CN114292368A - Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof - Google Patents
Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN114292368A CN114292368A CN202210095462.0A CN202210095462A CN114292368A CN 114292368 A CN114292368 A CN 114292368A CN 202210095462 A CN202210095462 A CN 202210095462A CN 114292368 A CN114292368 A CN 114292368A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphorus
- core
- containing acrylate
- organosilicon
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides an organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant and a preparation method thereof, belonging to the technical field of flame retardant design and synthesis. The organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant is prepared by taking octamethylcyclotetrasiloxane as a core layer (D4), KH570 as a cross-linking agent and diethyl methyl phosphonate acrylate (DEAMP) and DOPO acrylate as shell layers through an emulsion polymerization method. The toughening flame retardant prepared by the invention has double functions of a core-shell elastomer and a macromolecular flame retardant, and the glass transition temperature of a rubber phase is far lower than room temperature; the flame retardant has high phosphorus content and P-Si synergistic flame retardant effect; good thermal stability, the initial thermal decomposition temperature is higher than 360 ℃, the residual quality after decomposition is higher than 30%, and the like.
Description
Technical Field
The invention relates to the technical field of flame retardant design and synthesis, in particular to an organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and a preparation method thereof.
Background
At present, in order to improve the defect that the toughness of a thermoplastic polymer material is damaged after flame retardation, a method of physically blending core-shell rubber (CSR) particles is often adopted for toughening. Such CSR particles are typically formed by emulsion polymerization, having a core layer of soft rubber and a harder shell layer of a plastic phase. Typical core materials include polybutyl acrylate, polybutadiene, acrylate-urethane, silicone, etc., and shell materials are usually polymethyl methacrylate, etc ((CN 202011164362.6; CN 202111200846.6; CN 202111052659.8; grandma. synthesis and application of large particle size core-shell polysiloxane-acrylate elastomer [ D ]. university of south china, 2017)). However, since CSR particle materials are all thermoplastic resins, which themselves are flammable, in use there is a risk of reducing the flame retardant properties of the material.
In order to ensure the flame retardant property and mechanical property of the flame retardant polymer material, the polysiloxane core-shell elastomer and the flame retardant can be selected to be compounded and applied to material blending modification, such as: compounding an organosilicon-acrylate core-shell polymer with APP to obtain synergistic flame retardant PA6 (Liuqingqing, organosilicon-acrylate core-shell polymer toughening and synergistic flame retardant PA6[ D ]. southern China university, 2019); flame retardant PC/ABS (von Wilsoniana. core-shell polysiloxane-acrylate elastomer preparation and toughened PC/ABS alloy research [ D ]. south China university of Arian 2015) compounded with bisphenol A bis (diphenyl phosphate) oligomer (BDP). The polysiloxane-acrylate elastomer can effectively improve the notch impact strength of the flame retardant material, and particularly has little influence on the flame retardant performance in a flame retardant system. However, the use of silicone-acrylate core shell polymers alone did not have a flame retardant effect.
Phosphorus-silicon elements have good synergistic flame-retardant effect, and the polymeric flame retardant containing silicon elements and phosphorus elements comprises the following components: a silicon-containing bicyclic caged phosphorothioate was used to synergistically flame-retard rigid polyurethane foam with kaolin (study of Liujuan. phosphorus-silicon synergistic flame-retardant polyurethane foam [ D ]. university of North China, 2017 ]); the synergistic flame-retardant effect of polyester type phosphorus-silicon halogen-free flame retardant and APP flame-retardant ethylene-vinyl acetate copolymer (Liangdein, Tangan, Lixiyun, Mahan ice, Xukanglin. phosphorus-silicon containing polymeric flame retardant and ammonium polyphosphate on EVA [ J ] Chinese plastics, 2011, 25(09):85-89.) has little influence on material mechanics, but can not improve the toughness of the material. Chinese patent publication No. CN113788947A reports that a linear organosilicon modified toughening agent is obtained by introducing phosphorus-containing groups into polysiloxane molecular chains and has the dual functions of flame retardance and toughening in epoxy resin. However, the organosilicon modified toughening agent has the defects of low phosphorus content and unobvious flame retardant effect when being used alone.
