing effect is increased when the sucrose ester, the rosin sodium and the oleamide act together compared with the case that the sucrose ester, the rosin sodium and the oleamide act independently respectively: [11.69- (3.36+4.30+2.92) ]/(3.36 +4.30+2.92) × 100% > 10.5% >, the activation degree-improving effect increases [6.3- (1.9+2.3+1.5) ]/(1.9 +2.3+1.5) × 100% > 10%, and the whiteness-improving effect increases [7.2- (2.3+2.4+1.8) ]/(2.3 +2.4+1.8) × 100% > 10.8% > 10%. Therefore, when the sucrose ester, the rosin sodium and the oleamide are used together, a synergistic effect is generated, the oil absorption is synergistically reduced, and the activation degree and the whiteness are improved.
The oleamide has lubricating, anti-sticking and anti-static properties, and when the oleamide is used for modifying calcium carbonate powder, the performance of the calcium carbonate powder can be improved, chemical bonds can be formed between the calcium carbonate powder and vulcanized silicone rubber, and finally the adhesive property of the silicone adhesive is obviously improved. The aluminate coupling agent can improve the activation degree of calcium carbonate particles and has good thermal stability and lubricity. One end of the molecular structure of stearic acid is long-chain alkyl which is a lipophilic group and has good compatibility with high polymer materials, and the other end is carboxyl which is a hydrophilic group, RCOO-Can be mixed with Ca in calcium carbonate solution2+、CaHCO3 +、CaOH+And the fatty acid calcium generated by the reaction is coated on the surface of the calcium carbonate, so that the surface of the calcium carbonate is changed from hydrophilicity to lipophilicity. The rosin sodium can be combined with calcium ions on the surface of calcium carbonate to react to generate rosin calcium, the rosin calcium can form firm chemical bonds with each component, the loss of the rosin calcium is reduced, the long-acting property of the preservative is improved, and meanwhile, the mechanical property of the silicone adhesive is enhancedMeanwhile, the rosin has good lubricity and emulsibility, and can improve the dispersibility of the calcium carbonate powder. The molecular structure of the sucrose ester contains strong hydrophilic sucrose groups and lipophilic fatty acid groups, so that the sucrose ester has strong surface activity, can have good dispersing and emulsifying effects on one hand, can improve the dispersibility of calcium carbonate powder, ensures the uniformity of the silicone adhesive in the solidification process, and further improves the solidification effect and the anti-aging effect; on the other hand, the softening point of the rosin calcium is high, the brittleness is high, the binding power is strong, the plasticity is good, the sucrose ester emulsifies the rosin calcium, the emulsification, dispersion and stabilization effects can be simultaneously realized, and the interfacial tension of a dispersed phase and a dispersion medium can be reduced, namely the interfacial specific surface free energy is reduced, so that the coalescence of an oil phase can be prevented, and the stability of the rosin calcium emulsion is improved; the sucrose ester can form an adsorption layer regularly arranged around dispersed phase droplets, and the sucrose ester stays on an interface of two phases, the nonpolar lipophilic group of the sucrose ester is contacted with the rosin calcium, the hydrophilic group is contacted with water molecules, and the formed adsorption layer can prevent the coalescence of the oil phase. The oleamide can be used for synergistically improving the activation degree of calcium carbonate with the rosin sodium and the sucrose ester and reducing the oil absorption value.
Fourthly, preparing the silicone adhesive:
adding 536g of 107 glue and 24g of silicone oil into a kneader, and heating and stirring for 30 min; adding 640g of active calcium carbonate powder, heating to 100 ℃, vacuumizing to below-0.08 MPa, and stirring for 3 hours; then emptying, adding 80g of white oil, stirring for 30min, discharging to obtain a base material (cooling to room temperature, detecting viscosity and consistency); adding 1000g of base material and 52.5g of methyl tributyl ketoxime silane into a glue making machine, vacuumizing and stirring for 25min, adding 2.5g of catalyst, 2.5g of coupling agent KH-550 and 2.5g of KH-560 respectively, vacuumizing and stirring for 25min, extruding and pouring into a glue barrel.
The Bingham viscosity testing method comprises the steps of manually stirring a certain amount of 107 glue and calcium carbonate powder uniformly, placing the mixture into a three-dimensional high-speed mixer for high-speed dispersion for 30s, then placing the mixture into a constant temperature box for 24h, and detecting by using a Haake rheometer. The base material consistency is measured by a consistency measuring instrument after the base material without white oil is placed in a constant temperature box for 24 hours. Surface drying time is according to GB/T13477.5-2002 part 5 of test method for building sealing materials: measurement of tack-free time method test; extrudability as per GB/T13477.4-2002 section 4 of test methods for building sealants: the method in the original package single-component sealing material extrudability test records the time required by the whole extrusion of the sealing glue at one time; maximum strength, bond strength, elastic modulus, elongation at break, etc. are as per GB/T13477.8-2002 "test method for building sealants part 8: measurement of tensile adhesion "; elastic recovery rate according to GB/T13477.17-2002 section 17 of test method for building sealing materials: measurement of elastic recovery percentage the sample was prepared by method A and the elastic recovery percentage in a 100% elongation state was measured. The detailed test results are shown in table 2.
