CN104448830B - A kind of phosphorus silicon composite flame-retardant agent and its preparation method and application - Google Patents
A kind of phosphorus silicon composite flame-retardant agent and its preparation method and application Download PDFInfo
- Publication number
- CN104448830B CN104448830B CN201410680503.8A CN201410680503A CN104448830B CN 104448830 B CN104448830 B CN 104448830B CN 201410680503 A CN201410680503 A CN 201410680503A CN 104448830 B CN104448830 B CN 104448830B
- Authority
- CN
- China
- Prior art keywords
- caged
- preparation
- retardant
- silsesquioxane
- phosphorus
- 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.)
- Active
Links
Abstract
The invention discloses a kind of phosphorus silicon composite flame-retardant agent and its preparation method and application.Described phosphorus silicon composite flame-retardant agent is seven phenyl of caged, the three silicon phosphorus silsesquioxane with following structure：The preparation of the fire retardant is first to make POSS be hydrolyzed to unfilled corner POSS under organic base effect, unfilled corner POSS is reacted with Metaphosphoric acid.Experiment shows：The compound phosphorus silicon fire retardant that the present invention is provided has given full play to silicon-series five-retardant and the advantage both phosphorus flame retardant; compensate for respective defect; act on significant cooperative flame retardant and complementary; and brilliance heat-insulated suppression cigarette, break off the characteristic of oxygen supply; also there is Environmental Safety, the functions such as molten drop are prevented; may be directly applied to the preparation of silicone rubber; the anti-flammability of silicone rubber can not only be improved; and its heat-insulated suppression cigarette and mechanical property can be improved, have the advantages that to prepare and implement with application cost is low, be easy to large-scale industrial.
Description
Technical field
The present invention is to be related to a kind of phosphorus silicon composite flame-retardant agent and its preparation method and application, belongs to fire proofing technology neck
Domain.
Background technology
At present, in macromolecular material flame retardant area, using it is more be halogenated flame retardant, although the resistance of this based flame retardant
Fuel efficiency fruit very well, but as hydrogen halide and non-biodegradable are discharged when halogen burns, is limited and is used.
Silicon-series five-retardant starts from phase early 1980s as the up-and-coming youngster in fire retardant family.It not only has
Efficiently, low toxicity, suppression and promotes into the excellent fire resistance such as charcoal at cigarette, and relative to conventional flame retardant, silicon-series five-retardant plus
The aspect such as work performance and mechanical property is also obviously improved, deep to be favored by numerous researcheres.At present, silicon-series five-retardant master
Following four classes to be had：
1) silicone flame retardant：It is a kind of efficient, ecological friendly, anti-molten drop and presses down the of new generation non-halogen charcoal becoming of cigarette
Fire retardant, can not only improve the performance such as the processing of base material, mechanical and heat-resisting, and it is also very excellent to recycle effect, mainly
Including kinds such as polysiloxanes, poly-organosilicon silsesquioxanes.But single organic silicon fibre retardant is only main to part high polymer
It is that Merlon is fruitful, applicable surface is not wide；
2) inorganic silicon-series five-retardant：Under certain condition, inorganic silicon compound no matter as polymer additive, or with
Polymer constitutes mixture system, is respectively provided with preferable fire retardation.Its fire-retardant high polymer most nontoxic few cigarette, fuel value
Low, flame propagation velocity is slow, but generally requires and use cooperatively with other additives.
3) silicon INSTINCT FLAME RETARDANT POLYMERS technology：Because silicon-containing group polymer typically have high intrinsic fire resistance,
Heat stability, oxidation stability, hydrophobicity and good compliance, the siliceous INSTINCT FLAME RETARDANT POLYMERS of gained except possess it is fire-retardant,
High heat resistance, antioxidation, it is nonflammable the features such as outside, the flexibility also with higher moisture-proof and strand.Additionally, siliceous
The fire-retardant high polymer decomposes product of matter is mainly carbon dioxide, vapor and silicon dioxide, environmentally friendly, thus is subject to wide
General concern.But the application manufacturing process of siliceous INSTINCT FLAME RETARDANT POLYMERS is complicated, expensive.
