CN116355280A - Nano zinc oxide dispersion liquid for polyester in-situ polymerization and preparation method thereof - Google Patents
Nano zinc oxide dispersion liquid for polyester in-situ polymerization and preparation method thereof Download PDFInfo
- Publication number
- CN116355280A CN116355280A CN202310173599.8A CN202310173599A CN116355280A CN 116355280 A CN116355280 A CN 116355280A CN 202310173599 A CN202310173599 A CN 202310173599A CN 116355280 A CN116355280 A CN 116355280A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- nano zinc
- polyester
- dispersion liquid
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229920000728 polyester Polymers 0.000 title claims abstract description 75
- 239000007788 liquid Substances 0.000 title claims abstract description 59
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 34
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 67
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000006185 dispersion Substances 0.000 claims abstract description 49
- 239000007822 coupling agent Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004593 Epoxy Substances 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000011324 bead Substances 0.000 claims description 12
- 238000006011 modification reaction Methods 0.000 claims description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- -1 dodecylbenzenesulfonyloxy Chemical group 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- GVXYMVJBUCMDJE-UHFFFAOYSA-K C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CC)O[Ti+3].C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[O-] Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CC)O[Ti+3].C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[O-] GVXYMVJBUCMDJE-UHFFFAOYSA-K 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000032050 esterification Effects 0.000 abstract description 6
- 238000005886 esterification reaction Methods 0.000 abstract description 6
- 239000011858 nanopowder Substances 0.000 abstract description 6
- 238000010009 beating Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- 239000004576 sand Substances 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 239000004594 Masterbatch (MB) Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a nano zinc oxide dispersion liquid for polyester in-situ polymerization and a preparation method thereof, and the components comprise: nano zinc oxide, glycol, a compound modifier, a stabilizer and a dispersion aid agent; the compound modifier comprises a long carbon chain type coupling agent and a coupling agent containing a reaction group; the long carbon chain type coupling agent contains at least one alkyl chain with more than C6; the coupling agent containing the reactive group contains one or more of amino, epoxy and mercapto. The invention uses the compound modifier to carry out surface treatment on the nano zinc oxide to prepare stable dispersion liquid of an ethylene glycol system, can be added on line in a beating or esterification stage in the polyester synthesis process, greatly improves the dispersibility of nano powder, improves the polyester performance, has no special equipment expenditure, and is convenient for industrial production.
Description
Technical Field
The invention relates to the technical field of additives for polyesters, in particular to a nano zinc oxide dispersion liquid for polyester in-situ polymerization and a preparation method thereof.
Background
The addition of antimicrobial nanopowder to polyester fibers is one of the most effective methods for developing antimicrobial polyester fibers. The nano zinc oxide has broad-spectrum efficient antibacterial property, has the characteristics of photocatalysis antibacterial property, active oxide antibacterial property and metal ion dissolution antibacterial property, has the killing rate of 99 percent on strains such as escherichia coli, staphylococcus aureus and the like, has the ultraviolet resistance, and is an excellent nano additive. Zinc oxide is added to polyester materials to prepare antibacterial polyester fibers, and the antibacterial polyester fibers have been widely used.
Because the inorganic nano particles have a special surface structure, the surfaces of the inorganic nano particles lack adjacent coordination atoms, and the inorganic nano particles have high activity and are extremely easy to agglomerate; and the inorganic particles have poor compatibility with the polyester matrix, so that the inorganic particles cannot be directly blended with the polyester material for melt spinning. In the prior art, nano zinc oxide is added into polyester mostly by adopting a master batch technology, and nano powder functional master batch is firstly manufactured and then is blended with polyester for melt spinning. For example, a method for manufacturing inorganic nano zinc oxide multifunctional composite antibacterial polyester fiber disclosed in Chinese patent literature, publication No. CN102560725A, firstly, preparing hydrophilic modified polyester chips, blending zinc oxide powder below 100 nanometers with fiber-forming polymers according to the weight ratio of 20-35:80-65, and then processing the mixture by a special process to prepare master batches suitable for polyester fiber production. The special master batch is blended with the hydrophilic modified polyester chip in a proportion of 5 to 15 weight percent, and the inorganic nano zinc oxide multifunctional composite antibacterial polyester fiber is manufactured by a polyester fiber production process.
