CN112266430A - Nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and preparation method thereof - Google Patents
Nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and preparation method thereof Download PDFInfo
- Publication number
- CN112266430A CN112266430A CN202011112624.4A CN202011112624A CN112266430A CN 112266430 A CN112266430 A CN 112266430A CN 202011112624 A CN202011112624 A CN 202011112624A CN 112266430 A CN112266430 A CN 112266430A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- polybutadiene
- phosphorus flame
- reaction
- rigid reinforced
- 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.)
- Withdrawn
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and a preparation method thereof; by grafting a nitrogen-phosphorus flame retardant between polybutadiene molecular chains, a nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is obtained, so that polybutadiene molecules have flame retardancy; the problems that the flame retardant molecules and the polybutadiene substrate are only physically mixed, chemical bonding does not exist, the bonding acting force between the flame retardant molecules and the polybutadiene substrate is weak, the loss of flame retardant components affects the long-term flame retardant performance of a product, and the dispersion uniformity of the flame retardant is not easy to guarantee are solved.
Description
Technical Field
The invention belongs to the field of polymer chemical synthesis, and particularly relates to a nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and a preparation method thereof.
Background
Polybutadiene macromolecule chain segment contains double bonds and can be vulcanized by sulfur; the rubber shoe is mainly used for manufacturing various tires, rubber tubes, rubber shoes and other various rubber products; however, since butadiene rubber is flammable in air, its application is largely limited. In order to improve the flame retardant properties, flame retardants must be added, the function of which is to impart flame retardancy, self-extinguishing properties and smoke abatement properties to the base material.
At present, common flame retardants include halogen flame retardants, inorganic metal hydroxide flame retardants, intumescent flame retardants, phosphorus-containing flame retardants, montmorillonite, carbon nanotubes, graphene flame retardants, and the like; the metal oxide is used as a flame retardant of the rubber, so that the flame retardant property of the rubber can be improved, substances harmful to the environment can not be generated in the combustion process, but the mechanical property of a rubber matrix can be damaged by the addition of the metal oxide; the inorganic hydroxide as a flame retardant has low flame retardant efficiency, has good flame retardant effect only when the addition amount of the inorganic hydroxide in a rubber matrix is large, and the filling of the inorganic hydroxide can generate adverse effect on the mechanical property of the rubber material; the phosphorus-containing flame retardant is a flame retardant which develops rapidly in recent years, is environment-friendly, but has low flame retardant efficiency, and is particularly suitable for polymer matrixes only containing carbon and hydrogen elements; and the influence on the physical and mechanical properties of the polymer matrix is large; after montmorillonite is added into rubber as a flame retardant, the mechanical property, the thermal stability and the char formation of a rubber matrix can be improved, but the montmorillonite does not contribute significantly to the flame retardance of the matrix material; the carbon nano tube can effectively improve the flame retardance of the rubber, but the price is high, and the industrial production of the carbon nano tube flame retardant rubber is difficult to realize; based on the above, the invention provides a nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and a preparation method thereof.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a nitrogen-phosphorus flame-retardant rigidity-enhanced polybutadiene material and a preparation method thereof.
The invention aims to provide a nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material.
The invention also aims to provide a preparation method of the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material.
The above purpose of the invention is realized by the following technical scheme:
the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material has a structural formula shown as the following formula (I):
wherein n is 15 to 1000.
The preparation method of the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material comprises the following steps:
1. adding 2, 2-bis (4-hydroxyphenyl) propane, triethylamine and acetonitrile into a three-neck flask, stirring the mixture for 10 minutes, slowly heating to 8 ℃, adding phenylphosphonic dichloride, keeping the reaction temperature at 8 ℃ for reacting for 4 hours, cooling the reactant to room temperature, spin-drying the reaction solvent, purifying the reaction solvent by taking ethyl acetate/petroleum ether as a mobile phase through a column, spin-evaporating to remove the reaction solvent, and vacuum-drying to obtain the compound A.
Wherein the molar ratio of the phenylphosphonic dichloride, the 2, 2-bis (4-hydroxyphenyl) propane and the triethylamine is 1:2.2: 2.2.