4) the synergistic flame-retarded technology of silicon fire retardant：Silicone-containing Flame Retardant is used together with other conventional flame retardants, shows to show
The cooperative flame retardant effect of work and complementarity, in combustion, both can mutually promote, and form siliceous carbonization protective layer, have
The heat-insulated suppression cigarette of brilliance, the supply for breaking off oxygen, and prevent the functions such as molten drop；The processing characteristics of material can be improved, to physical mechanical
Performance impact is little.
Caged octaphenyl silsesquioxane (referred to as POSS) is that a kind of have that nanostructured, the compatibility be good, anti-flammability is strong
Hybrid inorganic-organic materials, it is provided simultaneously with the advantage of silicon-type and inorganic silicon-series five-retardant, shows preferable with base material
The compatibility, can be applied in the materials such as plastics, rubber.
Phosphorus flame retardant not only has an efficient, multi-functional feature, and safety and environmental protection, is most main in current halogenated flame retardant
The substitute species wanted, but its heat stability is relatively low, when processing under molten condition or lower temperature, can produce in plastics, rubber
Raw foam, so as to cause application surface wideless.
The content of the invention
For drawbacks described above and problem existing for prior art, it is an object of the invention to provide a kind of phosphorus silicon composite flame-proof
Agent and its preparation method and application, traditional phosphorus flame retardant is introduced in seven phenyl of caged, three silanol silsesquioxane, is played
The two respective advantage, realizes the fire-retardant purpose of synergistic of phosphorus flame retardant and seven phenyl of caged, three silanol silsesquioxane.
For achieving the above object, the technical solution used in the present invention is as follows：
A kind of phosphorus silicon composite flame-retardant agent, is seven phenyl of caged, the three silicon phosphorus silsesquioxane with following structure：
A kind of method for preparing phosphorus silicon composite flame-retardant agent of the present invention, comprises the steps：
A) make caged octaphenyl silsesquioxane (referred to as POSS) be hydrolyzed reaction under organic base effect, be obtained scarce
Angle POSS：Seven phenyl of caged, three silanol silsesquioxane；
B) by above-mentioned unfilled corner POSS：Seven phenyl of caged, three silanol silsesquioxane is reacted with Metaphosphoric acid, obtains described phosphorus
Silicon composite flame-retardant agent.
Preferably, the preparation of described caged octaphenyl silsesquioxane (referred to as POSS), including following step
Suddenly：
1) phenyl trichlorosilane is made to stand 6～12 hours after being stirred at room temperature 8～16 hours with benzene and aqueous systems；
2) divide liquid, remove the acid layer of bottom, organic faciess are rinsed to pH=7 with distilled water or basic solvent；
3) to step 2) process after organic faciess in add the methanol solution of benzyltrimethylammonium hydroxide, be stirred at reflux anti-
Answer 24～36 hours；
4) filter, be dried, obtain described caged octaphenyl silsesquioxane (referred to as POSS).
As further preferred scheme, count in mass ratio, phenyl trichlorosilane: benzene: water: benzyltrimethylammonium hydroxide first
Alcoholic solution=(50～80): (250～400): (20～40): (8～13)；Wherein, benzyltrimethylammonium hydroxide methanol solution
Concentration of volume percent be 30～50%.
Preferably, the organic base described in step a) is Tetramethylammonium hydroxide.
Used as further preferred scheme, the hydrolysis described in step a) are to make caged octaphenyl silsesquioxane (referred to as
For POSS) back flow reaction 4～6 hours in tetrahydrofuran, tetramethylammonium hydroxide aqueous solution.
As still more preferably scheme, count in mass ratio, caged octaphenyl silsesquioxane: tetrahydrofuran: tetramethyl
Ammonium hydroxide aqueous solution=(10～20): (100～250): (4～8)；Wherein, the volume hundred of tetramethylammonium hydroxide aqueous solution
Specific concentration is divided to be 25～40%.
Preferably, in step b), unfilled corner POSS：Seven phenyl of caged, three silanol silsesquioxane and Metaphosphoric acid are four
React 4～6 hours in 50～80 DEG C in hydrogen furan.
As further preferred scheme, count in mass ratio, seven phenyl of caged, three silanol silsesquioxane: Metaphosphoric acid：Tetrahydrochysene
Furan=(10～20): (15～25): (100～250).