The master batch technology is adopted to add nano zinc oxide, and the method is simple and flexible to operate, but has the problems of large master batch addition amount, uneven nano zinc oxide distribution, short period of a slice spinning component, high cost and high energy consumption, and is not suitable for large-scale industrial production.
Disclosure of Invention
The invention aims to overcome the problems existing in the prior art that the master batch technology is adopted to add nano zinc oxide, and provides the nano zinc oxide dispersion liquid for polyester in-situ polymerization and the preparation method thereof, wherein the nano zinc oxide dispersion liquid is prepared by carrying out surface treatment on nano zinc oxide by using a compound modifier, so that the dispersion liquid of a stable ethylene glycol system can be added on line in a beating or esterification stage in the polyester synthesis process, the dispersibility of nano powder is greatly improved, the polyester performance is improved, no special equipment expenditure is generated, and the industrial production is facilitated.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a nano zinc oxide dispersion liquid for polyester in-situ polymerization, which comprises the following components: nano zinc oxide, glycol, a compound modifier, a stabilizer and a dispersion aid agent; the compound modifier comprises a long carbon chain type coupling agent and a coupling agent containing a reaction group; the long carbon chain type coupling agent contains at least one alkyl chain with more than C6; the coupling agent containing the reactive group contains one or more of amino, epoxy and mercapto.
According to the invention, the reactant glycol during polyester synthesis is selected as the solvent of the nano zinc oxide dispersion liquid, and the operation steps of removing the solvent in the conventional nano powder modification process such as centrifugation, spraying or suction filtration are not required, so that the modification difficulty of nano zinc oxide is greatly reduced; the prepared nano zinc oxide dispersion liquid is convenient to use, has no special requirement on polymerization, and can be directly added in a beating or esterification section in the polyester synthesis process.
Meanwhile, the nano zinc oxide is modified by adopting the compound modifier, and the compound modifier comprises two different coupling agents, so that the long carbon chain coupling agent can change the surface of the nano zinc oxide from hydrophilic to hydrophobic, and the compatibility of the nano zinc oxide and a polyester matrix is improved; the amino, epoxy and mercapto groups in the coupling agent containing the reactive groups can react with carboxyl groups in reactants during the synthesis of the polyester, so that the nano zinc oxide can be connected in a polyester matrix through chemical bonds, and the polyester performance can be improved. In addition, the long carbon chain coupling agent and the coupling agent containing the reactive group can act together to adjust the particle size of the zinc oxide in the dispersion liquid to be in a proper range, so that the nano zinc oxide can be stably dispersed in the ethylene glycol, and the nano zinc oxide in the polyester obtained by polymerization can be uniformly distributed.
Preferably, in the compound modifier, the mass ratio of the long carbon chain coupling agent to the coupling agent containing the reactive group is 0.2-5:1; the total mass of the compound modifier is 0.5-5% of the mass of the nano zinc oxide. The dosage of the long carbon chain type coupling agent and the coupling agent containing the reactive group is controlled within the range, so that the particle size of the particles in the dispersion liquid can be adjusted to the optimal range, and the dispersion liquid has good dispersion stability. If the dosage of the long carbon chain type coupling agent is too small, the zinc oxide is not completely covered, and the particle size is larger; when the amount of the long carbon chain type coupling agent is too large, too many organic long chains are entangled with each other, which also results in a large particle size. The consumption of the coupling agent containing the reactive group is too small, nano zinc oxide cannot participate in the synthetic reaction of the polyester, zinc oxide cannot be uniformly distributed in the polyester, and the strength of the polyester is reduced; when the coupling agent containing the reactive group is used in an excessive amount, the polyester is seriously crosslinked, which is unfavorable for the post-fiber processing.
