CN115232313A - Preparation method of siloxane end-capped coated anti-dripping agent - Google Patents
Preparation method of siloxane end-capped coated anti-dripping agent Download PDFInfo
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- CN115232313A CN115232313A CN202210933992.8A CN202210933992A CN115232313A CN 115232313 A CN115232313 A CN 115232313A CN 202210933992 A CN202210933992 A CN 202210933992A CN 115232313 A CN115232313 A CN 115232313A
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- siloxane
- dripping
- dripping agent
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 52
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 48
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 48
- 239000000839 emulsion Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001694 spray drying Methods 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000012467 final product Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- SNQUFRZGWGOGEY-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(OCC)(OCC)OCC)O[Si](OCC)(OCC)C Chemical compound C1(=CC=CC=C1)C(C(OCC)(OCC)OCC)O[Si](OCC)(OCC)C SNQUFRZGWGOGEY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a preparation method of a siloxane end-capped coated anti-dripping agent. Uniformly stirring and mixing the coated siloxane monomer and the organic solvent A in a reactor in advance, dropwise adding an acidic catalyst solution or an alkaline catalyst solution, uniformly stirring, heating to 40-100 ℃, slowly dropwise adding a polytetrafluoroethylene emulsion, and uniformly stirring and mixing; stirring and mixing the end-capped siloxane monomer and the organic solvent B uniformly in advance, slowly dripping the mixture into the solution, adding deionized water after dripping, uniformly stirring the mixture to perform hydrolysis-dehydration condensation reaction for 0.5 to 2 hours, and carrying out end-capping treatment to obtain a product; filtering, washing and drying the product to obtain the siloxane end-capped coated anti-dripping agent; distilling the filtrate to recover organic solvent, and drying to recover emulsifier powder. The anti-dripping agent prepared by the invention improves the heat resistance of the resin; the dispersion in resin is extremely high, and the processability is very excellent; the anti-dripping agent provided by the invention can be recovered as a byproduct, and is environment-friendly and pollution-free.
Description
Technical Field
The invention relates to the technical field of anti-dripping agents, in particular to a preparation method of a siloxane end-capped coated anti-dripping agent.
Background
The plastic material has the characteristics of light weight, convenient manufacture, easy dyeing and convenient large-scale production, is widely applied to various environments such as families, offices, factories, public facilities and the like at present, and is particularly used as engineering plastics for manufacturing articles such as electronics, electric appliances, automobiles, communication, tools, toys, office test equipment and the like. The plastic material is inflammable and is easily softened and deformed by itself and even dropped.
In order to improve the anti-dripping property of the plastic material, an anti-dripping agent is usually added into the plastic material to improve the flame retardant anti-dripping property of the plastic material during burning. Recently, a fluorinated resin having a tendency to fibrillate has been mainly used as an anti-dripping agent, and various attempts have been made to improve the anti-dripping property of a synthetic resin by using a fluorinated polymer.
U.S. patents disclose the addition of pure polytetrafluoroethylene particles as an anti-drip agent to synthetic resin PC/ABS alloys to improve flame retardance and anti-drip performance. However, the dispersibility of the pure polytetrafluoroethylene anti-dripping agent particles is poor, which causes inconvenience in addition operation, surface defects during molding, and a decrease in mechanical strength of the molded article.
In order to improve the dispersibility of polytetrafluoroethylene anti-dripping agent particles, attempts have been made in the art to improve the surface properties of polytetrafluoroethylene particles by forming a surface coating layer thereon. For example, chinese patent CN02805583 discloses that hard polymer particles with fine particle size can be used as a separant to wrap polytetrafluoroethylene resin with coarser particle size, and the dispersion performance of polytetrafluoroethylene can be improved by simple physical blending and mixture extrusion granulation, but the fiber forming performance and the capability of solving surface defects are limited. EPA0166187 discloses a powder mixture of a polytetrafluoroethylene emulsion co-precipitated with an acrylonitrile-styrene emulsion to coagulate, the polytetrafluoroethylene content being low, not more than 25%, and being susceptible to blocking.
Chinese patent No. CN96105649.5 discloses a method for free radical emulsion polymerization of acrylonitrile-styrene in the presence of polytetrafluoroethylene emulsion, the obtained product has the defect of easy adhesion, and the content of polytetrafluoroethylene in the obtained product is low, not more than 50%.
U.S. Pat. No. 6,69072,1 discloses a method of adding polycarbonate solution to polytetrafluoroethylene emulsion and then spray drying to obtain core-shell structure anti-dripping agent with polytetrafluoroethylene content of 30%. The product has low polytetrafluoroethylene content and can only be used in polycarbonate.
Therefore, the existing polytetrafluoroethylene anti-dripping agent still has the defects of low polytetrafluoroethylene content and poor dispersibility. The plastic material product added with the polytetrafluoroethylene anti-dripping agent has the problems of surface defects, silver wires, pockmarks, broken strips and low anti-dripping property.
Aiming at the defects in the prior art, the preparation method of the siloxane end-capped coated anti-dripping agent is necessarily provided, the processing and production process is simple, and the whole production process is environment-friendly and pollution-free; in the anti-dripping agent prepared by the method, the polytetrafluoroethylene can be uniformly distributed in the plastic, and the anti-dripping agent has the advantages of improving heat resistance and surface gloss of products, along with high whiteness, finer particle size and better processing performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a siloxane end-capped coated anti-dripping agent.
A preparation method of a siloxane end-capped coated anti-dripping agent comprises the following steps:
(1) Uniformly stirring and mixing the coated siloxane monomer and the organic solvent A in a reactor in advance, dropwise adding an acidic catalyst solution or an alkaline catalyst solution, uniformly stirring, heating to 40-100 ℃, slowly dropwise adding a polytetrafluoroethylene emulsion, and uniformly stirring and mixing;
(2) Uniformly stirring and mixing a terminated siloxane monomer and an organic solvent B in advance, slowly dripping the mixture into the solution, adding deionized water after dripping, uniformly stirring the mixture to perform hydrolysis-dehydration condensation reaction for 0.5 to 2 hours, and carrying out terminated treatment to obtain a product;
(3) Filtering, washing and drying the product to obtain the siloxane end-capped coated anti-dripping agent; distilling the filtrate to recover organic solvent, and spray drying to recover emulsifier powder.
In the anti-dripping agent prepared by the method, the polytetrafluoroethylene can be uniformly distributed in the plastic, and the anti-dripping agent has the advantages of improving heat resistance, improving the surface gloss of products, high whiteness, finer particle size and better processing performance.
The dropping speed is intentionally controlled when the solution is dropped, so that the dropping speed is prevented from being too high, the reaction rate is accelerated, the reaction is violent and difficult to control, and the obtained siloxane end-capped coated anti-dropping agent has uneven particle size or influences the dispersibility of the polytetrafluoroethylene emulsion; meanwhile, after the polytetrafluoroethylene emulsion is added, the reaction is not needed for a period of time, and the end-capped siloxane monomer is immediately added, so that the uniformity of the particle size is also ensured.
Preferably, the coating siloxane monomer is selected from one or a mixture of several of D, T and Q type monomers forming a silicon resin structural unit.
As structural units of the silicone resin, M represents monofunctional structural units, i.e., only one siloxane bond can be hydrolyzed, and the structural unit is represented by R 3 SiO 1/2 D represents a bifunctional structural unit with the expression R 2 SiO, T represents a structural unit with 3 functionality, and the expression is RSi 3/2 Q represents a structural unit with a functionality of 4 and is expressed as SiO 2 The coating efficiency of the coating silicone resin by selecting T and Q is higher, because the hydroxyl content of the product with multiple functionality is high after hydrolysis; the class D silicone is selected from: diphenyldiethoxysilane, dimethyldiethoxysilane; the T-type silicone resin is selected from: phenyltriethoxy, methyltriethoxysilane, methylphenyldiethoxysilane; the Q-type silicon resin is selected from tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane.
Preferably, the organic solvent A is one or a mixture of several of diethyl ether, toluene, ethanol, acetone, isopropanol and glycerol; the organic solvent B is one or more of methanol, ethanol, isopropanol, glycerol, acetone, benzene, toluene and xylene.
Since the coated siloxane monomer and the end-capped siloxane monomer are different in solubility in different organic solvents, it is necessary to select an organic solvent or a mixed solution of organic solvents that can dissolve the coated siloxane monomer and the end-capped siloxane monomer well.
Preferably, the ratio of the organic solvent A to the coating siloxane monomer is 3.
Preferably, the acidic catalyst solution is one or a mixture of more of acidic solution HCl, H2SO4 and HNO 3; the alkaline catalyst solution is one or more of alkaline catalysts such as NaOH, KOH, ammonia water and K2CO 3.
As an improvement of the siloxane end-capping coated anti-dripping agent, a coated siloxane monomer and an organic solvent A are added into a reactor, and the reactor is ensured to be in a dry state before an acidic catalyst solution or a basic catalyst solution is dripped; meanwhile, when the acidic catalyst solution is selected, the corrosion resistance of the reactor needs to be considered, so that the influence on the reaction effect caused by the corrosion of the acidic catalyst solution on the reactor is avoided.
Preferably, under the condition of the acidic catalyst solution, the pH value is controlled to be 1-5; under the condition of the alkaline catalyst solution, the pH value is controlled to be 9-11.
The catalysis principle of the alkaline catalyst solution is that free hydroxyl negative ions carry out nucleophilic substitution on silicon atoms, and the catalysis principle of the acidic catalyst is that hydrogen positive ions firstly occupy empty orbitals of oxygen atoms in siloxane and then silicon hydroxyl carries out nucleophilic substitution on the silicon atoms; the alkaline catalyst solution or the acidic catalyst solution can accelerate the reaction rate, the reaction rate of dripping the alkaline catalyst solution is less than that of dripping the acidic catalyst solution, the particle size of the siloxane end-capped coated anti-dripping agent generated by the reaction is different, and the particle size of the product obtained by dripping the alkaline catalyst solution for reaction is uniform.
Preferably, the weight ratio of the polytetrafluoroethylene emulsion to the coating siloxane monomer is 10.
Preferably, the end-capping siloxane monomer is one or a mixture of M, D and T type monomers which form a structural unit of the silicone resin. The M-type silicone resin is selected from: triphenylethoxysilane, trimethylethoxysilane, hexamethyldisiloxane; the T-type silicon resin adopts methyl triethoxysilane; the D-type silicon resin is diphenyl diethoxy silane. The choice of capping treatment to choose M, D is better because the less the capping functionality, the more thorough the capping.
Preferably, the ratio of the organic solvent B to the end-capping siloxane monomer is 3.
As an improvement of the siloxane end-capping coated anti-dripping agent, the polytetrafluoroethylene emulsion is prepared by an emulsion polymerization method or a water phase method, and the solid content of the polytetrafluoroethylene emulsion is 30-70 percent.
As an improvement of the siloxane end-capped coated anti-dripping agent, the polytetrafluoroethylene emulsion with large molecular weight can play a role of preventing dripping, the molecular weight of the polytetrafluoroethylene emulsion is 200-500 ten thousand, and the polytetrafluoroethylene emulsion with small molecular weight reduces the friction coefficient of the surface of the material, improves the abrasion resistance of the material and effectively plays a role of demoulding.
As an improvement of the siloxane end-capped coated anti-dripping agent, the polytetrafluoroethylene emulsion is slowly dripped into the siloxane monomer in the invention, so that the siloxane monomer and the polytetrafluoroethylene emulsion are combined with each other through hydrolysis-dehydration condensation to form a tight combination, and a stable condensation compound is formed, thereby realizing the complementation of the performance or the function of the components; the formed condensation compound also has the characteristic of good processing performance; in addition, the invention utilizes the dispersibility of the siloxane monomer to improve the uniform dispersion of the polytetrafluoroethylene emulsion in the plastic material and help the thermoplastic material to reach higher flame retardant standard; the siloxane structure coated on the outer layer of the anti-dripping agent can greatly improve the temperature resistance of the resin material of the matrix.
As an improvement of the siloxane end-capping coated anti-dripping agent, the adopted organic solvent and the generated organic matters are all recyclable, and according to the structures of different siloxane monomers, if the siloxane monomers contain methoxyl groups, methanol is finally generated by reaction, if the siloxane monomers contain ethoxyl groups, ethanol is finally generated by reaction, the organic solvents with different boiling points are respectively recycled by high-temperature reduced pressure distillation by utilizing the difference of the volatility of components in a liquid mixture, namely, the organic solvents with different boiling points are different under the reduced pressure condition, in addition, the emulsifier powder is recycled after water is evaporated by a spray drying device, and the whole preparation reaction process is green and environment-friendly.