A kind of silicon rubber composite material prepared using phosphorus silicon composite flame-retardant agent of the present invention, according to the mass fraction,
At least include：74.5～94.5 mass parts raw-silastic continuouslies, 0.5～1.5 mass parts firming agent and 5～25 mass parts institute of the present invention
The phosphorus silicon composite flame-retardant agent stated.
Preferably, the preparation of described silicon rubber composite material comprises the steps：By phosphorus of the present invention
During silicon composite flame-retardant agent adds raw-silastic continuously, firming agent is added after being uniformly mixed, is poured into after continuing to be uniformly mixed
In mould, vacuum exhaust is carried out after 80～120 DEG C of curing reactions 60～90 minutes, be finally cooled to room temperature.
Used as further preferred scheme, the vacuum for carrying out vacuum exhaust is 150～160Pa.
Compared with prior art, the present invention has the advantages that：
The present invention by introducing traditional phosphorus flame retardant in silicon-series five-retardant caged octaphenyl silsesquioxane, fully
Silicon-series five-retardant and the advantage both phosphorus flame retardant have been played, respective defect has been compensate for, the compound phosphorus silicon fire retardant tool for obtaining
Have a significant cooperative flame retardant effect and complementary, and brilliance heat-insulated suppression cigarette, break off the characteristic of oxygen supply, also with environmental protection peace
Entirely, the functions such as molten drop are prevented.In addition, the phosphorus silicon composite flame-retardant agent that the present invention is provided is pulverulent solids, silicon is may be directly applied to
In the course of processing of rubber, process without the need for carry out loaded down with trivial details solution or fusion intercalation again, with preparing and application cost is low, be easy to
The advantages of large-scale industrial is implemented, can improve the processing characteristics of material, affect little to physical and mechanical propertiess.
Description of the drawings
Structural formulas of the Fig. 1 for caged octaphenyl silsesquioxane (POSS)；
Fig. 2 is unfilled corner POSS：The structural formula of seven phenyl of caged, three silanol silsesquioxane；
The phosphorus silicon composite flame-retardant agent that Fig. 3 is provided for the present invention：The structural formula of seven phenyl of caged, three silicon phosphorus silsesquioxane.
Specific embodiment
With reference to embodiment and comparative example, the present invention is described in further detail and completely.
Embodiment 1
50g phenyl trichlorosilanes, 250ml benzene are sequentially added in round-bottomed flask, 20mL water, body is slowly added to while stirring
System stands 10 hours after being stirred at room temperature 12 hours；The acid layer of bottom is removed using separatory funnel, it is molten with distilled water or alkalescence
Agent is rinsed and makes organic faciess to neutrality；The methanol solution of 8mL benzyltrimethylammonium hydroxides is added in organic faciess, is stirred at reflux anti-
Answer 24 hours；Filter, be dried, obtain final product caged octaphenyl silsesquioxane (POSS) of structure as shown in Figure 1.
Take 10g caged octaphenyl silsesquioxanes to be placed in round-bottomed flask, be added thereto to successively 100mL tetrahydrofurans,
The aqueous solution of 4mL25vol% Tetramethylammonium hydroxide, back flow reaction 4 hours；Dilute hydrochloric acid neutralization reaction liquid is added to neutrality；It is dense
Contracting removes volatilizable solvent therein, obtains white solid；Gained white solid is dissolved in benzene, and is processed with anhydrous magnesium sulfate,
Filter, the dry resulting solution of concentration obtains final product unfilled corner POSS of structure as shown in Figure 2：Seven phenyl of caged, three silanol silsesquioxane.
10g unfilled corners POSS are taken, and 15g Metaphosphoric acids and 100mL tetrahydrofuran solutions are added in 50 DEG C, are then heated to 60 DEG C,
Insulation reaction stopped reaction after 5 hours, filters, concentrates, obtain final product the phosphorus silicon composite flame-proof of the present invention of structure as shown in Figure 3
Agent：Seven phenyl of caged, three silicon phosphorus silsesquioxane.
Embodiment 2
75g phenyl trichlorosilanes, 350ml benzene are sequentially added in round-bottomed flask, 30mL water, body is slowly added to while stirring
System stands 6 hours after being stirred at room temperature 16 hours；The acid layer of bottom is removed using separatory funnel, with distilled water or basic solvent
Flushing makes organic faciess to neutrality；The methanol solution of 10mL benzyltrimethylammonium hydroxides is added in organic faciess, is stirred at reflux anti-
Answer 36 hours；Filter, be dried, obtain final product caged octaphenyl silsesquioxane (POSS) of structure as shown in Figure 1.