Disclosure of Invention
In view of the above, the invention takes octamethylcyclotetrasiloxane as a core layer (D4) through cationic ring-opening polymerization, KH-570 as a cross-linking agent, and diethyl methyl phosphonate acrylate (DEAMP) and DOPO acrylate as shell layers through radical polymerization from the perspective of molecular design, and prepares an organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant through an emulsion polymerization method, wherein the toughening flame retardant has both phosphorus-silicon coordinated flame retardant effect and polysiloxane toughening effect, and the glass transition temperature of a rubber phase is far lower than room temperature; the flame retardant has high phosphorus content and P-Si synergistic flame retardant effect; the thermal stability is good, the initial thermal decomposition temperature is higher than 360 ℃, the residual quality after decomposition is higher than 30%, and the flame retardant can be widely applied to toughening flame retardant modification of high polymer materials.
The first purpose of the invention is to provide an organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant which comprises the following components in parts by weight: 400-490 parts of octamethylcyclotetrasiloxane, 10-100 parts of cross-linking agent, 5-15 parts of emulsifier I, 50-100 parts of diethyl methylphosphonate acrylate, 100-250 parts of DOPO acrylate, 3-5 parts of emulsifier II and 3-5 parts of initiator.
Preferably, the crosslinking agent is gamma-methacryloxypropyltrimethoxysilane (KH-570) or vinyltrimethoxysilane (A-171), and the crosslinking agent may be other crosslinking agents commonly used in the art.
Preferably, the emulsifier I is sodium dodecyl sulfate in order to emulsify octamethylcyclotetrasiloxane monomers and ionize hydrogen ions to initiate ring-opening polymerization, and the emulsifier II is sodium dodecyl benzene sulfonate in order to emulsify DEAMP and DOPO acrylate monomers to form micelles.
Preferably, the initiator is potassium persulfate or ammonium persulfate, and the initiator may also be other initiators commonly used in the art.
The second purpose of the invention is to provide a preparation method of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant, which comprises the following steps:
(1) weighing raw materials according to a proportion, mixing and stirring octamethylcyclotetrasiloxane, a cross-linking agent, a part of emulsifier I and deionized water for pre-emulsification to obtain a pre-emulsion; the mass ratio of the emulsifier I to the deionized water is 1: 100;
(2) weighing 15-20 wt% of the pre-emulsion, adding the rest emulsifier I, stirring, heating to 80-85 ℃, and initiating polymerization;
(3) after blue light appears in the system, the residual pre-emulsion is dripped, and stirring is continued for 2.5-3.5 h after the dripping is finished, so that polysiloxane core emulsion is obtained;
(4) adjusting the pH value of the polysiloxane nuclear emulsion to 8-10 by using a NaOH solution to obtain an alkaline polysiloxane nuclear emulsion;
(5) mixing methyl phosphonic acid diethyl ester acrylate, DOPO acrylate and an emulsifier II, adding deionized water to prepare a mixed solution, stirring and pre-emulsifying, dropwise adding the mixed solution into an alkaline polysiloxane core emulsion, swelling for 5-10 min after dropwise adding, slowly dropwise adding an initiator, and continuously reacting for 3-4 h after dropwise adding to obtain polysiloxane-phosphorus-containing acrylate emulsion;
(6) adding CaCl with the mass concentration of 5-10% into the polysiloxane-phosphorus-containing acrylate emulsion in the step (5)2Demulsifying the aqueous solution to obtain a solid, and filtering, washing and drying to obtain a white powdery organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant.
Preferably, the stirring speed in the step (1) is 500-700 rpm, and the time is 0.3-0.5 h.
Preferably, the stirring speed in the step (2) is 180-200 rpm, and the stirring temperature is 80-85 ℃.
Preferably, the concentration of the NaOH solution in the step (4) is 2-5 wt%.
Preferably, the stirring speed in the step (5) is 180-200 rpm, and the stirring temperature is 75-80 ℃.
Preferably, the CaCl in step (6)2The adding amount of the aqueous solution is 2-5% of the volume of the polysiloxane-phosphorus-containing acrylate emulsion.
Compared with the prior art, the invention has the following beneficial effects: the toughening flame retardant provided by the invention has the structural characteristics of a core-shell elastomer and also has the function of a macromolecular flame retardant, the glass transition temperature of a core layer is-60 to-40 ℃, the glass transition temperature of a shell layer is 100 to 150 ℃, the initial thermal decomposition temperature is higher than 360 ℃, the residual quality after decomposition is higher than 30%, and the total heat release amount is lower than 43 kJ/g; the phosphorus content is high, and the P-Si synergistic flame retardant effect is achieved; high thermal stability and high residual quality after decomposition. The toughening flame retardant is expected to be used for flame retardance and toughening of flame retardant materials, and solves the problem of reduction of mechanical properties, especially impact toughness, of flame retardant materials.
