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CN-116253844-B - Process for the production of hydrophobically active inorganic and/or organic fillers, fillers produced therewith and molded articles made from such fillers

CN116253844BCN 116253844 BCN116253844 BCN 116253844BCN-116253844-B

Abstract

A process for the production of hydrophobically active inorganic and/or organic fillers comprising the steps of (a) providing a filler having a certain surface area, (b) mixing the filler with a solution of at least one hydrophobically and bio-based active compound in a mixing device at a rate of from 0.15X 10 ‑2 to 5.0X 10 ‑2 g/square meter of filler surface area, from 20 to 200 revolutions per minute for from 12 to 120 minutes, (c) evacuating the hydrophobically active inorganic and/or organic filler in a storage bag, tank or vat or directly in a casting compound.

Inventors

  • DATSYUK VITALIY
  • Adam Orlando

Assignees

  • 肖克有限公司

Dates

Publication Date
20260505
Application Date
20221111
Priority Date
20211209

Claims (16)

  1. 1. A process for the production of hydrophobically active inorganic and/or organic fillers comprising the steps of (a) providing a filler having a certain surface area, (b) mixing the filler with a solution of at least one hydrophobically and bio-based active compound in a mixing device at a rate of from 0.15X 10 -2 to 5.0X 10 -2 g/square meter of filler surface area, from 20 to 200 revolutions per minute for from 12 to 120 minutes, (c) evacuating the hydrophobically active inorganic and/or organic filler in a storage bag, tank or vat or directly in a casting compound; Wherein in step (a) the filler is an inorganic filler selected from SiO 2 、Al 2 O 3 、TiO 2 、ZrO 2 、Fe 2 O 3 、ZnO、Cr 2 O 5 、 carbon, siC, siN, BN or mixtures thereof, or the filler is an organic filler selected from ground fruit pits and/or shells selected from olive pits, peach pits, apricot pits, cherry pits, almond shells, morocco shells, walnut shells or mixtures thereof; Wherein in step (b) the weight concentration of the hydrophobicized and bio-based activating compound in the monomer present in the polymer matrix of the molded article is from 1 to 20% by weight and the monomer is used as solvent, the hydrophobicized and bio-based activating compound is selected from vegetable oil based methacryloyl monomers of the general formula H 2 C=C(R 1 )C(O)-NH-CH 2 -CH 2 -C(O)-O-R 2 wherein R 1 is H in the case of acrylic acid and CH 3 in the case of methacrylic acid wherein R 2 is a fatty acid residue from a vegetable oil based oil which reacts with N-hydroxyethyl (meth) acrylamide.
  2. 2. The method according to claim 1, wherein in step (a), the inorganic filler and the organic filler are used in combination in any mixing ratio.
  3. 3. The method according to claim 1, wherein in step (a), the particle diameters of the inorganic filler and the organic filler are 1 to 2000 μm.
  4. 4. The method according to claim 1, wherein in step (b) the hydrophobicized and bio-based activation active compound is dissolved in at least one monomer which is present in the polymer matrix of the molded article.
  5. 5. The method according to claim 1, wherein the monomer used as solvent for the hydrophobized and bio-based activated compound in step (b) is selected from the group consisting of mono-functional acrylate monomers selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, isodecyl acrylate, dihydroxycyclopentadienyl acrylate, diethylene glycol ethyl acrylate, seventeen acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxyethyl caprolactone, polycaprolactone, hydroxypropyl acrylate, lauryl acrylate, stearyl acrylate, 2- (2-ethoxy) ethyl acrylate, tetrahydrofuranyl acrylate, 2-phenoxyethyl acrylate, ethoxylated 4-phenyl acrylate, trimethylcyclohexyl acrylate, octyl decyl acrylate, tridecyl acrylate, ethoxylated 4-nonylphenyl acrylate, isobornyl acrylate, trimethylolpropane methylacrylate, ethoxylated 4-lauryl acrylate, polyester acrylate, hyperbranched polyester acrylate, epoxy acrylate, melamine acrylate.
  6. 6. The method according to claim 1, wherein the monomer used as solvent for the hydrophobized and bio-based activated compound in step (b) is selected from monofunctional methacrylate monomers selected from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, behenyl polyethylene glycol methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, isotridecyl methacrylate, ureido methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, methoxypolyethylene glycol methacrylate, glycidyl methacrylate.
  7. 7. The method according to claim 1, wherein the monomer used as solvent for the hydrophobized and bio-based activated compound in step (b) is selected from the group consisting of multifunctional acrylate monomers selected from the group consisting of 1, 6-hexanediol diacrylate, polyethylene glycol diacrylate, polybutadiene diacrylate, 3-methyl-1, 5-pentanediol diacrylate, dipropylene glycol diacrylate, 1, 10-decanediol diacrylate, alkoxylated diacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, aliphatic polyurethane diacrylates, aromatic polyurethane triacrylates, aromatic polyurethane hexaacrylates, polyester hexaacrylates, epoxidized soybean oil diacrylates.
  8. 8. The method according to claim 1, wherein the monomer used as solvent for the hydrophobized and bio-based activating compound in step (b) is selected from the group consisting of multifunctional methacrylate monomers selected from the group consisting of ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, 1, 10-decanediol dimethacrylate, 1, 3-butanediol dimethacrylate, tricyclodecanediol dimethacrylate, trimethylolpropane trimethacrylate.
  9. 9. The method of claim 1 wherein the oil base in the vegetable oil-based methacryloyl monomers is derived from vegetable oil.
  10. 10. The method according to claim 9, wherein, the vegetable oil is selected from coconut oil, germ oil, rapeseed oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower seed oil, almond oil, beech nut oil, cashew oil, hazelnut oil, manjieli oil, pistachio oil, walnut oil, pumpkin seed oil, grapefruit seed oil, gourd oil, walnut seed oil, watermelon seed oil, borage seed oil, gooseberry seed oil, black seed oil, brazil seed oil, evening primrose oil, linseed oil, amaranth oil, almond oil, apple seed oil, argan oil, avocado oil, carnauba oil, moringa oil, buckeye nut oil, cocoa butter, pinus oil, coconut seed oil, grape seed oil, kapok seed oil, kenaf seed oil, horse rura oil, mustard oil Ramie grass oil, nutmeg fat, okra seed oil, perilla seed oil, persimmon seed oil, brazil oil, pilocarpus oil, pomegranate seed oil, poppy seed oil, barcas fruit oil, plum kernel oil, quinoa oil, rice oil, kava fruit oil, barbar koku coconut oil, shea butter, tea seed oil, tiger nut oil, tobacco seed oil, tomato seed oil, wheat germ oil, castor oil, camelina oil, sea weed seed oil, tung oil, jatropha oil, jojoba oil, clematis oil, indian beech oil, catalpa oil, artichoke oil, wood Lu Xingguo palm fat, bladder pod oil, longum seed oil, burdock root oil, mao Ruilv fruit oil, stone chestnut oil, carrot seed oil, calyx flower oil, rose fruit oil, rubber seed oil, sea buckthorn oil, cranberry rose seed oil and red bean oil.
  11. 11. The method according to claim 1, wherein in step (b) the hydrophobized and biobased activating active compound is present in the polymer matrix of the molded article in a concentration of 3% to 17.5% by weight in the monomer and is used as solvent.
  12. 12. The method according to claim 1, wherein in step (b) the hydrophobized and biobased activating active compound is present in the polymer matrix of the molded article in a concentration of 5 to 15% by weight in the monomer and is used as solvent.
  13. 13. A hydrophobically active inorganic or organic filler made according to the method of any one of claims 1 to 12.
  14. 14. Use of the filler according to claim 13 as aggregate for polymer-based casting materials for the manufacture of composite mouldings or as part of the manufacture of dental filling composite systems.
  15. 15. A molded article made from the casting material of claim 14.
  16. 16. The molded article according to claim 15, wherein the molded article is a sanitary ware in the form of a kitchen sink, a lavatory, a shower tray, a bathtub, a toilet bowl or a bidet.

Description

Process for the production of hydrophobically active inorganic and/or organic fillers, fillers produced therewith and molded articles made from such fillers Technical Field The invention relates to a method for producing hydrophobically active inorganic and/or organic fillers. For example, such fillers are used as aggregate for polymer-based castable materials from which composite molded bodies are produced. Background Shrinkage and shrinkage stresses are a common problem in many applications based on fully cured thermoplastic materials such as molded kitchen sink, lavatory basin, bathtub or dental filling composite systems. Such composites typically comprise a fully cured polymeric binder, an initiator system, and silane-treated inorganic filler particles. During curing of these composite systems shrinkage can be observed, which on the one hand leads to micro-cracks and on the other hand generates strong intrinsic stresses in the material. For example, in a molded kitchen sink, this may lead to crack propagation in the material, resulting in water leakage or reduced mechanical properties. The same problems may occur with dental composites, stress, micro-leakage, adhesive fall off, and thus cause pain to the patient. These problems can be attributed to the high filler content in the composite and the use of 3-methacryloxypropyl trimethoxysilane, which is immobilized on the surface of quartz particles and has a low flowability due to its relatively short triplet chain. This limited flowability leads to rapid cleavage of the free radicals and formation of short polymer chains during polymerization, which, due to the high stiffness, leads to strong stresses on the system. Thermal shrinkage or expansion of the material and mechanical impact can be a source of microcracking at the filler-matrix interface. At the filler-matrix interface, the initial stress is concentrated on the rigid inorganic surface due to the presence of many reactive groups. Typically, the surface of the silica sand particles has 0.8 hydroxyl groups per 1 square nanometer of surface area. During the silylation process, almost every hydroxyl group reacts with a single silane molecule and forms a uniform hydrophobic silane layer, thereby creating a superhydrophobic effect that very densely immobilizes the active methacrylate groups. The high concentration of double bonds immobilized on the filler surface results in polymerization of short polymer chains, thereby forming regions of high internal stress. The methacrylate silane may be replaced with an inactive silane to reduce stress, but since there is no bond between the filler and the matrix, this will reduce mechanical properties such as impact strength. The inorganic and/or organic fillers treated with silane coupling agents require hydrolysis of the hydrolyzable ester functional groups of the silane. For example, hydrolysis of 1000 kg of 3-methacryloxypropyl trimethoxysilane would yield 387: 387 kg of methanol. Methanol is a flammable liquid with a very high vapor pressure and causes death after ingestion. Furthermore, silanization of the filler is technically achieved by thermal activation at temperatures of 60 ℃ or higher. The energy required for this process is typically achieved by burning natural gas or corresponding hydrocarbons, which results in carbon dioxide emissions and increases process costs. After the silylation process, a curing time of several days is typically required until the desired hydrophobicity of the filler is reached. Disclosure of Invention The task of the present invention is to eliminate the above technical and environmental problems of the prior art. To solve this task, a process for the production of hydrophobically active inorganic and/or organic fillers is proposed, which comprises the steps of (a) providing a filler having a certain surface area, (b) mixing the filler with a solution of at least one hydrophobically and biobased active substance in a mixing device in an amount of 0.15X 10 -2 to 5.0X 10 -2 g/square meter of filler surface area at a speed of 20 to 200 revolutions per minute for 12 to 120 minutes, (c) transferring the hydrophobically active inorganic and/or organic filler into a storage bag, tank or vat or pouring directly into a casting. The silylation process requires that the treated filler be stored for seven days for subsequent reactions. In contrast to this process, the present invention proposes a technique that allows the filler to be used immediately after treatment. Furthermore, the process according to the invention does not require a heating process, whereas the silylation reaction is carried out while heating to at least 60 ℃ for at least 30 minutes. The hydrophobic active filler of the present invention has a different interface with the matrix. The double bonds of the methacryloyl groups close to the filler surface encapsulate the filler surface during polymerization and prepare the double bonds on the fatty acid side chains for