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CN116675985B - Flame-retardant silicone rubber containing cage-shaped oligomeric silsesquioxane and preparation method thereof - Google Patents

Flame-retardant silicone rubber containing cage-shaped oligomeric silsesquioxane and preparation method thereof Download PDF

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CN116675985B
CN116675985B CN202310250038.3A CN202310250038A CN116675985B CN 116675985 B CN116675985 B CN 116675985B CN 202310250038 A CN202310250038 A CN 202310250038A CN 116675985 B CN116675985 B CN 116675985B
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silicone rubber
flame retardant
oligomeric silsesquioxane
cage
parts
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CN116675985A (en
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杭建兵
姚文华
周建锋
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Changshu Staples New Materials Co ltd
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    • 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
    • C08L83/04—Polysiloxanes
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
    • 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
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a flame-retardant silicone rubber containing cage-shaped oligomeric silsesquioxane and a preparation method thereof, wherein the rubber comprises the following raw materials in parts by weight: 100 parts of vinyl silicone rubber, 30-50 parts of gas-phase white carbon black, 10-20 parts of flame retardant and 1-3 parts of double dipentaerythritol vulcanizing agent; wherein the phosphorus-containing flame retardant is prepared by the following method: 1) Preparing alkynyl polyhedral oligomeric silsesquioxane; 2) Preparing azide phosphate; 3) Performing azide-alkyne ring clicking reaction on alkynyl polyhedral oligomeric silsesquioxane and azido phosphate to prepare a phosphorus-nitrogen-silicon-containing intumescent flame retardant; the flame-retardant silicone rubber containing the cage-shaped oligomeric silsesquioxane has good flame retardance, can reach the UL94-V0 combustion grade, has the characteristics of high efficiency, no halogen, no smoke, no toxicity, good elastic restoring force and the like, is suitable for complex electrical system protection materials such as new energy automobiles, electric power and the like, is particularly suitable for the field of electrical protection with severe requirements, and provides high-reliability safety protection for electrical components.

Description

Flame-retardant silicone rubber containing cage-shaped oligomeric silsesquioxane and preparation method thereof
Technical Field
The invention belongs to the technical field of flame-retardant high polymer materials, and particularly relates to flame-retardant silicone rubber containing cage-shaped oligomeric silsesquioxane and a preparation method thereof.
Background
The organic silicon rubber material is widely applied to industrial production and daily life, has certain self-extinguishing property of combustion, but has poor flame retardance, and high flame retardance silicon rubber is still the key point of current research. Flame retardants which can be used for silicone rubber at present can be divided into two main types, namely halogen-containing flame retardants and halogen-free flame retardants, and the halogen-free flame retardants are forbidden in many countries due to the great environmental protection pressure of the halogen-containing flame retardants, so that the halogen-free flame retardants are hot spots for research.
The flame retardant used for the halogen-free flame-retardant silicone rubber mainly comprises inorganic flame retardants (such as magnesium aluminum hydroxide and hydrated zinc borate), phosphorus flame retardants, nitrogen flame retardants, phosphorus-nitrogen intumescent flame retardants and the like. The flame retardant has the advantages of large addition amount, low flame retardant efficiency, low decomposition temperature, large specific gravity of the prepared flame retardant silicone rubber, serious mechanical property deterioration of the material, poor heat resistance and risk of precipitation of the flame retardant. In addition, the flame-retardant silicone rubber also adopts a platinum catalyst as a flame retardant, the flame retardant is expensive, and the flame retardant is used independently, has no obvious effect, and is generally compounded with a phosphorus-nitrogen flame retardant. The high-efficiency high-heat-resistance precipitation-free flame retardant is the key point of research on flame-retardant silicone rubber containing cage-shaped oligomeric silsesquioxane.
Disclosure of Invention
In view of the above state of the art, the present invention provides a flame retardant silicone rubber containing cage-like oligomeric silsesquioxanes, comprising the following components:
100 parts of vinyl silicone rubber, 30-50 parts of gas-phase white carbon black, 10-20 parts of flame retardant and 1-3 parts of double-disulfide vulcanizing agent.
The flame retardant has the following molecular structure:
in the above-mentioned formula (I),is a phosphorus-containing group selected from->Or->
The vinyl silica gel can be one or more of methyl vinyl silicone rubber, methyl vinyl phenyl silicone rubber and methyl vinyl trifluoropropyl silicone rubber, the molecular weight is 60-80 Da, and the vinyl content is 0.3-2.0 mol%.
The flame-retardant silicone rubber containing the cage-shaped oligomeric silsesquioxane is prepared by the following steps:
(1) The flame retardant is dried to constant weight before use, and is placed in a ball milling tank for high-energy ball milling, wherein the ball-material ratio is 10:1, the ball milling rotating speed is 3600r/min, and the ball milling time is 3-9 h.
(2) Uniformly kneading vinyl silicone rubber and gas-phase white carbon black in a kneader at 30 ℃, adding a flame retardant, and carrying out open milling on the mixture at room temperature on a two-roll open mill to obtain sheets; adding a vulcanizing agent, mixing uniformly, standing for 24 hours, tabletting on a flat vulcanizing machine, vulcanizing at 120-150 ℃ for 5-10 min, and vulcanizing for 2 hours in a 200 ℃ oven.
The flame retardant is prepared by the following steps:
(1) Preparation of alkynyl polyhedral oligomeric silsesquioxanes (POSS-Alkyne)
With dichloromethane as solvent, 1-Hydroxybenzotriazole (HOBT) as amido protectant, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl) as dehydrating agent, and 5-acetylene acid bonded to amino polyhedral oligomeric silsesquioxane (POSS-NH) 2 ) And obtaining POSS-Alkyne.
(2) Preparation of azido phosphate (AZ)
Reacting sodium azide with bromine-containing phosphate at normal temperature by taking DMF as a solvent to prepare azide phosphate (AZ);
the bromine-containing phosphate is diethyl 2-bromoethyl phosphonate or bromomethyl caged phosphate;
further, the bromomethyl cage phosphate has the following molecular structure:
the preparation method of the bromomethyl caged phosphate comprises the following steps: and taking dioxane as a solvent, and reacting 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propanediol with phosphorus oxychloride in a heating environment until no hydrogen chloride is released, so as to obtain bromomethyl caged phosphate.
(3) Click reaction for preparing cage-type oligomeric silsesquioxane flame retardant
And (3) taking DMSO as a solvent, and carrying out azide-Alkyne ring clicking reaction on POSS-Alkyne and AZ under the conditions of taking N, N, N ', N ', N ' -Pentamethyldiethylenetriamine (PMDETA) and CuBr as a catalytic system to prepare the cage-type oligomeric silsesquioxane flame retardant.
The invention has the following advantages and beneficial effects:
the flame-retardant silicone rubber containing the cage-shaped oligomeric silsesquioxane has good flame retardance, can reach the UL94-V0 combustion grade, has the characteristics of high efficiency, no halogen, no smoke, no toxicity, good elastic restoring force and the like, and in addition, an aging test shows that the flame retardant has good compatibility with a silica gel matrix, does not migrate, is suitable for complex electrical system protection materials such as new energy automobiles, electric power and the like, is particularly suitable for the field of electrical protection with severe requirements, and provides high-reliability safety protection for electrical components.
Drawings
FIG. 1 is a flame retardant prepared in example 1 1 H-NMR (Bruker AV-400 NMR, CDCl solvent) 3 (TMS internal standard)).
FIG. 2 is a flame retardant prepared in example 2 1 H-NMR (Bruker AV-400 NMR, CDCl solvent) 3 (TMS internal standard)).
FIG. 3 is a cross-sectional SEM images of samples 2 and 4 prepared in example 3 and of the sample silicone rubber prepared in comparative example 1.