2. Adding the A, phenylphosphonic dichloride and acetonitrile into a flask with a branch mouth, heating to 80 ℃ for reaction for 10 hours, cooling reactants to room temperature, performing spin-drying on a reaction solvent, performing column chromatography purification by taking ethyl acetate/petroleum ether as a mobile phase, removing the reaction solvent by spin-evaporation, and performing vacuum drying to obtain a compound B.
Wherein the molar ratio of A to phenylphosphonic dichloride is 1: 2.2.
3. Adding the B, melamine and acetonitrile into a flask with a branch mouth, heating to 90 ℃ for reaction for 4h, cooling reactants to room temperature, performing spin-drying on a reaction solvent, performing column chromatography purification by taking ethyl acetate/petroleum ether as a mobile phase, removing the reaction solvent by spin-evaporation, and performing vacuum drying to obtain a compound C.
Wherein the molar ratio of melamine to B is 1: 2.2.
4. Adding carboxyl-terminated polybutadiene and anhydrous tetrahydrofuran THF into a reactor, slowly dropwise adding SOCl after the reaction temperature rises to 70 DEG C2After the dropwise addition, the reaction was carried out for 2 hours, and after the completion of the reaction, SOCl was removed by distillation under reduced pressure2And THF to obtain carboxyl-terminated polybutadiene acyl chloride product; add C to Schlenk flask, N2Under protection, adding anhydrous toluene, heating to 70 ℃, adding pyridine, stirring for 30min, dropwise adding the carboxyl-terminated polybutadiene acyl chlorination product dissolved in toluene, heating to 80 ℃, continuing to react for 3h, cooling the product to room temperature, continuously dissolving/precipitating with toluene/methanol for two times, and performing vacuum drying to obtain the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material。
Wherein, C, carboxyl terminated polybutadiene and SOCl2In a molar ratio of 1:4: 10.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention provides a nitrogen-phosphorus flame-retardant rigidity-enhanced polybutadiene material, wherein a nitrogen-phosphorus flame retardant is grafted among polybutadiene molecular chains, so that polybutadiene molecules have flame retardancy, the molecules of the grafted flame retardant contain a large number of benzene rings, and the rigidity of polybutadiene is improved by introducing the flame retardant.
(2) The invention provides a nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material, which solves the problems that the bonding effect between flame retardant molecules and a polybutadiene substrate is weak, the dispersion uniformity of a flame retardant is not easy to guarantee, the loss of flame retardant components is difficult to avoid, and the long-term flame retardant performance of a product is directly influenced.
Drawings
FIG. 1 is a flow chart of the preparation of nitrogen phosphorus flame-retardant rigid reinforced polybutadiene material.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Adding 2, 2-bis (4-hydroxyphenyl) propane (2.2mmol), triethylamine (2.2mmol) and 10mL of acetonitrile into a 25mL three-neck flask, stirring the mixture for 10 minutes, slowly heating to 8 ℃, adding phenylphosphonyl dichloride (1.0mmol), reacting for 4 hours at 8 ℃, cooling the reaction product to room temperature, performing column purification by taking ethyl acetate/petroleum ether (v/v ═ 10:1) as a mobile phase, performing rotary evaporation to remove the reaction solvent, and performing vacuum drying at 45 ℃ to obtain the compound A, wherein the yield is 83.4%.
Example 2
Adding A (1.0mmol), phenylphosphonic dichloride (2.2mmol) and 20mL of acetonitrile into a 50mL flask with a branch mouth, heating to 80 ℃ for reaction for 10h, cooling the reaction product to room temperature, drying the reaction solvent in a rotary manner, purifying the reaction product by using ethyl acetate/petroleum ether (v/v ═ 9:1) as a mobile phase through a column, removing the reaction solvent by rotary evaporation, and drying the reaction product in vacuum at 45 ℃ to obtain a compound B, wherein the yield is 78.5%.