TABLE 2 influence of crystal form and particle size of calcium carbonate powder on the properties of silicone adhesive
The smaller the particle size of the calcium carbonate powder is, the more difficult it is to achieve uniform dispersion in the system, but as long as the dispersion is uniform, a silicone adhesive product with better strength can be prepared. The data in table 1 show that the calcium carbonate powder prepared by adding the composite modifier of sucrose ester, sodium rosin and oleamide is used for silicone adhesive products, and has higher elongation at break than the calcium carbonate powder prepared by adding the composite modifier of sucrose ester, sodium rosin and oleamide is used for silicone adhesive products; meanwhile, the calcium carbonate powder prepared by adding the composite modifier for the calcium carbonate powder is used for optimizing the comprehensive performance of the silicone adhesive product, and has higher strength and elongation at break meeting the application requirement.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive is characterized by comprising the following steps: the method comprises the following steps of ore storage, cleaning, ore dressing, crushing and homogenizing, grinding, grading, powder collection, quality inspection I, activation, cooling and quality inspection II in sequence;
the ore storage step is as follows: storing the ore raw materials separately according to the types and grades of the ores;
the cleaning steps are as follows: cleaning the mud adhered on the surface of the ore with water;
the beneficiation steps are as follows: selecting out the unqualified ores carried in the ores;
the crushing and homogenizing steps are as follows: crushing qualified ore into ore material with the particle size of less than 20mm, and then sending the ore material into a ten-thousand-ton-level homogenizing tank for homogenizing;
the grinding step is as follows: feeding the mineral aggregate into grinding equipment for grinding;
the grading step comprises the following steps: products with different fineness are obtained by setting different rotating speeds;
the powder collecting step is as follows: collecting the classified powder particles;
the quality inspection I comprises the following steps: sampling and inspecting the collected powder product, and taking the qualified powder product as a raw material for surface treatment of the heavy calcium carbonate for the silicone adhesive; if the product is not qualified, carrying out degradation or back beating treatment;
the activation step is as follows: adding a composite modifier into the heated powder product to wrap the surfaces of the powder particles with the composite modifier, so as to completely change the surface characteristics of the powder particles;
the composite modifier comprises a silane coupling agent, oleamide, a titanate coupling agent, an aluminate coupling agent, stearic acid, sodium rosin and sucrose ester;
the additive amount of the silane coupling agent is 0.7-0.9% of the mass of the powder, the additive amount of the oleamide is 0.3-0.5% of the mass of the powder, the additive amount of the titanate coupling agent is 0.2-0.5% of the mass of the powder, the additive amount of the aluminate coupling agent is 0.3-0.5% of the mass of the powder, the additive amount of the stearic acid is 0.5-0.7% of the mass of the powder, and the additive amount of the rosin is 0.1-0.5% of the mass of the powder; the addition amount of the sucrose ester is 0.1-0.5% of the mass of the powder;
the cooling step is as follows: cooling the modified product to room temperature;
the quality inspection II comprises the following steps: and (4) inspecting the activation degree and the oil absorption value of the cooled product, packaging and warehousing the qualified product, and degrading or returning the unqualified product.
2. The method for preparing heavy calcium carbonate for high-activation silicone adhesive according to claim 1, characterized in that: in the beneficiation step, the unqualified ores are ores with low whiteness and skins and other impurities.
3. The method for preparing heavy calcium carbonate for high-activation silicone adhesive according to claim 1, characterized in that: in the step I of quality inspection, the qualified powder product is 1250-mesh product.
4. The method for preparing heavy calcium carbonate for high-activation silicone adhesive according to claim 1, characterized in that: in the step II of quality inspection, the qualified product has an activation degree of more than or equal to 90 percent and an oil absorption value of less than or equal to 11g/100 g.
5. The method for preparing heavy calcium carbonate for the high-activation-degree silicone adhesive according to claim 1, wherein the method for adding the composite modifier comprises the following steps: adding rosin sodium at the temperature of 30-40 ℃, reacting for 20-40 minutes, heating to 80-90 ℃, adding oleamide and sucrose ester into the powder, reacting for 1-5 minutes, adding a silane coupling agent, a titanate coupling agent and an aluminate coupling agent, reacting for 3-5 minutes, adding stearic acid, and continuing to react for 1-10 minutes.
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