FIG. 4 is a cross-sectional SEM image of sample 6 prepared in example 4 and sample silicone rubber prepared in comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
(1) Preparation of POSS-Alkyne
Weighing 5-acetylene acid (5.35 g,0.05 mol), HOBT (5.16 g,0.04 mol), POSS-NH 2 (5.01 g,5.68 mmol) was added to a three-necked flask, 200mL of dehydrated dichloromethane was added thereto and sufficiently dissolved, and the mixture was stirred at room temperature under nitrogen protection for 30 minutes, then EDC. HCl (18.30 g,0.8388 mmol) dissolved in 50mL of dichloromethane was slowly added dropwise to the above mixed solution, and reacted at room temperature for 48 hours. After the reaction, the reaction solution was concentrated by rotary evaporation and then poured into a mixed solution of water/methanol (V/v=1/4) to precipitate out, followed by removal of the precipitateWashing with son water and drying to obtain POSS-Alkyne solid powder with the yield of 88.2%.
(2) Preparation of CPA-AZ
2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propanediol (6.21 g,0.03 mol) and phosphorus oxychloride (4.78 g,0.03 mol) were added into a three-necked flask equipped with a condensing unit and a hydrogen chloride absorbing unit, and 100mL of dioxane was added thereto, and the mixture was stirred and dissolved at room temperature, and the temperature was gradually raised to 90 ℃ (10 ℃ C./10 min) until no hydrogen chloride was released, and the reaction was stopped by stirring. The reaction solution is cooled and filtered, washed by ethanol for 5 times and dried to obtain white solid powder which is bromomethyl caged phosphate (CPA-Br) with the yield of 82.5 percent
CPA-Br (5.68 g,0.02 mol), sodium azide (1.67 g,0.03 mol) were weighed into a round bottom flask, 20mL DMF was added and dissolved, and after 12h reaction at room temperature, the solvent was removed by rotary evaporation to give a white powder. Dissolving with chloroform again, adding mixed solvent of water and methanol (vwater/vmethanol=2:1), washing for 3 times, and taking organic phase, and rotary evaporating and drying to obtain white solid powder with yield of 62.4%.
(3) Preparation of cage oligomeric silsesquioxane flame retardant (POSS-CPA)
POSS-Alkyne (3.84 g,2.35 mmol), CPA-AZ (g, 18.8 mmol), cuBr (0.03 g,0.24 mmol) and PMDETA (0.08 g,0.47 mmol) and 20mL DMSO were added by injection after 3 times of freezing-vacuum-thawing-introducing nitrogen, reacted in an oil bath at 70deg.C for 72h, tetrahydrofuran was added by injection, and the reaction solution was passed through neutral Al 2 O 3 The column was used to remove the catalyst and the remaining solution was transferred to a dialysis bag of 3kDa cut-off and dialyzed against 500mL THF for 3d to remove unreacted polymer and solvent. After dialysis, the solution was precipitated in glacial diethyl ether and dried to give POSS-CPA in a yield of 72.6%.
The molecular structural formula of the flame retardant is as follows:
example 2
(1) Preparation of POSS-Alkyne
5-acetylenic acid (5.35 g, 0) was weighed.05mol)、HOBT(5.16g，0.04mol)、POSS-NH 2 (5.01 g,5.68 mmol) was added to a three-necked flask, 200mL of dehydrated dichloromethane was added thereto and sufficiently dissolved, and the mixture was stirred at room temperature under nitrogen protection for 30 minutes, then EDC. HCl (18.30 g,0.8388 mmol) dissolved in 50mL of dichloromethane was slowly added dropwise to the above mixed solution, and reacted at room temperature for 48 hours. After the reaction, the reaction solution was concentrated by rotary evaporation, and then poured into a mixed solution of water/methanol (V/v=1/4) to precipitate out, and after washing with deionized water, the mixture was dried to obtain POSS-Alkyne solid powder with a yield of 88.2%.
(2) Preparation of AZP
Diethyl 2-bromoethylphosphonate (5.04 g,0.02 mol) and sodium azide (1.34 g,0.02 mol) were weighed into a round bottom flask, 20mL of DMF was added and dissolved by stirring, the solvent was removed by rotary evaporation after 12h reaction at room temperature, dichloromethane was used as eluent, and the AZP was obtained by silica gel column chromatography purification and drying in a yield of 72.3%.
(3) Preparation of phosphorus-containing Nitrogen-silicon intumescent flame retardant (POSS-NP)
POSS-Alkyne (2.32 g,1.42 mmol), AZP (2.35 g,11.36 mmol) and CuBr (0.02 g,0.14 mmol) are added into a reaction tube, PMDETA (0.05 g,0.28 mmol) and 15mL DMSO are added by injection after 3 times of freezing, vacuumizing, thawing and nitrogen introduction, the mixture is placed into an oil bath pot at 70 ℃ for reaction for 72 hours, tetrahydrofuran is added by injection, and the obtained reaction solution passes through neutral Al 2 O 3 The column was used to remove the catalyst and the remaining solution was transferred to a dialysis bag of 3kDa cut-off and dialyzed against THF for 3d to remove unreacted polymer and solvent. After dialysis, the solution was precipitated in glacial diethyl ether and dried to give POSS-NP in 65.2% yield.
The molecular structural formula of the flame retardant is as follows:
example 3
Flame retardant silicone rubber was prepared using the flame retardant prepared in example 1.
(1) The flame retardant is placed in a vacuum oven at 60 ℃ for drying for 24 hours, then placed in a ball milling tank, and subjected to high-energy ball milling by adopting a QM-3SP2 planetary ball mill (Nanjing university instrument factory), wherein the ball material ratio is 10:1, the ball milling rotating speed is 3600r/min, and the ball milling time is 12 hours.
(2) Uniformly kneading vinyl silicone rubber and gas-phase white carbon black in a kneader at 30 ℃, adding a flame retardant, and carrying out open milling on the mixture at room temperature on a two-roll open mill to obtain sheets; adding a vulcanizing agent, mixing uniformly, standing for 24 hours, tabletting on a flat vulcanizing machine, vulcanizing at 120-150 ℃ for 5-10 min, and vulcanizing for 2 hours in a 200 ℃ oven.
The formulations and curing conditions for each sample are shown in Table 1.
TABLE 1
The methyl vinyl silicone rubber has a molecular weight of 62X 10 4 Da, vinyl content 1.2%.
The molecular weight of the methyl vinyl trifluoropropyl silicone rubber is 68 multiplied by 10 4 Da, vinyl content 0.3mol%
Example 4
Flame retardant silicone rubber was prepared using the flame retardant prepared in example 2, in the same manner as in example 3.
The formulations and curing conditions for each sample are shown in Table 2.
TABLE 2
Comparative example 1
The difference from example 3 is that the flame retardant is not milled prior to use.
The formula of the rubber comprises the following steps: 100 parts of methyl vinyl silicone rubber, 30 parts of gas phase white carbon black, 20 parts of flame retardant, 2 parts of vulcanizing agent, and the vulcanizing temperature is 120 ℃ and the vulcanizing time is 5min.
Comparative example 2
And preparing the silicone rubber without the addition of the flame retardant.
The formula of the rubber comprises the following steps: 100 parts of methyl vinyl silicone rubber, 30 parts of gas phase white carbon black, 2 parts of vulcanizing agent, and the vulcanizing temperature is 120 ℃ and the vulcanizing time is 5min.
The properties of each sample silicone rubber were tested as follows:
limiting Oxygen Index (LOI) was measured according to GB 10707-1989.
The vertical burn test was as per GB/T13488-1992.
Tensile strength and elongation were measured according to GB/T528-1998, the tensile speed was 500mm/min;
tear strength was measured according to GB/T529-1999 and tensile speed was 500mm/min.
Shore A hardness was measured according to GB/T531-1999.
SEM: and observing the section of the sample by adopting a JSM-5610LV scanning electron microscope, wherein the accelerating voltage is 5 kV-10 kV.
TABLE 3 Table 3
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.

Claims (6)

1. The flame-retardant silicone rubber containing the cage-shaped oligomeric silsesquioxane is characterized by comprising the following components in parts by weight: 100 parts of vinyl silicone rubber, 30-50 parts of gas-phase white carbon black, 10-20 parts of flame retardant and 1-3 parts of bis-penta vulcanizing agent; the flame retardant has the structure of the following formula (I):
（I）
in the above-mentioned formula (I),is a phosphorus-containing group selected from->Or (b)。
2. The flame retardant silicone rubber containing cage oligomeric silsesquioxane according to claim 1, wherein: the vinyl silicone rubber is one or more of methyl vinyl silicone rubber, methyl vinyl phenyl silicone rubber and methyl vinyl trifluoropropyl silicone rubber, the molecular weight is 60-80 Da, and the vinyl content is 0.3-2.0 mol%.
3. The flame retardant silicone rubber containing cage oligomeric silsesquioxane according to claim 1, wherein: the flame retardant is dried to constant weight before use and is placed in a ball milling tank for high-energy ball milling.
4. The flame retardant silicone rubber containing cage oligomeric silsesquioxane according to claim 1, wherein the flame retardant is prepared by the steps of:
(1) Preparation of alkynyl polyhedral oligomeric silsesquioxanes (POSS-Alkyne)
With dichloromethane as solvent, 1-Hydroxybenzotriazole (HOBT) as amido protectant, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl) as dehydrating agent, and 5-acetylene acid bonded to amino polyhedral oligomeric silsesquioxane (POSS-NH) 2 ) Obtaining POSS-Alkyne;
(2) Preparation of azido phosphate (AZ)
Reacting sodium azide with bromine-containing phosphate at normal temperature by taking DMF as a solvent to prepare azide phosphate (AZ);
the bromine-containing phosphate is diethyl 2-bromoethyl phosphonate or bromomethyl caged phosphate;
further, the bromomethyl cage phosphate has the following molecular structure:
（II）
(3) Click reaction for preparing cage-type oligomeric silsesquioxane flame retardant
And (3) taking DMSO as a solvent, and carrying out azide-Alkyne ring clicking reaction on POSS-Alkyne and AZ under the conditions of taking N, N, N ', N', N '' -Pentamethyldiethylenetriamine (PMDETA) and CuBr as a catalytic system to prepare the cage-type oligomeric silsesquioxane flame retardant.
5. A cage oligomeric silsesquioxane flame retardant according to claim 4, wherein: the step (1) is 5-acetylene acid and POSS-NH 2 The molar ratio of HOBT to EDC/HCl was 8.4:1:6.5:16.5.
6. A cage oligomeric silsesquioxane flame retardant according to claim 4, wherein: the reaction feeding molar ratio of the POSS-Alkyne, AZ, cuBr, PMDETA in the step (3) is 1:8:0.1:0.2.
CN202310250038.3A 2023-03-15 2023-03-15 Flame-retardant silicone rubber containing cage-shaped oligomeric silsesquioxane and preparation method thereof Active CN116675985B (en)

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Publication number Priority date Publication date Assignee Title
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CN105801865A (en) * 2016-03-23 2016-07-27 合肥学院 Phosphorus and nitrogen containing polyhedral oligomeric silsesquioxane and preparation method thereof
CN106750317A (en) * 2017-01-13 2017-05-31 山东船舶技术研究院 One kind is based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof
CN111072973A (en) * 2019-05-28 2020-04-28 杭州师范大学 A kind of phosphorus-containing POSS and its preparation method and application in flame retardant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105143351A (en) * 2013-04-23 2015-12-09 三菱瓦斯化学株式会社 Polyamide resin composition, and molded article
CN105801865A (en) * 2016-03-23 2016-07-27 合肥学院 Phosphorus and nitrogen containing polyhedral oligomeric silsesquioxane and preparation method thereof
CN106750317A (en) * 2017-01-13 2017-05-31 山东船舶技术研究院 One kind is based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof
CN111072973A (en) * 2019-05-28 2020-04-28 杭州师范大学 A kind of phosphorus-containing POSS and its preparation method and application in flame retardant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张文超 等.POSS/DOPO硅磷协同"吹熄"阻燃环氧树脂研究.《 2013年全国高分子学术论文报告会论文摘要集——主题M：阻燃高分子》.2013,899. *

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