Example 3
Adding B (2.2mmol), melamine (1.0mmol) and 20mL of acetonitrile into a 50mL flask with a branch mouth, heating to 90 ℃ for reaction for 4 hours, cooling the reactant to room temperature, spinning to dry the reaction solvent, purifying by using ethyl acetate/petroleum ether as a mobile phase through a column, spinning to remove the reaction solvent, and drying in vacuum at 45 ℃ to obtain a compound C with the yield of 76.3%.
Example 4
Carboxyl-terminated polybutadiene (4.0mmol) and 20mL of anhydrous tetrahydrofuran THF were added to a 50mL branched flask, the branched flask was placed on a heater, the temperature was raised to 70 ℃, and SOCl was slowly added dropwise2(10.0mmol) and continuing the reaction for 2h after the dropwise addition, after the reaction is finished, removing SOCl by reduced pressure distillation2And THF to afford the carboxyl-terminated polybutadiene acylchlorination product.
C (1.0mmol) was charged into a 50ml Schlenk flask, which was placed on a heater, and after purging nitrogen three times, N2Under protection, 30ml of anhydrous toluene is added into a disposable injector, the temperature is raised to 70 ℃, after C is completely dissolved, 1ml of pyridine is injected, the mixture is stirred for 30min, the carboxyl-terminated polybutadiene acyl chlorination product dissolved in the toluene is dropwise added, the temperature is raised to 80 ℃, the reaction is continued for 2h, the product is cooled to room temperature, after two times of continuous dissolution/precipitation circulation of the toluene/methanol, the product is dried to constant weight under vacuum at 45 ℃, and the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is obtained, wherein the yield is 69.7%.
Example 5
Before processing, the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is dried in vacuum for 12 hours at the temperature of 80 ℃, 60 parts by mass of the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is added on an open type heat mixer with the double-roll temperature of 155 ℃, after the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is melted and wrapped by rolls, the mixture is mixed for 10min and then evenly taken out, the mixture is hot-pressed for 10min at the temperature of 160 ℃ on a flat vulcanizing machine, cold-pressed for 8min at room temperature and taken out, various standard sample strips are prepared on a universal sampling machine, and the flame retardant performance test is carried out.
Example 6
Before processing, the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is dried in vacuum for 12 hours at 80 ℃, 80 parts by mass of the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is added on an open type heat mixer with a double-roller temperature of 155 ℃, after the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is melted and wrapped by rollers, the mixture is mixed for 10min and then evenly taken out, the mixture is hot-pressed for 10min at 160 ℃ on a flat vulcanizing machine, cold-pressed for 8min at room temperature and taken out, various standard sample strips are prepared on a universal sampling machine, and the flame retardant performance test is carried out.
Example 7
Before processing, the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is dried in vacuum for 12 hours at the temperature of 80 ℃, 100 parts by mass of the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is added on an open type heat mixer with the double-roller temperature of 155 ℃, after the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is melted and wrapped by rollers, the mixture is mixed for 10min and then evenly taken out, the mixture is hot-pressed for 10min at the temperature of 160 ℃ on a flat vulcanizing machine, cold-pressed for 8min at room temperature and taken out, various standard sample strips are prepared on a universal sampling machine, and the flame retardant performance test is carried out.
Comparative example 1
Before processing, polybutadiene is dried in vacuum at 80 ℃ for 12h, 100 parts by mass of polybutadiene is added into an open type heat mixing machine with a double-roller temperature of 155 ℃, after the polybutadiene is melted and coated on a roller, the polybutadiene is mixed for 10min and then evenly taken out, hot pressing is carried out on a flat vulcanizing machine at 160 ℃ for 10min, cold pressing is carried out at room temperature for 8min, the polybutadiene is taken out, various standard sample strips are prepared on a universal sampling machine, and the flame retardant performance test is carried out.
Limiting oxygen index test: the instrument is FTAII (1600) type limit oxygen index instrument of RS company in UK, test standard GB/T2406.2-2009, spline specification 100mm x 6mm x 3mm, and a group of 5-10, before test, the spline is placed in an environment with temperature 23 + -2 deg.C and humidity 50 + -5% and adjusted for more than 88 h.
UL-94 vertical burning test: the instrument is an CZF-5A horizontal vertical combustion tester of Jiangning analytical instruments factory for carrying out UL-94 vertical combustion test, the specification of the sample bar is 125mm multiplied by 13mm multiplied by 3.2mm, and the test standard is UL94ISBN 0-7629 and 0082-2. Before testing, the sample is put in an environment with the temperature of 23 +/-2 ℃ and the humidity of 50 +/-5% and is adjusted for more than 48 h.
Tensile strength was determined according to standard HG/T2580-.
The bending strength was determined according to the standard GB/T12585-2001.
Table 1 shows the flame retardant properties and mechanical properties of nitrogen-phosphorus flame retardant rigid reinforced polybutadiene materials.
| Sample (I) | LOI(％) | UL-94 | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 5 | 32.0 | V-1 | 40 | 203.4 |
| Example 6 | 34.6 | V-1 | 37 | 196.2 |
| Example 7 | 35.9 | V-1 | 33 | 185.7 |
| Comparative example 1 | 17.6 | N.R | 57 | 236.2 |
As can be seen from Table 1, the organic molecules with flame retardant effect grafted between polybutadiene polymer chains can obviously improve the flame retardant property of polybutadiene; as can be seen from the comparison of the data of the example 5 and the comparative example 1, the LOI of the pure butadiene is only 17.6%, when the organic molecules with the flame-retardant effect are grafted between the polybutadiene molecular chains to modify the polyphenylabutadiene, the LOI can reach 35.9%, and the flame-retardant property of the polyphenylabutadiene is effectively improved; and the introduction of the phosphorus-containing flame retardant increases the rigidity of the polybutadiene.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material is characterized by having a structure shown in a formula (I):
wherein n is 15 to 1000.
2. The preparation method of the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material according to claim 1, wherein the preparation method comprises the following steps:
(1) adding 2, 2-bis (4-hydroxyphenyl) propane, triethylamine and acetonitrile into a three-neck flask, stirring the mixture for 10 minutes, slowly heating to 8 ℃, adding phenylphosphonic dichloride, keeping the reaction temperature at 8 ℃ for reacting for 4 hours, cooling the reactant to room temperature, spin-drying the reaction solvent, purifying the reaction solvent by taking ethyl acetate/petroleum ether as a mobile phase through a column, spin-evaporating to remove the reaction solvent, and vacuum-drying to obtain a compound A;
(2) adding the A, phenylphosphonic dichloride and acetonitrile into a flask with a branch mouth, heating to 80 ℃ for reaction for 10 hours, cooling reactants to room temperature, performing spin-drying on a reaction solvent, performing column chromatography purification by taking ethyl acetate/petroleum ether as a mobile phase, removing the reaction solvent by spin-evaporation, and performing vacuum drying to obtain a compound B;
(3) adding the B, melamine and acetonitrile into a flask with a branch mouth, heating to 90 ℃ for reaction for 4 hours, cooling reactants to room temperature, performing column chromatography purification by using ethyl acetate/petroleum ether as a mobile phase, removing the reaction solvent by rotary evaporation, and performing vacuum drying to obtain a compound C;
(4) adding carboxyl-terminated polybutadiene and anhydrous tetrahydrofuran THF into a reactor, slowly dropwise adding SOCl after the reaction temperature rises to 70 DEG C2After the dropwise addition, the reaction was carried out for 2 hours, and after the completion of the reaction, SOCl was removed by distillation under reduced pressure2And THF to obtain carboxyl-terminated polybutadiene acyl chloride product; add C to Schlenk flask, N2Under protection, adding anhydrous toluene, heating to 70 ℃, adding pyridine, stirring for 30min, dropwise adding the carboxyl-terminated polybutadiene acyl chlorination product dissolved in toluene, heating to 80 ℃, continuing to react for 3h, cooling the product to room temperature, continuously dissolving/precipitating with toluene/methanol for twice, and then performing vacuum drying to obtain the nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material.
3. The method for preparing nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material according to claim 2, wherein in step (1), the molar ratio of phenylphosphonic dichloride, 2-bis (4-hydroxyphenyl) propane and triethylamine is 1:2.2: 2.2.
4. The method for preparing nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material according to claim 2, wherein in step (2), the molar ratio of A to phenylphosphonic dichloride is 1: 2.2.
5. The method for preparing nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material according to claim 2, wherein in step (3), the molar ratio of melamine to B is 1: 2.2.
6. The method for preparing nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material according to claim 2, wherein in step (4), the C carboxyl-terminated polybutadiene and SOCl are mixed2In a molar ratio of 1:4: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011112624.4A CN112266430A (en) | 2020-10-16 | 2020-10-16 | Nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011112624.4A CN112266430A (en) | 2020-10-16 | 2020-10-16 | Nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112266430A true CN112266430A (en) | 2021-01-26 |
Family
ID=74337286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011112624.4A Withdrawn CN112266430A (en) | 2020-10-16 | 2020-10-16 | Nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112266430A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116903910A (en) * | 2023-09-14 | 2023-10-20 | 河南华佳新材料技术有限公司 | Metallized film for rail transit capacitor and preparation method thereof |
-
2020
- 2020-10-16 CN CN202011112624.4A patent/CN112266430A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116903910A (en) * | 2023-09-14 | 2023-10-20 | 河南华佳新材料技术有限公司 | Metallized film for rail transit capacitor and preparation method thereof |
| CN116903910B (en) * | 2023-09-14 | 2023-12-01 | 河南华佳新材料技术有限公司 | Metallized film for rail transit capacitor and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111072973B (en) | Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant | |
| CN109651595B (en) | Halogen-free flame-retardant bio-based epoxy resin precursor and preparation method and application thereof | |
| WO2021023226A1 (en) | Nitrogen-rich group functionalized graphene, preparation method, and application | |
| CN104277223A (en) | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant | |
| CN110483663B (en) | Modified chitosan flame retardant and preparation method thereof | |
| CN110563765B (en) | Synthesis method of Schiff base phosphazene double-base structure flame retardant and modified polyurethane flame retardant | |
| CN111690171B (en) | Flame retardant and flame-retardant PC plastic | |
| CN104559100B (en) | Functional cyclodextrin flame-retarding polylactic acid composite material and preparation method thereof | |
| CN111662332A (en) | Organophosphorus flame retardant with active amino groups and preparation method and application thereof | |
| You et al. | Synthesis and performance of a novel nitrogen‐containing cyclic phosphate for intumescent flame retardant and its application in epoxy resin | |
| CN112266430A (en) | Nitrogen-phosphorus flame-retardant rigid reinforced polybutadiene material and preparation method thereof | |
| CN103012847A (en) | Efficient nitrogen and phosphorus fire retardant for epoxy resin and preparation method of efficient nitrogen and phosphorus fire retardant | |
| Hu et al. | Roles of phosphoramide derivatives in flame retardancy, thermal degradation and crystallization behaviors of polylactic acid | |
| CN114085246A (en) | Bio-based phosphorus-containing flame retardant and preparation method and application thereof | |
| CN109705349B (en) | POSS (polyhedral oligomeric silsesquioxane) modified pentaerythritol ester containing sulfhydryl group cross-linked network polymer as well as preparation method and application thereof | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN105295092B (en) | A kind of phosphorous, nitrogen luxuriant molysite fire retardant and its preparation method and application | |
| CN112250959A (en) | Nitrogen-phosphorus flame-retardant polystyrene and preparation method thereof | |
| CN110272600A (en) | A kind of PVC pipe and preparation method thereof | |
| CN112250777A (en) | Nitrogen-phosphorus flame-retardant polystyrene block copolymer and preparation method thereof | |
| Sun et al. | Improving flame retardancy and mechanical properties of polyamide 6 induced by multiple reactions among flame retardants and matrix | |
| CN112708084A (en) | Degradable flame-retardant polystyrene material and preparation method thereof | |
| CN112266541A (en) | Nitrogen-phosphorus flame-retardant polypropylene material and preparation method thereof | |
| CN112266429A (en) | Nitrogen-phosphorus flame-retardant polybutadiene material and preparation method thereof | |
| CN111606948B (en) | Efficient phosphine-nitrogen flame retardant and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210126 |
|
| WW01 | Invention patent application withdrawn after publication |