Drawings
FIG. 1 is a TEM photograph of the core-shell toughened flame retardant of example 1;
FIG. 2 is a TGA curve of the core-shell toughening flame retardant of examples 1 to 3;
FIG. 3 is an MCC curve of the core-shell toughening agent of examples 1 to 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the starting materials and auxiliaries are, unless otherwise specified, obtained from customary commercial sources or prepared in customary manner.
The synthesis steps of the monomer of diethyl methylphosphonate acrylate (DEAMP) are as follows:
16.8g (0.1mol) of diethyl hydroxymethylphosphonate, 50mL of Dichloromethane (DCM) and 10.1g (0.1mol) of Triethanolamine (TEA) were added in sequence to a three-necked flask and reacted for 0.5h with stirring in a-5 ℃ ice salt bath. Then, 9g (0.1mol) of acryloyl chloride and 10mL of DCM are mixed uniformly and slowly dripped into a three-necked bottle, and after the dripping is finished, the temperature of the system is maintained at-5 ℃ for reaction for 1 h. Then the temperature is increased to 35 ℃ to react for 12 h. And after the reaction is finished, washing with water, and performing rotary evaporation to remove triethylamine salt, unreacted monomers and solvent to obtain orange yellow liquid. The ethyl acetate is taken as a mobile phase, purified by neutral silica gel column chromatography, and then removed by rotary evaporation to finally obtain light yellow DEAMP.
See also the invention patent of china with patent number "201910521898. X" a phosphorus-containing acrylate elastomer flame retardant and its preparation method "for preparing diethyl methylphosphonate acrylate (DEAMP).
The synthesis steps of the monomer DOPO acrylate monomer are as follows:
43.2324g (0.20mol) of DOPO and 100ml of ethanol are added into a three-necked flask provided with a constant pressure dropping funnel, a thermometer and a reflux condenser tube, after the temperature is raised to 60 ℃, 20.1303g of 37 percent formaldehyde aqueous solution is slowly dropped under magnetic stirring, and the dropping is finished within 30 min. Heating to 78 deg.C, refluxing for 5 hr, standing for cooling after reaction, filtering after solid is completely separated out, and drying in oven at 50 deg.C to obtain DOPO-CH2And (5) OH crude product. Then purifying the synthesized product by means of recrystallization and alcohol washing in sequence.
4.9440g (0.02mol) of DOPO-CH2OH, 20.00mL DCM, and 4.34mL (0.03mol) TEA were added sequentially to the three-necked flask and the electromagnetic stirring was turned on to dissolve them thoroughly. Then, 10mL of DCM solution containing 0.024mol of acryloyl chloride is added dropwise at the temperature below-10 ℃ within 45 min. Then the reaction was carried out at-5 ℃ for 12 hours, and the degree of reaction was determined by thin layer chromatography. After the reaction is completed, the triethylamine hydrochloride is removed by using deionized water for extraction, and then the solvent CH is removed by rotary evaporation2Cl2The product after solvent removal is purified by column chromatography (using ethyl acetate as mobile phase)Thus obtaining DOPO acrylate.
See also "Yan L, Liu J P, Zheng N, et al copolymerization of (10-oxo-10-hydro-9-oxa-10. lambda.)5-phospha-phenanthrene-10-yl)-methyl acrylate with styrene[J]Chinese Chemical Letters,2009,20: 881-.
Example 1
A preparation method of an organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant comprises the following steps:
(1) mixing 24.5g octamethylcyclotetrasiloxane (D4), 0.5g KH-570, 0.375g Sodium Dodecyl Sulfate (SDS) and 37.5mL deionized water, and pre-emulsifying at 600rpm for 0.5 h;
(2) adding 20% of pre-emulsion, 0.25g of SDS and 25mL of deionized water into a 250mL three-neck flask, heating the mixture in a constant-temperature water bath to 80 ℃ to initiate polymerization, and keeping the rotating speed at 180 rpm;
(3) dropwise adding the rest of pre-emulsion when blue light appears in the flask, stirring for reacting for 3h, and cooling to 25 ℃ to obtain polysiloxane core emulsion;
(4) adjusting the pH value of the polysiloxane core emulsion to 8 by using 3.0 wt% NaOH solution to obtain alkaline polysiloxane core emulsion;
(5) mixing 5g of diethyl methylphosphonate acrylate (DEAMP), 10g of DOPO acrylate, 0.15g of Sodium Dodecyl Benzene Sulfonate (SDBS) and 22.5ml of deionized water, pre-emulsifying for 0.5h at the stirring speed of 200rpm, then dropwise adding the mixture into the alkaline polysiloxane core emulsion, slowly dropwise adding 0.225g of potassium persulfate (KPS) after the dropwise adding is finished and swelling for 10 minutes, reacting for 3 hours after the dropwise adding is finished, cooling and discharging, and adding 3ml of CaCl with the concentration of 5 percent2Demulsifying the aqueous solution, filtering, washing with deionized water for multiple times, and drying to obtain the white powdery organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant.