Preferably, the long carbon chain coupling agent is selected from one or more of isopropoxytris (dioctyl pyrophosphoryl) titanate, isopropoxytrioleic acyloxy titanate, propoxytitanium tristearate, isopropoxytris (dodecylbenzenesulfonyloxy) titanate, octadecyltrimethoxysilane and hexadecyltrimethoxysilane; the coupling agent containing the reactive group is selected from one or more of isopropyl tri (ethylenediamine-N-ethoxy) titanate, 3-aminopropyl triethoxysilane, N-2-aminoethyl-3-aminopropyl triethoxysilane, 3-glycidol ether oxypropyl triethoxysilane and 3-mercaptopropyl triethoxysilane.
Preferably, the stabilizer is selected from one or more of trimethyl phosphate, triethyl phosphate, triphenyl phosphate and triethyl phosphoric acid; the mass of the stabilizer is 0.005-0.02% of the mass of the nano zinc oxide. The stabilizer can reduce the catalytic activity of nano zinc oxide and avoid the degradation of polyester catalyzed by zinc oxide.
Preferably, the dispersion aid agent comprises a first dispersion aid agent and a second dispersion aid agent; the first dispersing aid agent is polyethylene glycol (PEG) with molecular weight lower than 1000 and/or polyvinylpyrrolidone with molecular weight higher than 58000; the mass of the first auxiliary dispersing agent is 0.3-5% of the mass of the nano zinc oxide; the second dispersing aid is sodium polyacrylate and/or sodium hexametaphosphate; the mass of the second auxiliary dispersing agent is 0.25-1% of the mass of the nano zinc oxide.
The adsorption vacancies on the first dispersion aid agent can be complexed with the surface of zinc oxide or form hydrogen bonds, and are adsorbed on the surface of zinc oxide, so that the zinc oxide is maintained to be modified by the coupling agent of the next step with the size smaller than 3 mu m, and the zinc oxide is prevented from being modified in an agglomerate form and cannot be ground and opened in the later period. The second dispersing aid can be adsorbed on the surface of the modified zinc oxide, so that the surface potential is increased, the repulsive force is increased, and the storage stability and the thermal stability of the later-stage dispersion liquid are ensured.
Preferably, the mass concentration of nano zinc oxide in the dispersion is less than 15%.
The invention also provides a preparation method of the nano zinc oxide dispersion liquid for polyester in-situ polymerization, which comprises the following steps:
(1) Mixing nano zinc oxide with ethylene glycol, adding a dispersing aid agent, and grinding until the particle size D99 of the zinc oxide is smaller than 3 mu m to obtain an initial dispersion;
(2) Regulating the pH value of the initial dispersion liquid to 10-12, and dripping a compound modifier for modification reaction;
(3) Adding a stabilizer and a dispersing aid to the dispersion liquid after the modification reaction, and grinding again until the particle size of zinc oxide is smaller than 1 mu m to obtain the nano zinc oxide dispersion liquid for polyester in-situ polymerization.
Preferably, the auxiliary dispersant added in the step (1) is a first auxiliary dispersant, and the auxiliary dispersant added in the step (3) is a second auxiliary dispersant.
Preferably, the pH regulator used in the step (2) for regulating the pH is one or more of ammonia water, triethanolamine, organic amine and sodium hydroxide; the modification reaction temperature is 50-120 ℃.
Preferably, the particle size of the polishing beads used in the polishing in the step (1) and the step (3) is 0.3 to 0.6. Mu.m, and the polishing temperature is lower than 40 ℃.