The obtained siloxane end-capped coated anti-dripping agent can be subjected to melt blending granulation with a plastic material through a double screw, and high molecular weight polytetrafluoroethylene is fibrillated to form a net structure, so that a granulated product is obtained and is injected into a sample, the anti-dripping performance of resin is greatly improved, an injection molding product does not wrinkle, a black-white product has no crystal point, and the surface gloss is improved.
The invention has the following beneficial technical effects: coating the siloxane monomer on the surface of the polytetrafluoroethylene emulsion in a specific acidic or alkaline reaction environment by adopting a hydrolytic condensation method to prepare a siloxane end-capped coated anti-dripping agent; the siloxane end-capped coated anti-dripping agent has good compatibility and dispersibility when being applied to flame-retardant plastic materials; the coating of the siloxane structure has excellent processing performance on the material, greatly improves the heat resistance, and has good optical performance on the surface of the material; the siloxane end-capped coated anti-dripping agent has high whiteness, finer particle size and better processing performance; the production process is simple, the cost is low, the production efficiency is high, the by-product can be recycled, the whole production process is environment-friendly and pollution-free, and the method can be used for large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
Preparation of siloxane end-capped coated anti-dripping agent:
(1) Weighing 120g to 150g of toluene, 30g to 40g of diphenyl diethoxy silane and 30g to 40g of phenyl triethoxy silane, uniformly mixing the materials in a dry reactor, dripping hydrochloric acid to ensure that the reaction environment is in a state of pH value =4, immediately heating the reactor, controlling the reaction temperature to be 90 +/-2 ℃, and slowly dripping 50g to 100g of polytetrafluoroethylene emulsion.
(2) Immediately dropwise adding 15 g-30 g of triphenyl ethoxysilane and 10 g-15 g of toluene mixed solution after the polytetrafluoroethylene emulsion is dropwise added, slowly dropwise adding 200 g-300 g of deionized water, and performing co-hydrolysis-dehydration condensation at 90 ℃ for 30-40 minutes to perform end-capping treatment to obtain a reaction product;
(3) Filtering the reaction product by using a common filter screen to obtain a final product and a filtrate; and (3) after washing the final product by using a certain amount of deionized water, drying the final product by using spray drying equipment to obtain the siloxane end-capped coated anti-dripping agent.
(4) Recovering solvent such as toluene and ethanol from the filtrate by vacuum distillation recovery device, and recovering emulsifier powder by spray drying recovery device.
Example 2
(1) Weighing 150 g-180 g of acetone, 15 g-30 g of dimethyldiethoxysilane and 15 g-30 g of methyltriethoxysilane, uniformly mixing in a dry reactor, dripping KOH to ensure that the reaction environment is in a state of pH value =10, immediately heating the reactor, controlling the reaction temperature to be 50 +/-2 ℃, and slowly dripping 100 g-200 g of polytetrafluoroethylene emulsion.
(2) Immediately dropwise adding 10-30 g of trimethylethoxysilane and 10-15 g of acetone mixed solution after the polytetrafluoroethylene emulsion is dropwise added, slowly dropwise adding 200-300 g of deionized water, and performing co-hydrolysis-dehydration condensation at 50 ℃ for 50 minutes to perform end-capping treatment to obtain a reaction product;
(3) Filtering the reaction product by using a common filter screen to obtain a final product and a filtrate; and (3) washing the final product by using a certain amount of deionized water, and drying the final product by using spray drying equipment to obtain the siloxane end-capped coated anti-dripping agent.
(4) Recovering solvent such as acetone and ethanol from the filtrate by vacuum distillation recovery device, and recovering emulsifier powder by spray drying recovery device.
Example 3
(1) Weighing 180 g-200 g of isopropanol, 30 g-40 g of methyl phenyl diethoxysilane and 30 g-50 g of methyl triethoxysilane, uniformly mixing in a dry reactor, dripping KOH to ensure that the reaction environment is in a state of pH value =10, immediately heating the reactor, controlling the reaction temperature to be 70 +/-2 ℃, and slowly dripping 200 g-300 g of polytetrafluoroethylene emulsion.
(2) Immediately dropwise adding a mixed solution of 20g to 30g of methyltriethoxysilane and 15g to 20g of isopropanol after the polytetrafluoroethylene emulsion is dropwise added, slowly adding 200g to 300g of deionized water after the polytetrafluoroethylene emulsion is dropwise added, and carrying out co-hydrolysis-dehydration condensation for 50 minutes at 70 ℃ to carry out end-capping treatment to obtain a reaction product;
(3) Filtering the reaction product by using a common filter screen to obtain a final product and a filtrate; and (3) after washing the final product by using a certain amount of deionized water, drying the final product by using spray drying equipment to obtain the siloxane end-capped coated anti-dripping agent.
(4) Recovering solvent such as isopropanol and ethanol from the filtrate by vacuum distillation recovery device, and recovering emulsifier powder by spray drying recovery device.
Example 4
(1) Weighing 120g to 150g of ethanol and 60g to 80g of tetramethoxysilane, uniformly mixing the ethanol and the tetramethoxysilane in a dry reactor, dripping hydrochloric acid to ensure that the reaction environment is in a state of pH value =4, immediately heating the reactor, controlling the reaction temperature to be 50 +/-2 ℃, and slowly dripping 50g to 100g of polytetrafluoroethylene emulsion.
(2) Immediately dropwise adding 15 g-30 g of trimethylethoxysilane and 10 g-15 g of ethanol mixed solution after the polytetrafluoroethylene emulsion is dropwise added, slowly adding 200 g-300 g of deionized water after dropwise adding is finished, and carrying out co-hydrolysis-dehydration condensation at 50 ℃ for 30-40 minutes to carry out end-capping treatment to obtain a reaction product;
(3) Filtering the reaction product by using a common filter screen to obtain a final product and a filtrate; and (3) after washing the final product by using a certain amount of deionized water, drying the final product by using spray drying equipment to obtain the siloxane end-capped coated anti-dripping agent.
(4) Recovering solvent such as methanol and ethanol from the filtrate by vacuum distillation recovery device, and recovering emulsifier powder by spray drying recovery device.
Example 5
(1) Firstly weighing 120 g-150 g of ethanol and 60 g-80 g of tetramethoxysilane, mixing uniformly in a dry reactor, dripping ammonia water to ensure that the reaction environment is in a state of pH value =10, immediately heating the reactor, controlling the reaction temperature to be 50 +/-2 ℃, and slowly dripping 50 g-100 g of polytetrafluoroethylene emulsion.
(2) Immediately dropwise adding 15 g-30 g of mixed solution of hexamethyldisiloxane and 10 g-15 g of ethanol after the polytetrafluoroethylene emulsion is dropwise added, slowly dropwise adding 200 g-300 g of deionized water, and performing co-hydrolysis-dehydration condensation at 50 ℃ for 30-40 minutes to perform end-capping treatment to obtain a reaction product;
(3) Filtering the reaction product by using a common filter screen to obtain a final product and a filtrate; and (3) after washing the final product by using a certain amount of deionized water, drying the final product by using spray drying equipment to obtain the siloxane end-capped coated anti-dripping agent.
(4) Recovering solvent such as methanol and ethanol from the filtrate by vacuum distillation recovery device, and recovering emulsifier powder by spray drying recovery device.
Example 6
(1) Firstly weighing 40g to 60g of ethanol and 80g to 120g of glycerol, mixing the ethanol and 60g to 80g of tetramethoxysilane uniformly in a dry reactor, dripping ammonia water to ensure that the reaction environment is in a state of pH value =10, immediately heating the reactor, controlling the reaction temperature to be 50 +/-2 ℃, and slowly dripping 50g to 100g of polytetrafluoroethylene emulsion.
(2) Immediately dropwise adding 15 g-30 g of diphenyl diethoxy silane and 10 g-15 g of ethanol mixed solution after the polytetrafluoroethylene emulsion is dropwise added, slowly dropwise adding 200 g-300 g of deionized water, and performing co-hydrolysis-dehydration condensation at 50 ℃ for 30-40 minutes to perform end-capping treatment to obtain a reaction product;
(3) Filtering the reaction product by using a common filter screen to obtain a final product and a filtrate; and (3) after washing the final product by using a certain amount of deionized water, drying the final product by using spray drying equipment to obtain the siloxane end-capped coated anti-dripping agent.
(4) Recovering solvent such as methanol, ethanol, glycerol, etc. from the filtrate by vacuum distillation recovery device, and recovering emulsifier powder by spray drying recovery device.
Performance test
By the methods of the above examples 1, 2, 3, 4, 5 and 6, the silicon-fluorine coated high-gloss anti-dripping agent can be prepared, and the anti-dripping agent is applied to the flame-retardant plastic material as follows:
the silicon-fluorine coated high gloss anti-dripping agent prepared in each of examples 1 to 6 was melt-granulated with PC resin in a twin screw extruder at a ratio of 0.3%.
In order to further illustrate the excellent performance of the anti-dripping agent, a PC resin granulation product added with the anti-dripping agent, a PC granulation product added with a common anti-dripping agent and a PC resin without the anti-dripping agent are subjected to water-cooling drawing granulation on a double-screw granulator, and then are subjected to injection molding on an injection molding machine at a proper temperature to prepare a sample strip to be tested. And testing the horizontal and vertical combustion of the injection molded sample strip, testing the flame retardant property of the product, testing the processing property in the processing process and testing the surface gloss of the product by a gloss meter. The test effect is shown in table 1 below.
TABLE 1 Performance test Table
By combining the performance test tables of examples 1 to 6, comparative examples 1 to 2 and table 1, comparison can be found that:
the PC resin added with the siloxane end-capped coated anti-dripping agent prepared by any one embodiment of the invention has the advantages of best anti-dripping performance, high glossiness and most stable and uniform grain extraction in processing.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of siloxane end-capped coated anti-dripping agent is characterized by comprising the following steps: the method comprises the following steps:
(1) Stirring and mixing the coated siloxane monomer and the organic solvent A uniformly in a reactor in advance, dripping an acidic catalyst solution or a basic catalyst solution, uniformly stirring, heating to 40-100 ℃, slowly dripping a polytetrafluoroethylene emulsion, and uniformly stirring and mixing;
(2) Stirring and mixing the end-capped siloxane monomer and the organic solvent B uniformly in advance, slowly dripping the mixture into the solution, adding deionized water after dripping, uniformly stirring the mixture to perform hydrolysis-dehydration condensation reaction for 0.5 to 2 hours, and carrying out end-capping treatment to obtain a product;
(3) Filtering, washing and drying the product to obtain the siloxane end-capped coated anti-dripping agent; distilling the filtrate to recover organic solvent, and spray drying to recover emulsifier powder.
2. The method for preparing the siloxane-terminated coated anti-dripping agent according to claim 1, wherein the method comprises the following steps: the coating siloxane monomer is selected from one or a mixture of several D, T and Q type monomers forming a silicon resin structural unit.
3. The method for preparing the siloxane-terminated coated anti-dripping agent according to claim 1, wherein the method comprises the following steps: the organic solvent A is one or more of mixed solution of diethyl ether, toluene, ethanol, acetone, isopropanol and glycerol; the organic solvent B is one or more of methanol, ethanol, isopropanol, glycerol, acetone, benzene, toluene and xylene.
4. The method for preparing the siloxane-terminated coated anti-dripping agent according to claim 1, wherein the method comprises the following steps: the ratio of the organic solvent A to the coating siloxane monomer is 3.
5. The method for preparing the siloxane-terminated coated anti-dripping agent according to claim 1, wherein the method comprises the following steps: the acidic catalyst solution is one or a mixture of more of acidic solution HCl, H2SO4 and HNO 3; the alkaline catalyst solution is one or a mixture of more of alkaline catalysts such as NaOH, KOH, ammonia water and K2CO 3.
6. The method for preparing the siloxane-terminated coated anti-dripping agent according to claim 1, wherein the method comprises the following steps: under the condition of the acidic catalyst solution, the pH value is controlled to be 1-5; under the condition of the alkaline catalyst solution, the pH value is controlled to be 9-11.
7. The method for preparing the siloxane end-capping coated anti-dripping agent according to claim 1, characterized in that: the weight ratio of the polytetrafluoroethylene emulsion to the coating siloxane monomer is 10.
8. The method for preparing the siloxane-terminated coated anti-dripping agent according to claim 1, wherein the method comprises the following steps: the end-capped siloxane monomer is selected from one or a mixture of M, D and T type monomers forming a silicon resin structural unit.
9. The method for preparing the siloxane-terminated coated anti-dripping agent according to claim 1, wherein the method comprises the following steps: the ratio of the organic solvent B to the end-capped siloxane monomer is 3: 3.
10. a siloxane-terminated coated anti-drip agent obtained by the method of any one of claims 1 to 9.
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