The core-shell glass transition temperature of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared by the embodiment is-60 ℃ and the shell glass transition temperature is 110 ℃.
As shown in FIG. 1, the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared in example 1 has clear core-shell structure characteristics.
As shown in FIG. 2, the initial thermal decomposition temperature of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared in example 1 is higher than 360 ℃, and the thermal stability is good.
As can be seen from FIG. 3, the total heat release amount of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared in example 1 is 40.3KJ/g, which is much lower than that of a common commercial silicon-acrylic impact modifier S-2030 (provided by Mitsubishi Yang, Japan), and the flammability of the core-shell toughening agent is effectively reduced.
Example 2
A preparation method of an organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant comprises the following steps:
(1) 22g of octamethylcyclotetrasiloxane (D4), 3g of KH-570, 0.375g of Sodium Dodecyl Sulfate (SDS) and 37.5mL of deionized water were mixed and pre-emulsified for 0.5h at a stirring speed of 600 rpm;
(2) adding 20% of pre-emulsion, 0.25g of SDS and 25mL of deionized water into a 250mL three-neck flask, heating the mixture in a constant-temperature water bath to 80 ℃ to initiate polymerization, and keeping the rotating speed at 180 rpm;
(3) dropwise adding the rest of pre-emulsion when blue light appears in the flask, stirring for reacting for 3h, and cooling to 25 ℃ to obtain polysiloxane core emulsion;
(4) adjusting the pH value of the polysiloxane core emulsion to 8 by using 3.0 wt% NaOH solution to obtain alkaline polysiloxane core emulsion;
(5) mixing 5g of diethyl methylphosphonate acrylate (DEAMP), 10g of DOPO acrylate, 0.15g of Sodium Dodecyl Benzene Sulfonate (SDBS) and 22.5ml of deionized water, pre-emulsifying for 0.5h at the stirring speed of 200rpm, then dropwise adding the mixture into the alkaline polysiloxane core emulsion, slowly dropwise adding 0.225g of potassium persulfate (KPS) after the dropwise adding is finished and swelling for 10 minutes, reacting for 3 hours after the dropwise adding is finished, cooling and discharging, and adding 3ml of CaCl with the concentration of 5 percent2Demulsifying the aqueous solution, filtering, washing with deionized water for multiple times, and drying to obtain the white powdery organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant.
The core-shell toughening flame retardant of organosilicon-phosphorus-containing acrylate prepared in example 2 has a core-shell glass transition temperature of-53 ℃ and a shell glass transition temperature of 112 ℃.
As shown in FIG. 2, the initial thermal decomposition temperature of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared in example 2 is higher than 360 ℃, and the thermal stability is good.
As can be seen from FIG. 3, the total heat release amount of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared in example 2 is 42.8KJ/g, which is much lower than that of a common commercial silicon-propylene impact modifier S-2030, and the flammability of the core-shell toughening agent is effectively reduced.