Therefore, the invention has the following beneficial effects:
(1) The reactant glycol during the synthesis of the polyester is selected as a modification system of the nano zinc oxide, and the operation steps of removing solvents such as centrifugation, spraying or suction filtration in the conventional nano powder modification process are not needed, so that the modification difficulty of the nano zinc oxide is greatly reduced; the residue of the compound modifier is strictly controlled by the process conditions, the use is convenient, no special requirement is imposed on the polymerization, and the compound modifier can be directly added in the beating or esterification section in the polyester synthesis process;
(2) The nano zinc oxide is modified by two coupling agents with different properties in a strictly controlled proportion, so that on one hand, the problem of controlling the particle size when the nano zinc oxide is dispersed in an ethylene glycol system is solved, and on the other hand, the problems of compatibility and reactivity between the nano zinc oxide and a polyester matrix after polymerization are solved; the stability of the nano zinc oxide dispersion liquid is good, and the nano zinc oxide can be uniformly distributed in the polyester obtained by polymerization; (3) The antibacterial polyester fiber prepared by melt spinning can still keep the excellent performance of the polyester fiber, and the size of the spinnable single filament is regulated to be less than 1dtex by a process.
Detailed Description
The invention is further described below in connection with the following detailed description.
In the present invention, the equipment, materials, etc. used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a preparation method of a nano zinc oxide dispersion liquid for polyester in-situ polymerization comprises the following steps:
(1) Mixing 50g of nano zinc oxide (Ala-dine) with 450g of ethylene glycol, fully dispersing by a high-speed dispersing machine, grinding by a sand mill filled with zirconium beads of 0.4 mu m, and dropwise adding 0.45g of PEG600 in the grinding process until the granularity of D99 is less than 3 mu m to obtain an initial dispersion;
(2) Transferring into a flask, regulating the pH value to 10 by ammonia water, heating to 50 ℃, dropwise adding 0.5g of 3-aminopropyl triethoxysilane and 0.8g of isopropoxy trioleate acyloxy titanate within 1 hour, reacting for 16 hours under heat preservation, and naturally cooling;
(3) Transferring the dispersion liquid after the modification reaction in the step (2) into a sand mill, grinding by using zirconium beads with the diameter of 0.3 mu m, and dripping 0.05g of sodium polyacrylate and 0.05g of triethyl phosphate into the dispersion liquid to grind until the D99 is smaller than 0.6 mu m, so as to obtain the nano zinc oxide dispersion liquid for polyester in-situ polymerization.
Example 2:
a preparation method of a nano zinc oxide dispersion liquid for polyester in-situ polymerization comprises the following steps:
(1) Mixing 50g of nano zinc oxide (Ala-dine) with 450g of ethylene glycol, fully dispersing by a high-speed dispersing machine, grinding by a sand mill filled with zirconium beads of 0.4 mu m, and dropwise adding 0.6g of PEG600 in the grinding process until the granularity of D99 is less than 2 mu m to obtain an initial dispersion;
(2) Transferring into a flask, regulating the pH value to 11 by ammonia water, heating to 80 ℃, dropwise adding 1.3g of 3-aminopropyl triethoxysilane and 1.2g of octadecyl trimethoxysilane within 0.5 hour, reacting for 6 hours under heat preservation, and naturally cooling;
(3) Transferring the dispersion liquid after the modification reaction in the step (2) into a sand mill, grinding by using zirconium beads with the diameter of 0.3 mu m, and dripping 0.25g of sodium hexametaphosphate and 0.05g of triethyl phosphate into the dispersion liquid until the D99 is smaller than 0.6 mu m, thereby obtaining the nano zinc oxide dispersion liquid for polyester in-situ polymerization.
Example 3:
a preparation method of a nano zinc oxide dispersion liquid for polyester in-situ polymerization comprises the following steps:
(1) Mixing 50g of nano zinc oxide (Ala-dine) with 450g of ethylene glycol, fully dispersing by a high-speed dispersing machine, grinding by a sand mill filled with zirconium beads of 0.4 mu m, and dropwise adding 0.6g of PEG400 in the grinding process until the granularity of D99 is less than 2 mu m to obtain an initial dispersion;
(2) Transferring into a flask, regulating the pH value to 10.5 by ammonia water, heating to 85 ℃, dropwise adding 1g of 3-aminopropyl triethoxysilane and 0.5g of isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate within 0.5 hour, reacting for 3 hours under heat preservation, and naturally cooling; (3) Transferring the dispersion liquid after the modification reaction in the step (2) into a sand mill, grinding by using zirconium beads with the diameter of 0.3 mu m, and dripping 0.25g of sodium hexametaphosphate and 0.05g of triethyl phosphate into the dispersion liquid until the D99 is smaller than 0.6 mu m, thereby obtaining the nano zinc oxide dispersion liquid for polyester in-situ polymerization.
Example 4:
a preparation method of a nano zinc oxide dispersion liquid for polyester in-situ polymerization comprises the following steps:
(1) Mixing 50g of nano zinc oxide (Ala-dine) with 450g of ethylene glycol, fully dispersing by a high-speed dispersing machine, grinding by a sand mill filled with zirconium beads of 0.4 mu m, and dropwise adding 0.6g of PEG400 in the grinding process until the granularity of D99 is less than 2 mu m to obtain an initial dispersion;
(2) Transferring into a flask, regulating the pH value to 10 by ammonia water, heating to 85 ℃, dropwise adding 1g of 3-aminopropyl triethoxysilane and 0.6g of isopropoxy tris (dodecylbenzenesulfonyloxy) titanate within 0.5 hour, reacting for 4 hours under heat preservation, and naturally cooling; (3) Transferring the dispersion liquid after the modification reaction in the step (2) into a sand mill, grinding by using zirconium beads with the diameter of 0.3 mu m, and dripping 0.25g of sodium hexametaphosphate and 0.1g of triethyl phosphate into the dispersion liquid until the D99 is smaller than 0.6 mu m to obtain the nano zinc oxide dispersion liquid for polyester in-situ polymerization.
Example 5:
a preparation method of a nano zinc oxide dispersion liquid for polyester in-situ polymerization comprises the following steps:
(1) Mixing 25g of nano zinc oxide (Ala-dine) with 475g of ethylene glycol, fully dispersing by a high-speed dispersing machine, grinding by a sand mill filled with zirconium beads of 0.3 mu m, and dropwise adding 0.4g of PEG400 in the grinding process until the granularity of D99 is less than 1 mu m to obtain an initial dispersion;
(2) Transferring into a flask, regulating the pH value to 11 by ammonia water, heating to 85 ℃, dropwise adding 1g of 3-glycidoxypropyl triethoxysilane and 0.5g of propoxytitanium tristearate within 1 hour, reacting for 3 hours under heat preservation, and naturally cooling;
(3) And (3) adding 0.05g of triethyl phosphate into the dispersion liquid after the modification reaction in the step (2), and directly obtaining the nano zinc oxide dispersion liquid for polyester in-situ polymerization without secondary grinding.
Example 6:
a preparation method of a nano zinc oxide dispersion liquid for polyester in-situ polymerization comprises the following steps:
(1) Mixing 25g of nano zinc oxide (Ala-dine) with 475g of ethylene glycol, fully dispersing by a high-speed dispersing machine, grinding by a sand mill filled with zirconium beads of 0.3 mu m, and dropwise adding 0.4g of PEG400 and 0.2g of PEG1000 in the grinding process until the granularity of D99 is less than 1 mu m to obtain an initial dispersion;
(2) Transferring into a flask, regulating the pH value to 10.5 by ammonia water, heating to 70 ℃, dropwise adding 1g of 3-mercaptopropyl triethoxysilane and 1.3g of hexadecyl trimethoxy silane within 1 hour, reacting for 5 hours under heat preservation, and naturally cooling;
(3) And (3) adding 0.1g of triethyl phosphate into the dispersion liquid after the modification reaction in the step (2), and directly obtaining the nano zinc oxide dispersion liquid for polyester in-situ polymerization without secondary grinding.
Comparative example 1 (no reactive group-containing coupling agent added):
comparative example 1 was different from example 1 in that 3-aminopropyl triethoxysilane was not added in step (2), only 0.8g of isopropoxytrionoyloxy titanate was added dropwise, and the rest was the same as in example 1.
Comparative example 2 (coupling agent containing reactive groups added too much):
comparative example 2 differs from example 1 in that 5g of 3-aminopropyl triethoxysilane and 0.8g of isopropoxytrionoyloxy titanate were added dropwise in step (2), the remainder being the same as in example 1.
Comparative example 3 (no long carbon chain coupling agent added):
comparative example 3 was different from example 1 in that no isopropoxytriacryloyloxy titanate was added in step (2), only 0.5g of 3-aminopropyl triethoxysilane was added dropwise, and the rest was the same as in example 1.
Comparative example 4 (long carbon chain coupling agent addition too much):
comparative example 4 differs from example 1 in that 0.5g of 3-aminopropyl triethoxysilane and 3g of isopropoxytrionoyloxy titanate were added dropwise in step (2), the remainder being the same as in example 1.
The dispersions prepared in the above examples and comparative examples were subjected to particle size, semi-annual sedimentation stability analysis, centrifugal washing to make hydrophilic-hydrophobic contact angle test, and were each fabricated into polyester chips to observe agglomerated particles, and melt filtration performance test was performed (refer to novel DIN EN 13900-5 pigment and filler-diffusion method and evaluation of diffusibility in plastics and FZ T51019-2021 polyester fiber masterbatch), and the results are shown in Table 1.
The preparation method of the polyester chip comprises the following steps: terephthalic acid, ethylene glycol, the nano zinc oxide dispersion liquid and ethylene glycol antimony obtained by the invention are added into a 2.5L reaction kettle, the mol ratio of the terephthalic acid to the ethylene glycol is 1:1.25 (the ethylene glycol contained in the dispersion liquid is calculated in reactants), the adding mass of the nano zinc oxide dispersion liquid is 80g, and the adding amount of the ethylene glycol antimony is 30ppm; stirring and heating to 240 ℃, controlling the pressure in the kettle to reach 360kPa, slowly releasing pressure and discharging water, reacting for 2.5h, and ending the esterification when the esterification rate reaches 95%; starting a vacuum pump to perform polycondensation, keeping the pressure in the kettle at 100Pa, controlling the temperature at 278 ℃, discharging the polyester melt through a bottom valve after 3 hours of reaction, and granulating to obtain the polyester chips.
Table 1: and (5) the dispersion liquid and polyester chip performance test results.
As can be seen from table 1, by adjusting and controlling the ratio of the two coupling agents in the compound modifier, the particle size and the contact angle are used as the modification degree for representing zinc oxide, the method in the invention is adopted in examples 1 to 6, the D99 particle size of the nano zinc oxide dispersion liquid is smaller than 1 μm, the placement stability of the dispersion liquid is good, and the layering phenomenon is not generated; after modification by the compound coupling agent, the surface of the nano zinc oxide is changed into a hydrophobic surface, the contact angle is 97-108 degrees, at the moment, the nano zinc oxide is well dispersed in polyester, the melt filtering performance is good, no obvious pressure rise exists, and the less aggregated particles are, the smaller the pressure filtration difference is.
In comparative example 1, the coupling agent containing a reactive group is not added, when the long carbon chain coupling agent is used for modifying nano zinc oxide, the particle hydrophobicity is large, the particle size is overlarge, the stability is poor, the particles cannot be stably dispersed in ethylene glycol, the condensed particles in the slice cannot be counted, and the pressure boost is obvious in the filter pressing value test. Too much coupling agent containing reactive groups is added in comparative example 2, which exceeds the range of the invention, so that the particle diameter of zinc oxide is larger, and zinc oxide modified by too much reactive groups becomes a crosslinking point, so that polyester crosslinking is serious, agglomeration is obvious, and the pressure rapidly rises in a filter pressing value test.
In comparative example 3, no long carbon chain coupling agent is added, the nano zinc oxide is modified by using the coupling agent containing the reactive group, the situation is similar to that of comparative example 2, and the compatibility between the zinc oxide and the polyester matrix is poor due to the fact that the long carbon chain coupling agent is not added, and the pressure rise is obvious in the test of the filter pressing value. The long carbon chain type coupling agent added in the comparative example 4 is too much, the long carbon chains of the excessive coupling agent are intertwined, the zinc oxide agglomeration is serious, the long carbon chain type coupling agent is difficult to separate in the polymerization process, and the pressure rise is obvious in the filter pressing value test.
Claims (10)
1. A nano zinc oxide dispersion liquid for polyester in-situ polymerization is characterized by comprising the following components: nano zinc oxide, glycol, a compound modifier, a stabilizer and a dispersion aid agent;
the compound modifier comprises a long carbon chain type coupling agent and a coupling agent containing a reaction group; the long carbon chain type coupling agent contains at least one alkyl chain with more than C6; the coupling agent containing the reactive group contains one or more of amino, epoxy and mercapto.
2. The nano zinc oxide dispersion liquid for polyester in-situ polymerization according to claim 1, wherein the mass ratio of the long carbon chain type coupling agent to the coupling agent containing a reaction group in the compound modifier is 0.2-5:1; the total mass of the compound modifier is 0.5-5% of the mass of the nano zinc oxide.
3. The nano zinc oxide dispersion liquid for in-situ polymerization of polyester according to claim 1 or 2, wherein the long carbon chain coupling agent is selected from one or more of isopropoxytris (dioctyl pyrophosphoyloxy) titanate, isopropoxytrionoyloxy titanate, propoxytitanium tristearate, isopropoxytris (dodecylbenzenesulfonyloxy) titanate, octadecyltrimethoxysilane and hexadecyltrimethoxysilane;
the coupling agent containing the reactive group is selected from one or more of isopropyl tri (ethylenediamine-N-ethoxy) titanate, 3-aminopropyl triethoxysilane, N-2-aminoethyl-3-aminopropyl triethoxysilane, 3-glycidol ether oxypropyl triethoxysilane and 3-mercaptopropyl triethoxysilane.
4. The nano zinc oxide dispersion liquid for in-situ polymerization of polyester according to claim 1, wherein the stabilizer is one or more selected from trimethyl phosphate, triethyl phosphate, triphenyl phosphate and triethyl phosphate; the mass of the stabilizer is 0.005-0.02% of the mass of the nano zinc oxide.
5. The nano zinc oxide dispersion liquid for in situ polymerization of polyester according to claim 1, wherein the dispersion aid agent comprises a first dispersion aid agent and a second dispersion aid agent;
the first dispersing aid agent is polyethylene glycol with molecular weight lower than 1000 and/or polyvinylpyrrolidone with molecular weight higher than 58000; the mass of the first auxiliary dispersing agent is 0.3-5% of the mass of the nano zinc oxide;
the second dispersing aid is sodium polyacrylate and/or sodium hexametaphosphate; the mass of the second auxiliary dispersing agent is 0.25-1% of the mass of the nano zinc oxide.
6. The nano zinc oxide dispersion liquid for polyester in-situ polymerization according to claim 1, wherein the mass concentration of nano zinc oxide in the dispersion liquid is less than 15%.
7. A method for preparing the nano zinc oxide dispersion liquid for polyester in-situ polymerization according to any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) Mixing nano zinc oxide with ethylene glycol, adding a dispersing aid agent, and grinding until the particle size D99 of the zinc oxide is smaller than 3 mu m to obtain an initial dispersion;
(2) Adjusting the pH value of the initial dispersion liquid to 10-12, and dripping a compound modifier for modification reaction;
(3) Adding a stabilizer and a dispersing aid to the dispersion liquid after the modification reaction, and grinding again until the particle size of zinc oxide is smaller than 1 mu m to obtain the nano zinc oxide dispersion liquid for polyester in-situ polymerization.
8. The method of claim 7, wherein the dispersion aid agent added in step (1) is a first dispersion aid agent, and the dispersion aid agent added in step (3) is a second dispersion aid agent.
9. The method according to claim 7, wherein the pH adjustor used in the step (2) is one or more of ammonia water, triethanolamine, an organic amine, and sodium hydroxide; the modification reaction temperature is 50-120 ℃.
10. The method according to claim 7, wherein the particle size of the beads used in the polishing in the step (1) and the step (3) is 0.3 to 0.6. Mu.m, and the polishing temperature is lower than 40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310173599.8A CN116355280A (en) | 2023-02-28 | 2023-02-28 | Nano zinc oxide dispersion liquid for polyester in-situ polymerization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310173599.8A CN116355280A (en) | 2023-02-28 | 2023-02-28 | Nano zinc oxide dispersion liquid for polyester in-situ polymerization and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116355280A true CN116355280A (en) | 2023-06-30 |
Family
ID=86917894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310173599.8A Pending CN116355280A (en) | 2023-02-28 | 2023-02-28 | Nano zinc oxide dispersion liquid for polyester in-situ polymerization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116355280A (en) |
-
2023
- 2023-02-28 CN CN202310173599.8A patent/CN116355280A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109295532B (en) | Antibacterial composite functional fiber and preparation method thereof | |
| CN105694438A (en) | Nano inorganic antibacterial fiber masterbatch and preparation method thereof | |
| US6699316B2 (en) | Process for the preparation of nano-zinc oxide dispersions stabilized by hydroxyl group-containing inorganic polymers | |
| Luo et al. | Preparation of silica nanoparticles using silicon tetrachloride for reinforcement of PU | |
| CN110713820B (en) | Preparation method of hydrophobic modified diamond abrasive | |
| CN102040868B (en) | Method for preparation and surface modification of alkaline silicon sol | |
| WO2009077412A2 (en) | Aqueous slurry comprising inorganic oxygen-containing particulates | |
| CN116288768B (en) | Far infrared anion antibacterial anti-mite health care multifunctional fiber and preparation and application thereof | |
| CN111748084A (en) | Antibacterial flame-retardant polyester resin and preparation method thereof | |
| KR101327922B1 (en) | Organized ultra-fine aluminum hydroxide and preparation method thereof | |
| KR101753606B1 (en) | Surface-modified crystalline metal oxide and method for preparing the same | |
| CN1887716A (en) | Monodisperse micron level spherical vaterite-type calcium carbonate and its prepn process | |
| CN116355280A (en) | Nano zinc oxide dispersion liquid for polyester in-situ polymerization and preparation method thereof | |
| KR100969132B1 (en) | Method for preparing cerium carbonate powder using urea | |
| CN112442745B (en) | Polyester with temperature response anion release antibacterial function and preparation method of fiber thereof | |
| CN107723833B (en) | Preparation method of α -nano-alumina modified polyester fiber | |
| CN1291991C (en) | Preparation method of multihydroxy sesqui siloxane | |
| CN112391003A (en) | Special resin with antibacterial property for polyethylene pipe and preparation method thereof | |
| CN1704452A (en) | Process for preparing nano silicon dioxide particles | |
| CN107936619A (en) | A kind of composite titanium dioxide and its manufacture method | |
| CN111073354A (en) | Method for modifying ultra-dispersion of rubber filler nano white carbon black | |
| CN101423624B (en) | Miniaturization organic phoshate nucleating agent and preparation method thereof | |
| CN111943217A (en) | Preparation method of ultrafine wollastonite with high length-diameter ratio | |
| CN112552708A (en) | Dispersible barium sulfate composite powder for water-based paint and preparation method thereof | |
| CN108971516B (en) | Platinum nano-particles and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |