CN112920767A - Composite modifier capable of improving activation degree of heavy calcium carbonate for silicone adhesive and use method thereof - Google Patents
Composite modifier capable of improving activation degree of heavy calcium carbonate for silicone adhesive and use method thereof Download PDFInfo
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- CN112920767A CN112920767A CN202110349889.4A CN202110349889A CN112920767A CN 112920767 A CN112920767 A CN 112920767A CN 202110349889 A CN202110349889 A CN 202110349889A CN 112920767 A CN112920767 A CN 112920767A
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- calcium carbonate
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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 167
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 83
- 239000003607 modifier Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 230000004913 activation Effects 0.000 title claims abstract description 42
- 239000013464 silicone adhesive Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 16
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 70
- 239000008158 vegetable oil Substances 0.000 claims abstract description 70
- 239000000843 powder Substances 0.000 claims abstract description 66
- 239000007822 coupling agent Substances 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 32
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 32
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008117 stearic acid Substances 0.000 claims abstract description 32
- 150000004645 aluminates Chemical class 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims description 80
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 60
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 159000000000 sodium salts Chemical class 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 230000026731 phosphorylation Effects 0.000 claims description 10
- 238000006366 phosphorylation reaction Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000000865 phosphorylative effect Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 239000010495 camellia oil Substances 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 24
- 235000019198 oils Nutrition 0.000 abstract description 24
- 238000010521 absorption reaction Methods 0.000 abstract description 21
- 239000002245 particle Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 229940043237 diethanolamine Drugs 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 229920002545 silicone oil Polymers 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
- 239000011575 calcium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 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
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 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
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- -1 feed Substances 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 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
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005070 sampling Methods 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
- 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
- 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
- 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)
Abstract
The invention discloses a composite modifier capable of improving the activation degree of heavy calcium carbonate for silicone adhesive, which comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, stearic acid and a POSS-phosphorylated vegetable oil polymer. The invention also discloses a use method of the composite modifier capable of improving the activation degree of the ground calcium carbonate for the silicone adhesive according to the claim, which comprises the following steps: adding the POSS-phosphorylated vegetable oil polymer 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. The composite modifier is used for modifying heavy calcium carbonate for silicone adhesive, 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 preparation of calcium carbonate modifiers, and particularly relates to a composite modifier capable of improving the activation degree of heavy calcium carbonate for silicone adhesive and a using method thereof.
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 composite modifier capable of improving the activation degree of heavy calcium carbonate for 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:
the composite modifier capable of improving the activation degree of the heavy calcium carbonate for the silicone adhesive comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, stearic acid and a POSS-phosphorylated vegetable oil polymer, wherein the addition amount of the silane coupling agent is 0.7-0.9% of the mass of powder, the addition amount of the titanate coupling agent is 0.2-0.5% of the mass of the powder, the addition amount of the aluminate coupling agent is 0.3-0.5% of the mass of the powder, the addition amount of the stearic acid is 0.5-0.7% of the mass of the powder, and the addition amount of the POSS-phosphorylated vegetable oil polymer is 0.1-0.5% of the mass of the powder.
Further, the preparation method of the POSS-phosphorylated vegetable oil polymer comprises the following steps:
s1: adding ethanolamine and a catalyst I into vegetable oil, heating to 110-130 ℃, continuously reacting for 3-5 h, and then cooling to 40-50 ℃ to obtain a material A;
s2: adding a phosphorylation reagent into the material A, uniformly stirring, heating to 60-80 ℃, and carrying out heat preservation reaction for 3-5 hours to obtain a material B;
s3: adding acetic acid, a catalyst II and hydrogen peroxide into 10g of the material B, carrying out heat preservation reaction for 3-5 h, washing the product to be neutral, removing water and drying to obtain a material C;
s4: adding acetic acid into the material C at the temperature of 45-55 ℃, reacting for 1-3 h under heat preservation, washing the product to be neutral, removing water and drying to obtain a material D;
s5: respectively dissolving POSS sodium salt, succinyl chloride and a material D in dichloromethane, mixing the POSS sodium salt solution and the succinyl chloride solution in a nitrogen atmosphere, reacting for 2-4 h in an ice water bath, reacting for 2-4 h at room temperature, then adding the material D solution and triethanolamine, reacting for 2-4 h in the ice water bath and the nitrogen atmosphere, reacting for 3h at room temperature, filtering and washing a product to be neutral, removing water and drying to obtain the POSS-phosphorylated vegetable oil polymer.
Further, in the step S1, the addition amount of diethanolamine is 10-30% by mass of the vegetable oil.
Further, in the step S1, the catalyst i is sodium borohydride acetate, and the addition amount thereof is 0.1-0.5% of the mass of the vegetable oil.
Further, in the step S2, the phosphorylating reagent is prepared by introducing P2O5Uniformly mixing the phosphoric acid solution with the volume fraction of 85% according to the material-liquid ratio of 1: 2-8, heating to 90-100 ℃, continuously reacting for 1-4 h, and then cooling to room temperature to obtain the product; the addition amount of the phosphorylation reagent is 5-10% of the mass of the material A.
Further, in the step S3, the adding amount of acetic acid is 1-10% of the mass of the material B; the catalyst II is hydrogen peroxide, and the addition amount of the catalyst II is 0.2-1% of the mass of the material B.
Further, in the step S4, the adding amount of acetic acid is 1-8% of the mass of the material C.
Further, in the step S5, the mass ratio of the POSS sodium salt to the succinyl chloride to the triethanolamine to the material D is 21-55: 34-73: 11-19: 94-123.
Further, the vegetable oil is one of rapeseed oil, tea seed oil, palm oil and cottonseed oil.
A method for using a composite modifier capable of improving the activation degree of heavy calcium carbonate for silicone adhesive comprises the steps of adding a POSS-phosphorylated vegetable oil polymer into 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 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; titanate coupling agentsHas the effects of improving the whiteness of calcium carbonate powder and enabling the product to have bright color. 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+The calcium carbonate is coated on the surface of calcium carbonate to change the surface of the calcium carbonate from hydrophilicity to lipophilicity; the POSS-phosphorylated vegetable oil polymer can obviously improve the dispersibility of calcium carbonate, and the polyhedral oligomeric silsesquioxane has small POSS critical surface tension, good chemical inertia and hydrophobicity, better reduces and isolates the agglomeration acting force among calcium carbonate particles, and reduces agglomeration; the introduction of the phosphate can react with calcium ions on the surfaces of calcium carbonate particles to generate calcium phosphate to coat the surfaces of the calcium carbonate particles, so that the surface modification function is achieved, the processing and mechanical properties of the calcium carbonate can be improved, and the flame retardance and the corrosion resistance of the silicone adhesive product can be improved; the POSS-phosphorylated vegetable oil polymer has good antistatic property and stability, and the dispersibility of calcium carbonate particles is further improved. Stearic acid can synergistically improve the activation degree of calcium carbonate with an aluminate coupling agent and a POSS-phosphorylated vegetable oil polymer and reduce the oil absorption value.
2. The POSS-phosphorylated vegetable oil polymer takes natural vegetable oil as a raw material, and the vegetable oil-based modifier as an environment-friendly modifier, so that the POSS-phosphorylated vegetable oil polymer has the advantages of being renewable, biodegradable and harmless to human bodies, on one hand, the POSS-phosphorylated vegetable oil polymer fully utilizes the renewable resource of the vegetable oil, greatly improves the added value of the vegetable oil, promotes the development of the deep processing industry of the vegetable oil, and has very important significance for the development of national and local economy, the reasonable development and utilization of agricultural resources in China and the protection of ecological environment. Most importantly, the surface quality of the calcium carbonate powder can be improved by using the vegetable oil-based modifier, and the composite modifier disclosed by the invention is low in price, high in activity, non-toxic and environment-friendly.
3. The invention reasonably designs the use method of the composite modifier, 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 can effectively improve the thixotropy and tensile strength of the silicone adhesive. 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
The composite modifier capable of improving the activation degree of the heavy calcium carbonate for the silicone adhesive comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, stearic acid and a POSS-phosphorylated vegetable oil polymer, wherein the addition amount of the silane coupling agent is 0.7% of the mass of the powder, the addition amount of the titanate coupling agent is 0.5% of the mass of the powder, the addition amount of the aluminate coupling agent is 0.3% of the mass of the powder, the addition amount of the stearic acid is 0.5% of the mass of the powder, and the addition amount of the POSS-phosphorylated vegetable oil polymer is 0.3% of the mass of the powder.
The preparation method of the POSS-phosphorylated vegetable oil polymer comprises the following steps:
s1: adding diethanolamine and sodium borohydride acetate into vegetable oil, heating to 130 ℃, continuously reacting for 3 hours, and then cooling to 45 ℃ to obtain a material A; the addition amount of the diethanol amine is 10 percent of the mass of the vegetable oil, and the addition amount of the diethanol amine is 0.1 percent of the mass of the vegetable oil;
s2: adding a phosphorylation reagent into the material A, uniformly stirring, heating to 80 ℃, and carrying out heat preservation reaction for 3 hours to obtain a material B; the phosphorylating agent is prepared by reacting P2O5Uniformly mixing the mixture with a phosphoric acid solution with the volume fraction of 85% according to the material-liquid ratio of 1:2, heating to 95 ℃, continuously reacting for 2 hours, and then cooling to room temperature to obtain the compound; phosphorylation ofThe adding amount of the reagent is 10 percent of the mass of the material A;
s3: adding acetic acid and hydrogen peroxide into the material B, reacting for 3 hours under the condition of heat preservation, washing the product to be neutral, removing water and drying to obtain a material C; the adding amount of the acetic acid is 1 percent of the mass of the material B; the adding amount of the hydrogen peroxide is 0.2 percent of the mass of the material B;
s4: adding acetic acid into the material C at 45 ℃, reacting for 2 hours under heat preservation, washing the product to be neutral, removing water and drying to obtain a material D; the adding amount of acetic acid is 1 percent of the mass of the material C;
s5: respectively dissolving POSS sodium salt, succinyl chloride and a material D in dichloromethane, mixing the POSS sodium salt solution and the succinyl chloride solution in a nitrogen atmosphere, reacting for 2 hours in an ice water bath, reacting for 3 hours at room temperature, then adding the material D solution and triethanolamine, reacting for 2 hours in the ice water bath and the nitrogen atmosphere, reacting for 4 hours at room temperature, filtering and washing a product to be neutral, removing water and drying to obtain the POSS-phosphorylated vegetable oil polymer; the mass ratio of the POSS sodium salt to the succinyl chloride to the triethanolamine to the material D is 21:34:15: 94.
The use method of the composite modifier comprises the steps of adding the POSS-phosphorylated vegetable oil polymer into powder, reacting for 1 minute, adding the silane coupling agent, the titanate coupling agent and the aluminate coupling agent, reacting for 3 minutes, adding stearic acid, and continuing to react for 5 minutes.
Example 2
The composite modifier capable of improving the activation degree of the heavy calcium carbonate for the silicone adhesive comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, stearic acid and a POSS-phosphorylated vegetable oil polymer, wherein the addition amount of the silane coupling agent is 0.9% of the mass of the powder, the addition amount of the titanate coupling agent is 0.4% of the mass of the powder, the addition amount of the aluminate coupling agent is 0.4% of the mass of the powder, the addition amount of the stearic acid is 0.6% of the mass of the powder, and the addition amount of the POSS-phosphorylated vegetable oil polymer is 0.1% of the mass of the powder.
The preparation method of the POSS-phosphorylated vegetable oil polymer comprises the following steps:
s1: adding diethanolamine and sodium borohydride acetate into vegetable oil, heating to 120 ℃, continuously reacting for 4 hours, and then cooling to 40 ℃ to obtain a material A; the addition amount of the diethanol amine is 20 percent of the mass of the vegetable oil, and the addition amount of the diethanol amine is 0.3 percent of the mass of the vegetable oil;
s2: adding a phosphorylation reagent into the material A, uniformly stirring, heating to 70 ℃, and carrying out heat preservation reaction for 4 hours to obtain a material B; the phosphorylating agent is prepared by reacting P2O5Uniformly mixing the mixture with a phosphoric acid solution with the volume fraction of 85% according to the material-liquid ratio of 1:5, heating to 90 ℃, continuously reacting for 4 hours, and then cooling to room temperature to obtain the compound; the adding amount of the phosphorylation reagent is 7 percent of the mass of the material A;
s3: adding acetic acid and hydrogen peroxide into the material B, reacting for 4 hours under heat preservation, washing the product to be neutral, removing water and drying to obtain a material C; the adding amount of the acetic acid is 5 percent of the mass of the material B; the adding amount of the hydrogen peroxide is 0.5 percent of the mass of the material B;
s4: adding acetic acid into the material C at 45 ℃, reacting for 1h under heat preservation, washing the product to be neutral, removing water and drying to obtain a material D; the adding amount of the acetic acid is 5 percent of the mass of the material C;
s5: respectively dissolving POSS sodium salt, succinyl chloride and a material D in dichloromethane, mixing the POSS sodium salt solution and the succinyl chloride solution in a nitrogen atmosphere, reacting for 3 hours in an ice water bath, reacting for 4 hours at room temperature, then adding the material D solution and triethanolamine, reacting for 3 hours in the ice water bath and the nitrogen atmosphere, reacting for 2 hours at room temperature, filtering and washing a product to be neutral, removing water and drying to obtain the POSS-phosphorylated vegetable oil polymer; the mass ratio of the POSS sodium salt to the succinyl chloride to the triethanolamine to the material D is 33:55:19: 100.
The use method of the composite modifier comprises the steps of adding the POSS-phosphorylated vegetable oil polymer into powder, reacting for 3 minutes, adding the silane coupling agent, the titanate coupling agent and the aluminate coupling agent, reacting for 4 minutes, adding stearic acid, and continuing to react for 10 minutes.
Example 3
The composite modifier capable of improving the activation degree of the heavy calcium carbonate for the silicone adhesive comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, stearic acid and a POSS-phosphorylated vegetable oil polymer, wherein the addition amount of the silane coupling agent is 0.8% of the mass of the powder, the addition amount of the titanate coupling agent is 0.2% of the mass of the powder, the addition amount of the stearic acid is 0.7% of the mass of the powder, the addition amount of the aluminate coupling agent is 0.5% of the mass of the powder, and the addition amount of the POSS-phosphorylated vegetable oil polymer is 0.5% of the mass of the powder.
The preparation method of the POSS-phosphorylated vegetable oil polymer comprises the following steps:
s1: adding diethanolamine and sodium borohydride acetate into vegetable oil, heating to 110 ℃, continuously reacting for 5 hours, and then cooling to 50 ℃ to obtain a material A; the addition amount of the diethanol amine is 30 percent of the mass of the vegetable oil, and the addition amount of the diethanol amine is 0.5 percent of the mass of the vegetable oil;
s2: adding a phosphorylation reagent into the material A, uniformly stirring, heating to 60 ℃, and carrying out heat preservation reaction for 3 hours to obtain a material B; the phosphorylating agent is prepared by reacting P2O5Uniformly mixing the mixture with a phosphoric acid solution with the volume fraction of 85% according to the material-liquid ratio of 1:8, heating to 100 ℃, continuously reacting for 4 hours, and then cooling to room temperature to obtain the compound; the adding amount of the phosphorylation reagent is 10 percent of the mass of the material A;
s3: adding acetic acid and hydrogen peroxide into the material B, reacting for 5 hours under heat preservation, washing the product to be neutral, removing water and drying to obtain a material C; the adding amount of the acetic acid is 10 percent of the mass of the material B; the adding amount of the hydrogen peroxide is 1 percent of the mass of the material B;
s4: adding acetic acid into the material C at 55 ℃, reacting for 3 hours under heat preservation, washing the product to be neutral, removing water and drying to obtain a material D; the adding amount of the acetic acid is 8 percent of the mass of the material C;
s5: respectively dissolving POSS sodium salt, succinyl chloride and a material D in dichloromethane, mixing the POSS sodium salt solution and the succinyl chloride solution in a nitrogen atmosphere, reacting for 4 hours in an ice water bath, reacting for 2 hours at room temperature, then adding the material D solution and triethanolamine, reacting for 4 hours in the ice water bath and the nitrogen atmosphere, reacting for 3 hours at room temperature, filtering and washing a product to be neutral, removing water and drying to obtain the POSS-phosphorylated vegetable oil polymer; the mass ratio of the POSS sodium salt to the succinyl chloride to the triethanolamine to the material D is 55:73:11: 123.
The use method of the composite modifier comprises the steps of adding the POSS-phosphorylated vegetable oil polymer into powder, reacting for 5 minutes, adding the silane coupling agent, the titanate coupling agent and the aluminate coupling agent, reacting for 5 minutes, adding stearic acid, and continuing to react for 1 minute.
Comparative example 1
Essentially the same as example 2, except that the POSS-phosphorylated vegetable oil polymer was not added to the composite modifier feed.
Comparative example 2
The composition was substantially the same as the raw material used in example 2, except that stearic acid was not added to the composite modifier raw material.
Comparative example 3
Basically the same as the raw materials of example 2, except that the POSS-phosphorylated vegetable oil polymer and stearic acid were not added to the raw materials of the composite modifier.
Comparative experiment
Firstly, preparing calcium carbonate powder:
storing the ore raw materials separately according to the types and grades of the ores; cleaning the mud adhered on the surface of the ore with water; selecting out the unqualified ores with low whiteness, bark and other impurities carried in the ores; 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; feeding the mineral aggregate into grinding equipment for grinding; products with different fineness are obtained by setting different rotating speeds; collecting the classified powder particles; sampling and inspecting the collected powder products, wherein the powder products with the fineness and the distribution of 1250-mesh products are qualified products and are used as raw materials for surface treatment of calcium carbonate for silicone adhesive, and degradation or beating back is performed if the powder products are unqualified; heating a powder product to be subjected to surface modification to 80-90 ℃; respectively adding the composite modifiers prepared in the examples 1-3 and the comparative examples 1-3 into the heated powder product, and respectively adding the composite modifiers according to the using methods of the examples 1-3 and the comparative examples 1-3, so that the surfaces of the powder particles are wrapped by the composite modifiers, and the surface characteristics of the powder particles are completely changed; cooling the modified product to room temperature; and (3) inspecting the activation degree and the oil absorption value of the cooled product, wherein the activation degree is more than or equal to 90 percent, the oil absorption value is less than or equal to 11g/100g, the product is qualified, the product is packaged and stored, and the unqualified product is degraded or returned.
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
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Oil absorption (g/100g) | 10.88 | 9.23 | 10.19 | 13.12 | 13.43 | 18.14 |
| Degree of activation/%) | 96.1 | 96.6 | 96.3 | 94.8 | 94.1 | 91.8 |
| Whiteness/% | 97.0 | 98.3 | 97.5 | 95.4 | 95.9 | 92.4 |
As can be seen from table 1, the calcium carbonate powder products modified by the composite modifiers of embodiments 1 to 3 of the present invention all have an activation degree of 91% or more, and particularly, the calcium carbonate powder products modified by the composite modifiers of embodiments 1 to 3 of the present invention all have an activation degree of 96% or more, an oil absorption of 11g/100g or less, and a whiteness of 97% or more, and have excellent properties; the calcium carbonate powder products modified by the composite modifier prepared in the comparative examples 1-3 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 POSS-phosphorylated vegetable oil polymer is not added in the raw materials, the oil absorption is increased by 3.89g/100g, the activation is reduced by 1.8 percent, and the whiteness is reduced by 2.9 percent;
compared with the data of the comparative example 3, the stearic acid is not added in the raw materials, the oil absorption is increased by 4.20g/100g, the activation degree is reduced by 2.5 percent, and the whiteness is reduced by 2.4 percent;
compared with the data of the comparative example 4, when the POSS-phosphorylated vegetable oil polymer and the stearic acid are added simultaneously, the oil absorption is increased by 8.91g/100g, the activation degree is reduced by 4.8 percent, and the whiteness is reduced by 5.9 percent;
as can be seen, the POSS-phosphorylated vegetable oil polymer acts independently, so that the oil absorption can be reduced by 3.89g/100g, the activation degree is improved by 1.8%, and the whiteness is improved by 2.9%; stearic acid acts independently, the oil absorption can be reduced by 4.20g/100g, the activation degree is improved by 2.5 percent, and the whiteness is improved by 2.4 percent; the combined action of the POSS-phosphorylated vegetable oil polymer, the aluminate coupling agent and the stearic acid can reduce the oil absorption by 8.91g/100g, improve the activation degree by 1.8 percent and improve the whiteness by 5.9 percent; therefore, the oil absorption reduction effect is increased when the POSS-phosphorylated vegetable oil polymer and the stearic acid act together compared with the oil absorption reduction effect when the POSS-phosphorylated vegetable oil polymer and the stearic acid act independently: [8.91- (3.89+4.20) ]/(3.89 +4.20) × 100% >, 10.1%, the activation degree-improving effect is increased by [4.8- (1.8+2.5) ]/(1.8 +2.5) × 100% >, 11.6% > 10%, and the whiteness-improving effect is increased by [5.9- (2.9+2.4) ]/(2.9 +2.4) × 100% >, 11.3% > 10%. Therefore, when the POSS-phosphorylated vegetable oil polymer, the aluminate coupling agent and the stearic acid are used together, a synergistic effect is generated, the oil absorption is synergistically reduced, and the activation degree and the whiteness are improved.
The POSS-phosphorylated vegetable oil polymer can obviously improve the dispersibility of calcium carbonate, has small POSS critical surface tension, good chemical inertia and hydrophobicity, better reduces and isolates the agglomeration acting force among calcium carbonate particles, and reduces agglomeration; the introduction of the phosphate can react with calcium ions on the surfaces of calcium carbonate particles to generate calcium phosphate to coat the surfaces of the calcium carbonate particles, so that the surface modification function is achieved, the processing and mechanical properties of the calcium carbonate can be improved, and the flame retardance and the corrosion resistance of the silicone adhesive product can be improved; the POSS-phosphorylated vegetable oil polymer has good antistatic property and stability, and the dispersibility of calcium carbonate particles is further improved; the aluminate coupling agent contains groups capable of reacting with active hydrogen, so that the aluminate coupling agent can generate bonding effect with hydroxyl on the surface of calcium carbonate powder, the activation degree of calcium carbonate particles can be improved, the affinity and the binding force of the calcium carbonate powder and silicone adhesive are improved, an anti-settling effect is generated, and the bonding strength of the silicone adhesive can be improved; 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 calcium carbonate solutionCa in (1)2+、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, and the affinity and the binding force of the calcium carbonate powder and the silicone adhesive are further improved. Stearic acid can synergistically improve the activation degree of calcium carbonate with an aluminate coupling agent and a POSS-phosphorylated vegetable oil polymer and reduce 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
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Bingham viscosity/(Pa s) | 30.05 | 30.33 | 30.15 | 28.07 | 28.04 | 25.23 |
| Consistency of base material/cm | 9.2 | 9.5 | 9.3 | 8.7 | 8.9 | 7.9 |
| Surface drying time/min | 15 | 13 | 14 | 16 | 15 | 19 |
| extrusion/(mL/min) | 283 | 295 | 289 | 275 | 279 | 255 |
| Tensile strength/MPa | 2.70 | 2.83 | 2.76 | 2.55 | 2.60 | 2.26 |
| Elongation at break/%) | 709.58 | 710.19 | 709.58 | 705.20 | 708.44 | 702.69 |
| Modulus of elasticity/MPa | 1.126 | 1.357 | 1.203 | 1.100 | 1.089 | 0.817 |
| Elastic recovery rate/%) | 98.6 | 98.8 | 98.5 | 96.8 | 97.2 | 94.8 |
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. As can be seen from the data in table 1, the calcium carbonate powder prepared by the composite modification with the addition of the POSS-phosphorylated vegetable oil polymer, the aluminate coupling agent and the stearic acid has higher elongation at break than the calcium carbonate powder prepared by the composite modification without the addition of the POSS-phosphorylated vegetable oil polymer, the aluminate coupling agent and the stearic acid; 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 (10)
1. A composite modifier capable of improving the activation degree of heavy calcium carbonate for silicone adhesive is characterized in that: the powder comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, stearic acid and a POSS-phosphorylated vegetable oil polymer, wherein the adding amount of the silane coupling agent is 0.7-0.9% 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 POSS-phosphorylated vegetable oil polymer is 0.1-0.5% of the mass of the powder.
2. The composite modifier capable of improving the activation degree of ground calcium carbonate for silicone adhesive according to claim 1, wherein the preparation method of POSS-phosphorylated vegetable oil polymer comprises the following steps:
s1: adding ethanolamine and a catalyst I into vegetable oil, heating to 110-130 ℃, continuously reacting for 3-5 h, and then cooling to 40-50 ℃ to obtain a material A;
s2: adding a phosphorylation reagent into the material A, uniformly stirring, heating to 60-80 ℃, and carrying out heat preservation reaction for 3-5 hours to obtain a material B;
s3: adding acetic acid, a catalyst II and hydrogen peroxide into the material B, reacting for 3-5 hours under heat preservation, washing the product to be neutral, removing water and drying to obtain a material C;
s4: adding acetic acid into the material C at the temperature of 45-55 ℃, reacting for 1-3 h under heat preservation, washing the product to be neutral, removing water and drying to obtain a material D;
s5: respectively dissolving POSS sodium salt, succinyl chloride and a material D in dichloromethane, mixing the POSS sodium salt solution and the succinyl chloride solution in a nitrogen atmosphere, reacting for 2-4 h in an ice water bath, reacting for 2-4 h at room temperature, then adding the material D solution and triethanolamine, reacting for 2-4 h in the ice water bath and the nitrogen atmosphere, reacting for 2-4 h at room temperature, filtering and washing a product to be neutral, removing water and drying to obtain the POSS-phosphorylated vegetable oil polymer.
3. The composite modifier capable of improving the activation degree of ground calcium carbonate for silicone adhesive according to claim 2, characterized in that: in the step S1, the addition amount of diethanolamine is 10-30% of the mass of the vegetable oil.
4. The composite modifier capable of improving the activation degree of ground calcium carbonate for silicone adhesive according to claim 2, characterized in that: in the step S1, the catalyst I is sodium borohydride acetate, and the addition amount of the catalyst I is 0.1-0.5% of the mass of the vegetable oil.
5. The composite modifier capable of improving the activation degree of ground calcium carbonate for silicone adhesive according to claim 2, characterized in that: in the step S2, the adding amount of the phosphorylation reagent is 5-10% of the mass of the material A; the phosphorylating agent is prepared by reacting P2O5Uniformly mixing the mixture with 85% by volume of phosphoric acid solution according to the material-to-liquid ratio of 1: 2-8, heating to 90-100 ℃, continuously reacting for 1-4 h, and then cooling to room temperature to obtain the product.
6. The composite modifier capable of improving the activation degree of ground calcium carbonate for silicone adhesive according to claim 2, characterized in that: in the step S3, the adding amount of acetic acid is 1-10% of the mass of the material B; the catalyst II is hydrogen peroxide, and the addition amount of the catalyst II is 0.2-1% of the mass of the material B.
7. The composite modifier capable of improving the activation degree of ground calcium carbonate for silicone adhesive according to claim 2, characterized in that: in the step S4, the adding amount of acetic acid is 1-8% of the mass of the material C.
8. The composite modifier capable of improving the activation degree of ground calcium carbonate for silicone adhesive according to claim 2, characterized in that: in the step S5, the mass ratio of the POSS sodium salt, the succinyl chloride, the triethanolamine and the material D is 21-55: 34-73: 11-19: 94-123.
9. The composite modifier capable of improving the activation degree of ground calcium carbonate for silicone adhesive according to any one of claims 1 to 8, characterized in that: the vegetable oil is one of rapeseed oil, tea seed oil, palm oil and cottonseed oil.
10. The use method of the composite modifier capable of improving the activation degree of the ground calcium carbonate for the silicone adhesive according to any one of claims 1 to 9 is characterized by comprising the following steps: adding the POSS-phosphorylated vegetable oil polymer 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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