Example 3
A preparation method of an organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant comprises the following steps:
(1) 20g of octamethylcyclotetrasiloxane (D4), 5g of KH-570, 0.375g of Sodium Dodecyl Sulfate (SDS) and 37.5mL of deionized water were mixed and pre-emulsified for 0.5h at a stirring speed of 600 rpm;
(2) adding 20% of pre-emulsion, 0.25g of SDS and 25mL of deionized water into a 250mL three-neck flask, heating the mixture in a constant-temperature water bath to 80 ℃ to initiate polymerization, and keeping the rotating speed at 180 rpm;
(3) dropwise adding the rest of pre-emulsion when blue light appears in the flask, stirring for reacting for 3h, and cooling to 25 ℃ to obtain polysiloxane core emulsion;
(4) adjusting the pH value of the polysiloxane core emulsion to 8 by using 3.0 wt% NaOH solution to obtain alkaline polysiloxane core emulsion;
(5) mixing 5g of diethyl methylphosphonate acrylate (DEAMP), 10g of DOPO acrylate, 0.15g of Sodium Dodecyl Benzene Sulfonate (SDBS) and 22.5ml of deionized water, pre-emulsifying for 0.5h at the stirring speed of 200rpm, then dropwise adding the mixture into the alkaline polysiloxane core emulsion, slowly dropwise adding 0.225g of potassium persulfate (KPS) after the dropwise adding is finished and swelling for 10 minutes, reacting for 3 hours after the dropwise adding is finished, cooling and discharging, and adding 3ml of CaCl with the concentration of 5 percent2Demulsifying the aqueous solution, filtering, washing with deionized water for multiple times, and drying to obtain the white powdery organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant.
The core-shell toughening flame retardant of organosilicon-phosphorus-containing acrylate prepared in example 3 has a core-shell glass transition temperature of-45 ℃ and a shell glass transition temperature of 123 ℃.
As shown in FIG. 2, the initial thermal decomposition temperature of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared in example 3 is higher than 360 ℃, and the thermal stability is good.
As can be seen from FIG. 3, the total heat release amount of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared in example 3 is 43.0KJ/g, which is much lower than that of the ordinary commercial silicon-propylene impact modifier S-2030, and the flammability of the core-shell toughening agent is effectively reduced.
Example 4
15g of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant prepared in examples 1-3 was weighed, mixed with polylactic acid (PLA), ammonium polyphosphate and cyclodextrin in the following weight parts, uniformly mixed in an extruder at 180 ℃, and injected at 180 ℃ to prepare standard combustion test and mechanical test samples.
As can be seen from the above table, the limiting oxygen index, tensile strength and elongation at break of the PLA added with the core-shell toughening flame retardant prepared in the embodiments 1-3 of the invention are greatly improved in various aspects compared with the PLA without the flame retardant.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant is characterized by comprising the following components in parts by weight: 400-490 parts of octamethylcyclotetrasiloxane, 10-100 parts of cross-linking agent, 5-15 parts of emulsifier I, 50-100 parts of diethyl methylphosphonate acrylate, 100 parts of DOPO acrylate, 3-5 parts of emulsifier II and 3-5 parts of initiator.
2. The organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant of claim 1, wherein the cross-linking agent is gamma-methacryloxypropyltrimethoxysilane or vinyltrimethoxysilane.
3. The organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant of claim 1, wherein the emulsifier I is sodium dodecyl sulfate, and the emulsifier II is sodium dodecyl benzene sulfonate.
4. The organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant of claim 1, wherein the initiator is potassium persulfate or ammonium persulfate.
5. The preparation method of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant according to claim 1, characterized by comprising the following steps:
(1) weighing raw materials according to a proportion, mixing and stirring octamethylcyclotetrasiloxane, a cross-linking agent, a part of emulsifier I and deionized water for pre-emulsification to obtain a pre-emulsion;
(2) weighing 15-20 wt% of the pre-emulsion, adding the rest emulsifier I, stirring, heating to 80-85 ℃, and initiating polymerization;
(3) after blue light appears in the system, the residual pre-emulsion is dripped, and stirring is continued for 2.5-3.5 h after the dripping is finished, so that polysiloxane core emulsion is obtained;
(4) regulating the pH value of the polysiloxane core emulsion to 8-10 by using a NaOH solution to obtain an alkaline polysiloxane core emulsion;
(5) mixing methyl phosphonic acid diethyl ester acrylate, DOPO acrylate and an emulsifier II, adding deionized water to prepare a mixed solution, stirring and pre-emulsifying, dropwise adding the mixed solution into an alkaline polysiloxane core emulsion, swelling for 5-10 min after dropwise adding, slowly dropwise adding an initiator, and continuously reacting for 3-4 h after dropwise adding to obtain polysiloxane-phosphorus-containing acrylate emulsion;
(6) adding CaCl with the mass concentration of 5-10% into the polysiloxane-phosphorus-containing acrylate emulsion in the step (5)2Demulsifying the aqueous solution to obtain a solid, and filtering, washing and drying to obtain a white powdery organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant.
6. The preparation method of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant according to claim 5, wherein the stirring speed in the step (1) is 500-700 rpm, and the time is 0.3-0.5 h.
7. The preparation method of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant according to claim 5, wherein the stirring speed in the step (2) is 180-200 rpm, and the stirring temperature is 80-85 ℃.
8. The preparation method of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant according to claim 5, wherein the concentration of the NaOH solution in the step (4) is 2-5 wt%.
9. The preparation method of the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant according to claim 5, wherein the stirring speed in the step (5) is 180-200 rpm, and the stirring temperature is 75-80 ℃.
10. The method for preparing the organosilicon-phosphorus-containing acrylate core-shell toughening flame retardant of claim 5, wherein the CaCl in the step (6)2The addition amount of the aqueous solution is 2-5% of the volume of the polysiloxane-phosphorus-containing acrylate emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210095462.0A CN114292368B (en) | 2022-01-26 | 2022-01-26 | Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210095462.0A CN114292368B (en) | 2022-01-26 | 2022-01-26 | Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114292368A true CN114292368A (en) | 2022-04-08 |
| CN114292368B CN114292368B (en) | 2023-04-11 |
Family
ID=80977248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210095462.0A Active CN114292368B (en) | 2022-01-26 | 2022-01-26 | Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114292368B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685943A (en) * | 2022-05-11 | 2022-07-01 | 泉州师范学院 | Preparation method of nano silicon rubber core-shell structure polymer toughened epoxy resin |
| CN114716798A (en) * | 2022-06-08 | 2022-07-08 | 河南源宏高分子新材料有限公司 | Environment-friendly flame-retardant transparent polyester material and preparation method thereof |
| CN114853959A (en) * | 2022-05-11 | 2022-08-05 | 泉州师范学院 | Preparation method of clean nano organosilicon core-shell toughening powder |
| CN115160509A (en) * | 2022-07-15 | 2022-10-11 | 吉祥三宝高科纺织有限公司 | Preparation method of core-shell particles with flame-retardant toughening function and polylactic acid material |
| CN115284703A (en) * | 2022-09-01 | 2022-11-04 | 山东博拓新材料科技股份有限公司 | Wide low-temperature impact-resistant bending-resistant PVC foamed co-extruded sheet and preparation method thereof |
| CN116355276A (en) * | 2023-02-17 | 2023-06-30 | 中国科学院宁波材料技术与工程研究所 | Halogen-free silica gel material with core-shell structure, preparation method and application |
| CN116854995A (en) * | 2023-05-30 | 2023-10-10 | 铨盛聚碳科技股份有限公司 | Preparation and application of organic coated SiO2 particles with flame retardant and toughening effects |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050234212A1 (en) * | 2002-07-01 | 2005-10-20 | Lieven Depuydt | Water-thinnable polymer precursors, their preparation and use |
| JP2013151642A (en) * | 2011-12-27 | 2013-08-08 | Hitachi Chemical Co Ltd | Liquid resin composition for electronic component, method of producing the liquid resin composition, and electronic component device |
| US20140187688A1 (en) * | 2012-12-28 | 2014-07-03 | Cheil Industries Inc. | (Meth)Acrylic Copolymer, Method for Preparing the Same and Thermoplastic Resin Composition Comprising the Same |
| CN105001264A (en) * | 2015-07-07 | 2015-10-28 | 苏州凯马化学科技有限责任公司 | Fire retardant, namely hydroxymethyl phosphine heterocyclic methylphosphonate compound, and preparation method therefor |
| US9187597B1 (en) * | 2014-10-21 | 2015-11-17 | International Business Machines Corporation | Flame-retardant polylactic acid (PLA) by grafting through of phosphorus-containing polymers directly to PLA backbone |
| CN106432332A (en) * | 2016-09-12 | 2017-02-22 | 华北理工大学 | Preparation method of phosphorus and nitrogen contained acrylate and copolymer core-shell particles of phosphorus and nitrogen contained acrylate |
| CN109293856A (en) * | 2018-09-11 | 2019-02-01 | 铨盛聚碳科技股份有限公司 | A kind of the organosilicon toughener and its synthetic method of polymer overmold nano-inorganic substance |
| CN110157133A (en) * | 2019-06-17 | 2019-08-23 | 华北理工大学 | A kind of phosphoric acrylic ester elastomer fire retardant and preparation method thereof |
| US20200002365A1 (en) * | 2018-06-28 | 2020-01-02 | Elite Electronic Material (Kunshan) Co., Ltd | Phosphorus-containing compound, phosphorus-containing flame retardant, preparation method thereof, and article made therefrom |
| CN113307916A (en) * | 2021-06-22 | 2021-08-27 | 普信氟硅新材料（衢州）有限公司 | Silsesquioxane modified acrylate flame-retardant toughening agent and preparation method thereof |
| US20210277239A1 (en) * | 2020-03-06 | 2021-09-09 | Nissin Chemical Industry Co., Ltd. | Emulsion composition, a coating agent and a laminate |
| CN113442537A (en) * | 2020-03-27 | 2021-09-28 | 味之素株式会社 | Resin sheet |
| WO2021254993A1 (en) * | 2020-06-17 | 2021-12-23 | Renolit Se | Flameproof acrylate |
-
2022
- 2022-01-26 CN CN202210095462.0A patent/CN114292368B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050234212A1 (en) * | 2002-07-01 | 2005-10-20 | Lieven Depuydt | Water-thinnable polymer precursors, their preparation and use |
| JP2013151642A (en) * | 2011-12-27 | 2013-08-08 | Hitachi Chemical Co Ltd | Liquid resin composition for electronic component, method of producing the liquid resin composition, and electronic component device |
| US20140187688A1 (en) * | 2012-12-28 | 2014-07-03 | Cheil Industries Inc. | (Meth)Acrylic Copolymer, Method for Preparing the Same and Thermoplastic Resin Composition Comprising the Same |
| US9187597B1 (en) * | 2014-10-21 | 2015-11-17 | International Business Machines Corporation | Flame-retardant polylactic acid (PLA) by grafting through of phosphorus-containing polymers directly to PLA backbone |
| CN105001264A (en) * | 2015-07-07 | 2015-10-28 | 苏州凯马化学科技有限责任公司 | Fire retardant, namely hydroxymethyl phosphine heterocyclic methylphosphonate compound, and preparation method therefor |
| CN106432332A (en) * | 2016-09-12 | 2017-02-22 | 华北理工大学 | Preparation method of phosphorus and nitrogen contained acrylate and copolymer core-shell particles of phosphorus and nitrogen contained acrylate |
| US20200002365A1 (en) * | 2018-06-28 | 2020-01-02 | Elite Electronic Material (Kunshan) Co., Ltd | Phosphorus-containing compound, phosphorus-containing flame retardant, preparation method thereof, and article made therefrom |
| CN109293856A (en) * | 2018-09-11 | 2019-02-01 | 铨盛聚碳科技股份有限公司 | A kind of the organosilicon toughener and its synthetic method of polymer overmold nano-inorganic substance |
| CN110157133A (en) * | 2019-06-17 | 2019-08-23 | 华北理工大学 | A kind of phosphoric acrylic ester elastomer fire retardant and preparation method thereof |
| US20210277239A1 (en) * | 2020-03-06 | 2021-09-09 | Nissin Chemical Industry Co., Ltd. | Emulsion composition, a coating agent and a laminate |
| CN113442537A (en) * | 2020-03-27 | 2021-09-28 | 味之素株式会社 | Resin sheet |
| WO2021254993A1 (en) * | 2020-06-17 | 2021-12-23 | Renolit Se | Flameproof acrylate |
| CN113307916A (en) * | 2021-06-22 | 2021-08-27 | 普信氟硅新材料（衢州）有限公司 | Silsesquioxane modified acrylate flame-retardant toughening agent and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LI YAN，等: "Copolymerization of(10-oxo-10-hydro-9-oxa-10λ5-phospha-phenanthrene-10-yl)-methyl acrylate with styrene" * |
| XIAOSHENG DU，等: "Preparation and characterization of flame-retardant nanoencapsulated phase change materials with poly(methylmethacrylate) shells for thermal energy storage" * |
| 汤仲标: "磷硅协同阻燃增强树脂的制备及其在汽车滤纸中的应用" * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685943A (en) * | 2022-05-11 | 2022-07-01 | 泉州师范学院 | Preparation method of nano silicon rubber core-shell structure polymer toughened epoxy resin |
| CN114853959A (en) * | 2022-05-11 | 2022-08-05 | 泉州师范学院 | Preparation method of clean nano organosilicon core-shell toughening powder |
| CN114685943B (en) * | 2022-05-11 | 2023-05-12 | 泉州师范学院 | Preparation method of nano silicone rubber core-shell structure polymer toughened epoxy resin |
| CN114853959B (en) * | 2022-05-11 | 2023-05-26 | 泉州师范学院 | Preparation method of clean nano organic silicon core-shell toughening powder |
| CN114716798A (en) * | 2022-06-08 | 2022-07-08 | 河南源宏高分子新材料有限公司 | Environment-friendly flame-retardant transparent polyester material and preparation method thereof |
| CN115160509A (en) * | 2022-07-15 | 2022-10-11 | 吉祥三宝高科纺织有限公司 | Preparation method of core-shell particles with flame-retardant toughening function and polylactic acid material |
| CN115284703A (en) * | 2022-09-01 | 2022-11-04 | 山东博拓新材料科技股份有限公司 | Wide low-temperature impact-resistant bending-resistant PVC foamed co-extruded sheet and preparation method thereof |
| CN115284703B (en) * | 2022-09-01 | 2023-10-24 | 山东博拓新材料科技股份有限公司 | Wide low-temperature impact-resistant bending-resistant PVC (polyvinyl chloride) foaming co-extrusion plate and preparation method thereof |
| CN116355276A (en) * | 2023-02-17 | 2023-06-30 | 中国科学院宁波材料技术与工程研究所 | Halogen-free silica gel material with core-shell structure, preparation method and application |
| CN116355276B (en) * | 2023-02-17 | 2023-11-03 | 中国科学院宁波材料技术与工程研究所 | Halogen-free silica gel material with core-shell structure, preparation method and application |
| CN116854995A (en) * | 2023-05-30 | 2023-10-10 | 铨盛聚碳科技股份有限公司 | Preparation and application of organic coated SiO2 particles with flame retardant and toughening effects |
| CN116854995B (en) * | 2023-05-30 | 2024-04-19 | 铨盛聚碳科技股份有限公司 | Preparation and application of organic coated SiO2 particles with flame retardant and toughening effects |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114292368B (en) | 2023-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114292368B (en) | Organic silicon-phosphorus-containing acrylate core-shell toughening flame retardant and preparation method thereof | |
| CA1330605C (en) | Vinyl chloride resin composition | |
| EP0166900B1 (en) | Polyorganosiloxane-based graft copolymer and process for producing same | |
| TWI263661B (en) | Flameproof thermoplastic resin compositions | |
| CN102391488B (en) | Preparation method for fluorine silicon phosphorus-containing anti-dropping flame-retardant polyethylene terephthalate | |
| WO2022089459A1 (en) | Reactive phosphorus-silicon synergistic flame retardant, polymeric phosphorus-silicon synergistic flame retardant, preparation methods therefor and applications thereof | |
| CN103819634A (en) | Block copolymer containing phosphorus and silicon and preparation method of block copolymer | |
| CN104211880A (en) | Inflaming retarding segmented copolymer containing phosphorus and silicon and preparation method thereof | |
| CN112961363A (en) | Polymeric phosphorus-silicon synergistic flame retardant and preparation method and application thereof | |
| CN109135189A (en) | A kind of epoxy resin poly- phosphorus silazane fire retardant of multielement containing P/N/Si and preparation method thereof | |
| CN110157133B (en) | Phosphorus-containing acrylate elastomer flame retardant and preparation method thereof | |
| US5532302A (en) | Flame retardant composition and method for use in synthetic thermoplastic resins | |
| CN1121083A (en) | Graft (co) polymers useful as flame retardant additives | |
| JP6743371B2 (en) | Thermoplastic resin composition and molded article using the same | |
| DE69925166T2 (en) | Flame retardant for a thermoplastic resin and flame-retardant resin composition | |
| CN106589881A (en) | Polycarbonate composition and preparing method thereof | |
| CN114874456B (en) | Method for modifying natural lignin of halogen-free flame-retardant degradable plastic | |
| CN103130952B (en) | Core-shell type nanostructured polymeric microsphere fire retardant, preparation method and application of core-shell type nanostructured polymeric microsphere fire retardant | |
| CN116515041A (en) | Phosphaphenanthrene/siloxane double-based macromolecular flame retardant and preparation method thereof | |
| KR20100067235A (en) | Flameproof crosslinked copolymer and method of preparing the same | |
| KR101411825B1 (en) | Char generating agent, and abs resin composition using thereof | |
| CN110734514A (en) | transparent flame-retardant polyunsaturated phosphate and preparation method thereof | |
| JP2020073697A (en) | Thermoplastic resin composition and molded product obtained by molding the same | |
| CN110981977A (en) | Flame-retardant cellulose and preparation method and application thereof | |
| CN113429726B (en) | Preparation method of environment-friendly flame-retardant high impact polystyrene |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |