CN106750317A - One kind is based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof - Google Patents
One kind is based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof Download PDFInfo
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- CN106750317A CN106750317A CN201710025145.0A CN201710025145A CN106750317A CN 106750317 A CN106750317 A CN 106750317A CN 201710025145 A CN201710025145 A CN 201710025145A CN 106750317 A CN106750317 A CN 106750317A
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- 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
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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
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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
Abstract
The invention discloses one kind based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof, the fire retardant is the oxide of 10 dihydro, 9 oxa-, 10 phospho hetero phenanthrene 10 by 9（DOPO）And its DOPO derivatives and VTES（VTES）Generation hydrogenates addition and prepared by acid-catalyzed hydrolysis condensation reaction, the fire retardant, phosphorus content is high, flame retarding efficiency is high, heat-resist, influences small to the mechanical property of materials, for products such as high-temperature silicon disulfide rubber and room temperature vulcanized silicone rubbers, can also be used as the heat-resistance type fire retardant of thermoplastic macromolecule material simultaneously, while phosphorus content is high, a small amount of addition can play excellent flame retardant effect, distinctive POSS structures belong to half inorganic type organosilicon material, improve the heat resistance of fire retardant.
Description
Technical field
The invention belongs to fire proofing technical field, and in particular to the one kind for organic silicon rubber highly effective flame-retardant is based on cage
Shape polysilsesquioxane phosphonium flame retardant and preparation method thereof.
Background technology
During organic silicon rubber material is extensively using industrial production and daily life, with certain burning self-extinguishment, but resistance
Combustion property is poor, and high flame retardancy silicon rubber is still the emphasis of current research.Can be used at present the fire retardant of silicon rubber can be divided into it is halogen
Fire retardant and the major class of halogen-free flame retardants two, because halogen containing flame-retardant has very big environmental protection pressure, many countries have forbidden making
With halogen-free anti-flaming silicon rubber is the focus of research.
The fire retardant that halogen-free anti-flaming silicon rubber is used mainly has inorganic combustion inhibitor（Such as magnesium aluminum hydroxide, hydration boric acid
Zinc）, phosphorus flame retardant, nitrogenated flame retardant, phosphorus nitrogen expansion type combustion inhibitor etc..There is addition greatly in these fire retardants, flame retarding efficiency
Low, decomposition temperature is low, and the flame-proof silicon rubber proportion of preparation is larger, and the mechanical performance of material deteriorates seriously, and heat resistance is poor.This
Outer flame-proof silicon rubber is also had and is used as fire retardant using platinum catalyst, and this based flame retardant is expensive, and is used alone, effect
Fruit substantially, will typically not compound phosphorus-nitrogen containing flame retardant.Efficient high-temp resistant fire-retarding agent is the emphasis of flame-proof silicon rubber research.
The content of the invention
In order to overcome above-mentioned technical problem, the invention provides one kind based on caged polysilsesquioxane phosphonium flame retardant and
Its preparation method, for products such as high-temperature silicon disulfide rubber and room temperature vulcanized silicone rubbers, while can also be used as thermoplasticity high score
The heat-resistance type fire retardant of sub- material is used.Phosphorus content is high simultaneously, and a small amount of addition can play excellent flame retardant effect, distinctive
POSS structures（Cage modle polysilsesquioxane, English name polyhedral oligomeric silsesquioxane, referred to as
POSS）Belong to half inorganic type organosilicon material, improve the heat resistance of fire retardant.
One kind is based on caged polysilsesquioxane phosphonium flame retardant, is by DOPO（, the miscellaneous -10- phosphas of 9,10- dihydro-9-oxies
Phenanthrene -10- oxides）And VTES（VTES）According to certain mol proportion, catalytic addition prepares DOPO-VTES,
Then prepared under acid catalysis and be based on caged polysilsesquioxane phosphonium flame retardant.The fire retardant has following chemical structural formula：
R：
The 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide（DOPO）Chemical structural formula is as follows：
Described VTES（VTES）Chemical structural formula is as follows：
Reaction equation is as follows:
Present invention also offers one kind based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof, including：Including step
It is rapid as follows：
1）By DOPO at 80 ~ 120 DEG C, it is vacuum dried at preferably 100 ~ 110 DEG C 4 ~ 8 hours, preferably 4 hours, drying is finished
After DOPO is completely dissolved using organic solvent A, it is placed in autoclave, is passed through nitrogen protection simultaneously mechanical agitation 1 ~ 4 hour, it is excellent
Select 2 ~ 3 hours；
2）To catalyst is added in above-mentioned autoclave, be warming up to 70 ~ 95 DEG C, preferably 80 ~ 90 DEG C, and continue stirring 0.2 ~
0.8 hour, preferably 0.5 hour；
3）VTES is slowly dropped in above-mentioned autoclave, 70 ~ 95 DEG C of keeping temperature, persistently stirs 20 by preferably 80 ~ 90 DEG C
~ 25 hours.Split-phase solution is obtained, upper strata light yellow liquid is taken, vacuum distillation is addition product DOPO-VTES after removing solvent；
4）Take DOPO-VTES and be dissolved in and the reaction vessel equipped with condenser is added after methyl alcohol, acid solution is added dropwise, be warming up to 40 ~ 80 DEG C, it is excellent
40 ~ 70 DEG C are selected, most preferably 60 ~ 70 DEG C, continues to stir, mixing speed 50r/min, mixing time 10-30 hours, suction filtration after cooling
It is preferred that 20-25 hours white powder, is washed with deionized, obtain phosphorous based on caged polysilsesquioxane after 100 DEG C of dryings
Fire retardant.
Above-mentioned preparation method is related to a kind of dehydration condensation hydrogenated under addition reaction and acid catalysis, by phosphorous DOPO and
POSS silicon materials are combined together, and by the fire-retardant with phosphorus content higher of the method synthesis, POSS structures have one in itself
Fixed anti-flammability and heat-resistant quality high, while POSS has good compatibility with silicon rubber, the fire retardant for thus preparing is in silicon
In the absence of the problem of difficulties in dispersion in rubber, smaller, excellent fireproof performance is influenceed on silicone rubber mechanical performance.
Further, step of the present invention（1）Described organic solvent A is ethanol, chloroform, dimethylformamide, dioxane
In at least one.
Further, the present invention added in autoclave by organic solvent A dissolve DOPO when, DOPO solution it is dense
It is 0.5 ~ 2mol/L to spend.
Further, step of the present invention（2）Described catalyst is the aqueous isopropanol wherein chloroplatinic acid quality point of chloroplatinic acid
In number 1%, platinum-tetrahydrofuran complex, platinum (0) -1,3- divinyl -1,1,3,3- tetramethyl disiloxane complex compounds at least
One kind, adding proportion is the 0.05 ~ 0.5% of DOPO and VTES gross masses, preferably 0.1 ~ 0.3%, most preferably 0.2 ~ 0.3%.
The use of catalyst can strengthen the further heterolytic fission of phosphorus hydrogen bond on DOPO molecular structures, so as to the second of vinyl three
TMOS reacts, and improves reaction rate and yield, shortens the reaction time.
Further, described in step of the present invention DOPO and the mol ratio of VTES is 1:1 ~ 2, preferably 1:1 ~ 1.5, most preferably 1:
1~1.2。
Further, step of the present invention（4）Described acid solution is concentrated hydrochloric acid that mass fraction is 37%, mass fraction is 98%
Dilute sulfuric acid, the dust technology that mass fraction is 65%, the phosphoric acid that mass fraction is 85% at least one, addition is
The 0.5 ~ 5% of DOPO-VTES, preferably 1 ~ 3.5%, more preferably 1.5 ~ 2.5%.
Specific embodiment
The technology of the present invention method is described further with reference to specific embodiment.But the present invention be not limited to
The embodiment of lower proposition.
Embodiment 1
1）216g DOPO are vacuum dried 8h at 110 DEG C, the DOPO that drying is finished is completely molten with DMF
Xie Hou, is placed in autoclave, is passed through nitrogen protection simultaneously mechanical agitation 3 hours；
2）To the aqueous isopropanol that chloroplatinic acid is added in above-mentioned autoclave（Chloroplatinic acid mass fraction 1%）, 80 DEG C are warming up to,
And continue to stir 0.5 hour,；
3）228g VTES are slowly dropped in above-mentioned autoclave, 80 DEG C of keeping temperature, persistently stirred 25 hours.Obtain
Split-phase solution, takes upper strata light yellow liquid, and vacuum distillation is addition product DOPO-VTES, yield 88% after removing solvent.
4）150g DOPO-VTES are added into the reaction vessel equipped with condenser, 40 ~ 80 DEG C are warming up to, 3g 37% is added dropwise dense
Hydrochloric acid, continues to stir, mixing speed 50r/min mixing time 30h, and suction filtration obtains white powder after cooling, is washed with deionized water
Wash, obtained after 100 DEG C of dryings based on caged polysilsesquioxane phosphonium flame retardant, yield 82%.
Embodiment 2
1）216g DOPO are vacuum dried 4h at 110 DEG C, after the DOPO isopropanols that drying is finished are completely dissolved, are placed in
In autoclave, nitrogen protection simultaneously mechanical agitation 3 hours are passed through；
2）To platinum-tetrahydrofuran complex is added in above-mentioned autoclave, 90 DEG C are warming up to, and continue stirring 0.4 hour,；
3）190g VTES are slowly dropped in above-mentioned autoclave, 90 DEG C of keeping temperature, persistently stirred 20 hours.Obtain
Split-phase solution, takes upper strata light yellow liquid, and vacuum distillation is addition product DOPO-VTES, yield 80% after removing solvent.
4）150g DOPO-VTES are added into the reaction vessel equipped with condenser, 70 DEG C are warming up to, 1.75g 85% is added dropwise dense
Phosphoric acid, continues to stir, mixing speed 50r/min mixing time 20h, and suction filtration obtains white powder after cooling, is washed with deionized water
Wash, obtained after 100 DEG C of dryings based on caged polysilsesquioxane phosphonium flame retardant, yield 86%.
Embodiment 3
1）216g DOPO are vacuum dried 8h at 110 DEG C, DOPO Isosorbide-5-Nitraes-dioxane that drying is finished is completely dissolved
Afterwards, it is placed in autoclave, is passed through nitrogen protection simultaneously mechanical agitation 3 hours；
2）To platinum (0) -1,3- divinyl -1 is added in above-mentioned autoclave, 1,3,3- tetramethyl disiloxane complex compound rises
Temperature continues stirring 0.8 hour to 85 DEG C；
3）202g VTES are slowly dropped in above-mentioned autoclave, 85 DEG C of keeping temperature, persistently stirred 25 hours.Obtain
Split-phase solution, takes upper strata light yellow liquid, and vacuum distillation is addition product DOPO-VTES, yield 79% after removing solvent.
4）150g DOPO-VTES are added into the reaction vessel equipped with condenser, 75 DEG C are warming up to, the dense nitre of 2g 65% is added dropwise
Acid, continues to stir, mixing speed 50r/min mixing time 25h, and suction filtration obtains white powder after cooling, is washed with deionized,
Obtained after 100 DEG C of dryings based on caged polysilsesquioxane phosphonium flame retardant, yield 90%.
Embodiment 4
1）216g DOPO are vacuum dried 6h at 100 DEG C, the DOPO that drying is finished is completely molten with DMF
Xie Hou, is placed in autoclave, is passed through nitrogen protection simultaneously mechanical agitation 2 hours；
2）To platinum-vinyl methyl siloxane complex compound is added in above-mentioned autoclave, 80 DEG C are warming up to, and continue stirring
0.5 hour；
3）190g VTES are slowly dropped in above-mentioned autoclave, 80 DEG C of keeping temperature, persistently stirred 20 hours.Obtain
Split-phase solution, takes upper strata light yellow liquid, and vacuum distillation is addition product DOPO-VTES, yield 76% after removing solvent.
4）150g DOPO-VTES are added into the reaction vessel equipped with condenser, 75 DEG C are warming up to, the dense sulphur of 2g 98% is added dropwise
Acid, continues to stir, mixing speed 50r/min mixing time 22h, and suction filtration obtains white powder after cooling, is washed with deionized,
Obtained after 100 DEG C of dryings based on caged polysilsesquioxane phosphonium flame retardant, yield 91%.
Fire resistance is tested：By 100g end-vinyl silicon rubber（Molecular weight is 60-80 × 104Da）, the silicon of 50g hexamethyls two
Azane is modified gas-phase silica（Specific surface area 250m2/g）, it is 10g, 15g, 20g that fire retardant is added respectively, is mixed in kneader
After closing uniformly, double two or five vulcanizing agents are added, 10min, then the secondary sulphur in 200 DEG C of baking ovens are vulcanized on 140 DEG C of vulcanizing presses
Change 4 hours, test sample performance, such as table（1）.
It is of the present invention a kind of based on caged polysilsesquioxane phosphonium flame retardant, resistance from the point of view of experimental data more than
Combustion efficiency high, the influence to the mechanical performance of material is smaller, and especially the combination property of example 1 is best, when addition is 11 parts, just
UL94 V-0 ranks are reached.
Claims (7)
1. it is a kind of to be based on caged polysilsesquioxane phosphonium flame retardant, it is characterised in that the fire retardant has the change as shown in (I)
Learn structural formula：
Wherein R has such as（Ⅱ）Shown chemical structural formula.
2. a kind of preparation method based on caged polysilsesquioxane phosphonium flame retardant according to claim 1, its feature
It is, including step is as follows：
1）DOPO is vacuum dried 4 ~ 8h at 80 ~ 120 DEG C, after the DOPO organic solvent As that drying is finished are completely dissolved, is put
In autoclave, nitrogen protection simultaneously mechanical agitation 1 ~ 4 hour is passed through；
2）To catalyst is added in above-mentioned autoclave, 70 ~ 95 DEG C are warming up to, and continue stirring 0.2 ~ 0.8 hour,；
3）VTES is slowly dropped in above-mentioned autoclave, 70 ~ 95 DEG C of keeping temperature, persistently stirred 20 ~ 25 hours,
Split-phase solution is obtained, upper strata light yellow liquid is taken, vacuum distillation is addition product DOPO-VTES, as after removing solvent
Intermediate product；
4）DOPO-VTES is added into the reaction vessel equipped with condenser, 40 ~ 80 DEG C are warming up to, acid solution is added dropwise, continue to stir, stirred
Speed 50r/min mixings time _ 10-30h is mixed, suction filtration obtains white powder after cooling, is washed with deionized, 100 DEG C of dryings
After obtain based on caged polysilsesquioxane phosphonium flame retardant.
3. a kind of preparation method based on caged polysilsesquioxane phosphonium flame retardant according to claim 2, its feature exists
In step 1）Described organic solvent A is at least one in ethanol, chloroform, dimethylformamide, dioxane.
4. the preparation method based on caged polysilsesquioxane phosphonium flame retardant according to claim 2, it is characterised in that：
When the DOPO dissolved by organic solvent A is added in autoclave, the concentration of DOPO solution is 0.5 ~ 2mol/L.
5. a kind of preparation method based on caged polysilsesquioxane phosphonium flame retardant according to claim 2, its feature
It is, step 1）Described catalyst is the aqueous isopropanol of chloroplatinic acid, wherein chloroplatinic acid mass fraction 1%, platinum-tetrahydrofuran
Complex compound, platinum (0) -1,3- divinyl -1, at least one in 1,3,3- tetramethyl disiloxane complex compound, adding proportion is
The 0.05 ~ 0.5% of DOPO and VTES gross masses.
6. a kind of preparation method based on caged polysilsesquioxane phosphonium flame retardant according to claim 2, its feature
It is that described DOPO and the mol ratio of VTES are 1:1~2.
7. a kind of preparation method based on caged polysilsesquioxane phosphonium flame retardant according to claim 1, its feature
It is, step 1）Described acid solution is concentrated hydrochloric acid that mass fraction is 37%, the concentrated sulfuric acid that mass fraction is 98%, mass fraction are
At least one of 65% dust technology, the phosphoric acid that mass fraction is 85%, addition is the 0.5 ~ 5% of DOPO-VTES mass.
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| CN107936572A (en) * | 2017-11-17 | 2018-04-20 | 华南理工大学 | A kind of high transparency heat oxygen aging resistance add-on type liquid silicon rubber and preparation method thereof |
| CN108299737A (en) * | 2017-12-26 | 2018-07-20 | 上海普利特复合材料股份有限公司 | A kind of halogen-free polypropylene flame redardant aesthetic resin composite material and preparation method |
| CN109135197A (en) * | 2018-08-30 | 2019-01-04 | 北京理工大学 | A kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition and its preparation method and application |
| CN110294846A (en) * | 2018-03-21 | 2019-10-01 | 中国科学院化学研究所 | A kind of cage web frame of the group containing DOPO mixes silsesquioxane fire retardant and the preparation method and application thereof |
| CN110627999A (en) * | 2019-08-14 | 2019-12-31 | 江西瀚泰新材料科技有限公司 | Epoxy resin anti-ultraviolet flame-retardant curing agent and preparation thereof |
| CN111072973A (en) * | 2019-05-28 | 2020-04-28 | 杭州师范大学 | Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant |
| CN111269461A (en) * | 2020-03-09 | 2020-06-12 | 贵州民族大学 | Phosphaphenanthrene silane grafted and modified graphene and preparation method thereof |
| CN111748091A (en) * | 2020-06-18 | 2020-10-09 | 浙江恒澜科技有限公司 | P-N-Si synergistic flame-retardant polyamide 6 and preparation method thereof |
| CN112812712A (en) * | 2021-02-25 | 2021-05-18 | 北华大学 | Flame-retardant adhesive and application thereof |
| CN113174283A (en) * | 2021-04-02 | 2021-07-27 | 安徽中天石化股份有限公司 | High-performance phosphate flame-retardant hydraulic oil |
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| CN114605717A (en) * | 2022-04-18 | 2022-06-10 | 中广核研究院有限公司 | Halogen-free environment-friendly flame-retardant rubber and preparation method thereof |
| CN114835902A (en) * | 2022-05-06 | 2022-08-02 | 江南大学 | POSS (polyhedral oligomeric silsesquioxane) -based flame retardant containing phosphorus, nitrogen and silicon elements and preparation method thereof |
| CN114854091A (en) * | 2021-02-03 | 2022-08-05 | 中国科学院化学研究所 | Flame-retardant vinyl resin and preparation method and application thereof |
| CN114891227A (en) * | 2022-06-09 | 2022-08-12 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation method of halogen-free flame-retardant modified epoxy resin |
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| CN116572603A (en) * | 2023-07-13 | 2023-08-11 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
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Application publication date: 20170531 |