Take 15g caged octaphenyl silsesquioxanes to be placed in round-bottomed flask, be added thereto to successively 200mL tetrahydrofurans,
The aqueous solution of 6mL25vol% Tetramethylammonium hydroxide, back flow reaction 5 hours；Dilute hydrochloric acid neutralization reaction liquid is added to neutrality；It is dense
Contracting removes volatilizable solvent therein, obtains white solid；Gained white solid is dissolved in benzene, and is processed with anhydrous magnesium sulfate,
Filter, the dry resulting solution of concentration obtains final product unfilled corner POSS of structure as shown in Figure 2：Seven phenyl of caged, three silanol silsesquioxane.
10g unfilled corners POSS are taken, and 18g Metaphosphoric acids and 200mL tetrahydrofuran solutions are added in 40 DEG C, are then heated to 50 DEG C,
Insulation reaction stopped reaction after 6 hours, filters, concentrates, obtain final product the phosphorus silicon composite flame-proof of the present invention of structure as shown in Figure 3
Agent：Seven phenyl of caged, three silicon phosphorus silsesquioxane.
Embodiment 3
80g phenyl trichlorosilanes, 400ml benzene are sequentially added in round-bottomed flask, 40mL water, body is slowly added to while stirring
System stands 12 hours after being stirred at room temperature 8 hours；The acid layer of bottom is removed using separatory funnel, with distilled water or basic solvent
Flushing makes organic faciess to neutrality；The methanol solution of 13mL benzyltrimethylammonium hydroxides is added in organic faciess, is stirred at reflux anti-
Answer 36 hours；Filter, be dried, obtain final product caged octaphenyl silsesquioxane (POSS) of structure as shown in Figure 1.
Take 20g caged octaphenyl silsesquioxanes to be placed in round-bottomed flask, be added thereto to successively 250mL tetrahydrofurans,
The aqueous solution of 8mL25vol% Tetramethylammonium hydroxide, back flow reaction 6 hours；Dilute hydrochloric acid neutralization reaction liquid is added to neutrality；It is dense
Contracting removes volatilizable solvent therein, obtains white solid；Gained white solid is dissolved in benzene, and is processed with anhydrous magnesium sulfate,
Filter, the dry resulting solution of concentration obtains final product unfilled corner POSS of structure as shown in Figure 2：Seven phenyl of caged, three silanol silsesquioxane.
20g unfilled corners POSS are taken, and 25g Metaphosphoric acids and 250mL tetrahydrofuran solutions are added in 60 DEG C, are then heated to 80 DEG C,
Insulation reaction stopped reaction after 4 hours, filters, concentrates, obtain final product the phosphorus silicon composite flame-proof of the present invention of structure as shown in Figure 3
Agent：Seven phenyl of caged, three silicon phosphorus silsesquioxane.
The characterize data of POSS, unfilled corner POSS and phosphorus silicon composite flame-retardant agent of the present invention prepared by embodiment 1-3
And the detection data of thermal weight loss central temperature is as shown in Table 1 below.Wherein, thermal weight loss central temperature is to adopt《Polymer/laminated silicon
Silicate nanometer composite theory and practice》(QiZongNeng, Shang Wenyu are write, Chemical Industry Press, the heat mistake for 2002) specifying
Weight method detection.
Table 1
Thermal weight loss central temperature data as shown in Table 1 are visible：The phosphorus silicon composite flame-retardant agent that the present invention is provided has notable
Cooperative flame retardant effect.
Application examples 1
To in 95 grams of silicone rubber first components, 5g phosphorus silicon composite flame-retardant agents of the present invention are added, is stirred in 2000 revs/min
Mixing makes mix homogeneously (about 5 minutes)；0.8 gram of firming agent is added, and (about 0.5 point of mix homogeneously is made then at 2000 revs/min of stirrings
Clock)；It is poured in Teflon mould, vacuum exhaust is carried out under 150Pa vacuums after 80 DEG C of curing reactions 90 minutes, is obtained
To the silicon rubber composite material of the present invention.
Comparative example 1
This comparative example is the difference is that only with application examples 1：Phosphorus silicon of the present invention is not added with this comparative example multiple
Fire retardant is closed, remaining content is identical with described in application examples 1, i.e.,：
To in 95 grams of silicone rubber first components, 0.8 gram of firming agent is added, mix homogeneously is made in 2000 revs/min of stirrings；By its
Pour in Teflon mould, vacuum exhaust is carried out under 150Pa vacuums after 80 DEG C of curing reactions 90 minutes, obtains what is contrasted
Silicon rubber composite material.
Application examples 2
To in 96.5 grams of silicone rubber first components, 10g phosphorus silicon composite flame-retardant agents of the present invention are added, in 1500 revs/min
Clock stirring makes mix homogeneously (about 10 minutes)；1.0 grams of firming agent are added, and mix homogeneously (about 1 are made then at 1500 revs/min of stirrings
Minute)；It is poured in Teflon mould, vacuum exhaust is carried out under 156Pa vacuums after 75 points of 100 DEG C of curing reactions
Clock, obtains the silicon rubber composite material of the present invention.
Comparative example 2
This comparative example is the difference is that only with application examples 2：Phosphorus silicon of the present invention is not added with this comparative example multiple
Fire retardant is closed, remaining content is identical with described in application examples 2, i.e.,：
To in 96.5 grams of silicone rubber first components, 1.0 grams of firming agent are added, mix homogeneously is made in 1500 revs/min of stirrings；Will
Which is poured in Teflon mould, carries out vacuum exhaust after 100 DEG C of curing reactions 75 minutes, obtain right under 156Pa vacuums
The silicon rubber composite material of ratio.
Application examples 3
To in 98 grams of silicone rubber first components, 15g phosphorus silicon composite flame-retardant agents of the present invention are added, in 1000 revs/min
Stirring makes mix homogeneously (about 15 minutes)；1.4 grams of firming agent are added, and mix homogeneously (about 1.5 are made then at 1000 revs/min of stirrings
Minute)；It is poured in Teflon mould, vacuum exhaust is carried out under 160Pa vacuums after 60 points of 120 DEG C of curing reactions
Clock, obtains the silicon rubber composite material of the present invention.
Comparative example 3
This comparative example is the difference is that only with application examples 3：Phosphorus silicon of the present invention is not added with this comparative example multiple
Fire retardant is closed, remaining content is identical with described in application examples 3, i.e.,：
To in 98 grams of silicone rubber first components, 1.4 grams of firming agent are added, mix homogeneously is made in 1000 revs/min of stirrings；By its
Pour in Teflon mould, vacuum exhaust is carried out under 160Pa vacuums after 120 DEG C of curing reactions 60 minutes, is contrasted
Silicon rubber composite material.
Using《Nano composite polymer/laminated silicate material theory and practice》(QiZongNeng, Shang Wenyu are write, chemistry
Industrial publishing house, the thermogravimetry for 2002) specifying test the thermal weight loss central temperature of fire retardant powder body；Using GB/T 1701-
2001st, the mechanical property and fire resistance of GB10707-2008 national standards test silastic material.
With regard in the tensile strength of silastic material, elongation at break, thermal weight loss obtained by application examples 1-3 and comparative example 1-3
The test data of heart temperature and oxygen index (OI) is as shown in Table 2 below.
Table 2.
From 2 test result of table：The silastic material of compound phosphorus silicon fire retardant of the present invention is added with, is not only hindered
Combustion property is improved, and its heat-insulated suppression cigarette and mechanical property are improved.
Finally be necessary it is described herein be, above example only to illustrate technical scheme and unrestricted
Invention, although being described in detail to the present invention with reference to preferred embodiment, it will be understood by those within the art that, can
Modified or equivalent with the technical scheme to inventing, without deviating from the spirit and scope of technical solution of the present invention, its
All should cover in scope of the presently claimed invention.
Claims (6)
1. a kind of preparation method of phosphorus silicon composite flame-retardant agent, described phosphorus silicon composite flame-retardant agent have seven benzene of caged of following structure
Three silicon phosphorus silsesquioxane of base：
Characterized in that, the preparation method comprises the steps：
A) caged octaphenyl silsesquioxane (referred to as POSS) is made to be hydrolyzed reaction under organic base effect, prepared unfilled corner
POSS：Seven phenyl of caged, three silanol silsesquioxane；
B) by above-mentioned unfilled corner POSS：Seven phenyl of caged, three silanol silsesquioxane is reacted with Metaphosphoric acid, obtains described phosphorus silicon multiple
Close fire retardant.
2. preparation method as claimed in claim 1, it is characterised in that the preparation bag of described caged octaphenyl silsesquioxane
Include following steps：
1) phenyl trichlorosilane is made to stand 6～12 hours after being stirred at room temperature 8～16 hours with benzene and aqueous systems；
2) divide liquid, remove the acid layer of bottom, organic faciess are rinsed to pH=7 with distilled water or basic solvent；
3) to step 2) process after organic faciess in add benzyltrimethylammonium hydroxide methanol solution, be stirred at reflux reaction 24
～36 hours；
4) filter, be dried, obtain described caged octaphenyl silsesquioxane.
3. preparation method as claimed in claim 1, it is characterised in that：Organic base described in step a) is tetramethyl hydroxide
Ammonium；Described hydrolysis are caged octaphenyl silsesquioxane is returned in tetrahydrofuran, tetramethylammonium hydroxide aqueous solution
Stream reaction 4～6 hours.
4. preparation method as claimed in claim 3, it is characterised in that：Count in mass ratio, caged octaphenyl silsesquioxane: four
Hydrogen furan: tetramethylammonium hydroxide aqueous solution=(10～20): (100～250): (4～8)；Wherein, Tetramethylammonium hydroxide water
The concentration of volume percent of solution is 25～40%.
5. preparation method as claimed in claim 1, it is characterised in that：In step b), unfilled corner POSS：Seven phenyl of caged, three silanol
Silsesquioxane is reacted 4～6 hours in 50～80 DEG C in tetrahydrofuran with Metaphosphoric acid.
6. preparation method as claimed in claim 5, it is characterised in that：Count in mass ratio, seven phenyl of caged, three silanol sesquialter silicon
Oxygen alkane: Metaphosphoric acid：Tetrahydrofuran=(10～20): (15～25): (100～250).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410680503.8A CN104448830B (en) | 2014-11-24 | 2014-11-24 | A kind of phosphorus silicon composite flame-retardant agent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410680503.8A CN104448830B (en) | 2014-11-24 | 2014-11-24 | A kind of phosphorus silicon composite flame-retardant agent and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104448830A CN104448830A (en) | 2015-03-25 |
| CN104448830B true CN104448830B (en) | 2017-04-05 |
Family
ID=52895616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410680503.8A Active CN104448830B (en) | 2014-11-24 | 2014-11-24 | A kind of phosphorus silicon composite flame-retardant agent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104448830B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105086449B (en) * | 2015-09-11 | 2017-05-24 | 西北工业大学 | Phosphorus-containing POSS (polyhedral oligomeric silsesquioxane) flame-retardant bismaleimide resin and preparation method thereof |
| CN106118583A (en) * | 2016-06-26 | 2016-11-16 | 欧振云 | A kind of environment friendly flame-retardant silicone sealant |
| CN106220854B (en) * | 2016-07-26 | 2019-03-19 | 上海工程技术大学 | A kind of hyperbranched POSS fire retardant and its preparation method and application |
| CN106750328B (en) | 2016-11-23 | 2019-07-30 | 厦门大学 | A kind of fluorine silicon polyphosphate and its preparation method and application |
| CN108034246A (en) * | 2017-12-28 | 2018-05-15 | 南京鸿瑞塑料制品有限公司 | A kind of fire-retardant non-reinforcing PA66 composite materials of phosphorus silicon and preparation method thereof |
| CN111019135A (en) * | 2019-11-28 | 2020-04-17 | 广东宇星阻燃新材股份有限公司 | Hydrophobic unfilled corner POSS-BCPPO composite flame retardant and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2290452A1 (en) * | 2009-08-31 | 2011-03-02 | Xerox Corporation | Poss melamine overcoated photoconductors |
| US7985523B2 (en) * | 2008-12-18 | 2011-07-26 | Xerox Corporation | Toners containing polyhedral oligomeric silsesquioxanes |
| CN102702575A (en) * | 2012-06-07 | 2012-10-03 | 北京化工大学 | Unimolecular phosphorus-silicon-nitrogen intumescent flame retardant and preparation method thereof |
| CN103819634A (en) * | 2014-01-28 | 2014-05-28 | 厦门大学 | Block copolymer containing phosphorus and silicon and preparation method of block copolymer |
-
2014
- 2014-11-24 CN CN201410680503.8A patent/CN104448830B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7985523B2 (en) * | 2008-12-18 | 2011-07-26 | Xerox Corporation | Toners containing polyhedral oligomeric silsesquioxanes |
| EP2290452A1 (en) * | 2009-08-31 | 2011-03-02 | Xerox Corporation | Poss melamine overcoated photoconductors |
| CN102702575A (en) * | 2012-06-07 | 2012-10-03 | 北京化工大学 | Unimolecular phosphorus-silicon-nitrogen intumescent flame retardant and preparation method thereof |
| CN103819634A (en) * | 2014-01-28 | 2014-05-28 | 厦门大学 | Block copolymer containing phosphorus and silicon and preparation method of block copolymer |
Non-Patent Citations (2)
| Title |
|---|
| Mechanical and thermal properties and flame retardancy of phosphorus-containing polyhedral oligomeric silsesquioxane(DOPO-POSS)/polycarbonate composites;Wenchao Zhang et al.;《Polymer Degradation and Stability》;20101231;第95卷(第12期);2541-2546 * |
| 含苯基多面齐聚倍半硅氧烷的高分子的结构与性能研究;倪勇;《中国博士学位论文全文数据库（电子期刊）工程科技I辑》;20110415;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104448830A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448830B (en) | A kind of phosphorus silicon composite flame-retardant agent and its preparation method and application | |
| CN103980430B (en) | A kind of preparation method of unsaturated polyester (UP) flame-proof composite material | |
| CN102977613B (en) | Method for preparing halogen-free and flame-retardant silicon rubber | |
| CN110396284B (en) | Intumescent flame retardant, flame-retardant polylactic acid material and preparation method thereof | |
| CN102850622B (en) | Organic halogen-free flame-retardant silane cross-linked polyethylene and its preparation method and composition | |
| Yu et al. | Interfacial engineering to construct P-loaded hollow nanohybrids for flame-retardant and high-performance epoxy resins | |
| CN102827409A (en) | Halogen-free flame-retardant organosilane cross-linked polyethylene, and preparation method and composition thereof | |
| CN109054023B (en) | Preparation method of organic silicon-phosphorus synergistic flame retardant | |
| CN108410066B (en) | SiO (silicon dioxide)2Preparation method of nano particle modified expandable graphite and flame-retardant polypropylene | |
| CN106118065B (en) | A kind of expandable flame retardant silicon rubber and preparation method thereof | |
| CN110498952A (en) | A kind of intumescent high-efficiency compound fire-proof agent and preparation method thereof | |
| CN106189092A (en) | A kind of fiber reinforcement flame-retarded light high-strength composite material and preparation method thereof | |
| CN103396459A (en) | Method for preparing phosphorus silicate hybridization flame retardant from organic silicon waste liquid | |
| CN103073889B (en) | Flame retardant thermosetting resin and preparation method thereof | |
| Wu et al. | Design of P-decorated POSS towards flame-retardant, mechanically-strong, tough and transparent epoxy resins | |
| CN105315492B (en) | A kind of phosphorus silicon boron fire retardant preservative based on cage-type silsesquioxane and preparation method thereof | |
| CN102796283B (en) | Compound intumescent flame retardant and preparation method thereof | |
| CN114349968B (en) | POSS (polyhedral oligomeric silsesquioxane) modified phosphazene flame retardant and preparation method thereof, polycarbonate flame-retardant composite material and preparation method thereof | |
| CN106220854B (en) | A kind of hyperbranched POSS fire retardant and its preparation method and application | |
| Yu et al. | Cyclotriphosphazene hyperbranched P/N/Si prepared flame retardants improve mechanical properties and flame retardancy of epoxy resins | |
| CN106589656A (en) | Flame retardant masterbatch and flame retardant PVC wood-plastic wallboard prepared with masterbatch | |
| CN102675691B (en) | Organosilicone modified aluminum hydroxide fire retardant and preparation method thereof | |
| CN114213707B (en) | Intumescent flame retardant, preparation method and application thereof | |
| CN106633187A (en) | Safe and environment-friendly inorganic aluminum hypophosphite flame retardant and application thereof in PBT (polybutylene terephthalate) | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |