CN107099034A - A kind of phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures and its preparation method and application - Google Patents
A kind of phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures and its preparation method and application Download PDFInfo
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- CN107099034A CN107099034A CN201710278584.2A CN201710278584A CN107099034A CN 107099034 A CN107099034 A CN 107099034A CN 201710278584 A CN201710278584 A CN 201710278584A CN 107099034 A CN107099034 A CN 107099034A
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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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- 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
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- C08G77/06—Preparatory processes
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- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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- 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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- 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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention belongs to engineering plastics flame retardant area, and in particular to a kind of phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures and its preparation method and application.By technical scheme provided by the present invention, the phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures can be obtained.Its preparation method includes step：1) ODOPB reacts with bromo alkene or bromo alkynes, obtains intermediate product；2) step 1) obtained intermediate product carries out hydrosilylation with DDSQ, obtains the phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures.Phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures can be obtained by technical scheme provided by the present invention, such a fire retardant environmental protection, heat endurance is high, raw material is simple and easy to get, preparation method facilitates easy to operate, it is adaptable to PC/ABS alloys, with excellent anti-flammability.
Description
Technical field
The invention belongs to engineering plastics flame retardant area, and in particular to a kind of phosphorus silicon line containing DDSQ and ODOPB structures
Property copolymer fire retardant and its preparation method and application.
Background technology
Halogen flame, discharges a large amount of poisonous and harmful, corrosive gas when being used because of it, to human body and natural ring
Cause high risks and be gradually prohibited in border.Developing novel halogen-free flame-retardant agent turns into critical task, organic phosphorus flame retardant energy
Effectively the HRR of reduction material, reduces toxic gas and smoke release, is that one kind of halogenated flame retardant is substituted well
Thing, with good market prospects.
The oxide (DOPO) of -10 phospho hetero phenanthrene of -9 oxa- of 9,10- dihydro -10 and its derivative have high heat endurance, excellent
Good dissolubility, is often used as typical organophosphorous fire retardant, is widely used in high polymer material.Applied in DOPO derivatives
Most commonly used is 10- (2,5- dihydroxy phenyl)-miscellaneous phenanthrene -10- oxides of the miscellaneous -10- phosphinylidynes of 9,10- dihydro-9-oxies, referred to as
ODOPB.ODOPB contains the miscellaneous phenanthryl group of phosphinylidyne and obvious influence, contrast is produced on aggregated structure, organic-dissolvable and hot property
Other phosphate flame retardants, fire resistance is more preferable.
Silicon-series five-retardant due to its excellent fire resistance, be easy to processing, it is environmentally friendly, by extensive the advantages of low toxicity
Concern.Multiaspect cage type silsesquioxane (POSS) is a kind of poly- silica of organic-inorganic nano hydridization interesting in recent years
Alkane, possesses the inorganic caged kernel of Si-O-Si keys composition, by changing the organic group that Si atoms are connected, can prepare full
The polysiloxanes of the functional group of sufficient different demands, is used for modified polymer material as modifying agent either comonomer.Double fastener
The cage-type silsesquioxane (DDSQ) of plate shape has accurate two reactive functionalities, therefore can apply to linear organic-nothing
The synthesis of machine hybrid material.Catabolite can be prevented high poly- in polymer surfaces formation silica diaphragm under DDSQ high temperature
Thing is further aoxidized, and makes DDSQ is polymer-modified to have good heat endurance.But in the prior art, temporarily have no and direction of the present invention
Consistent technical scheme.
The content of the invention
It is linearly common the invention provides a kind of phosphorus silicon containing DDSQ and ODOPB structures to solve the deficiencies in the prior art
Polymers fire retardant and its preparation method and application.The present invention is anti-by Si―H addition reaction by DDSQ and the compound of the structure containing ODOPB
Should, a kind of phosphorus silicon linear copolymer containing DDSQ and ODOPB structures is synthesized, and be applied to the fire-retardant of PC/ABS alloys
In, the fire resistance of alloy can be improved, the flame retarding efficiency of fire retardant is improved, good flame retardant effect is obtained.
Technical scheme provided by the present invention is as follows：
Phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures, its general structure is as shown in Equation 1：
Wherein, R=-CH2-CH2-CH2- or-CH=CH-CH2-, n is 8~10 integer.
Phosphorus silicon linear copolymer fire retardant provided by the present invention containing DDSQ and ODOPB structures is environmentally friendly, contains
Silicon phosphorus content is high, and with cooperative flame retardant effect, flame retarding efficiency is high.Element silicon and P elements can form collaboration system, P elements
Promote into carbon in combustion process, element silicon improves the heat endurance of carbon-coating, and element silicon and P elements are introduced simultaneously is greatly improved resistance
Fuel efficiency fruit.
Present invention also offers a kind of preparation side of the phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures
Method, it is characterised in that comprise the following steps：
1) ODOPB reacts with bromo alkene or bromo alkynes, obtains intermediate product；
2) step 1) obtained intermediate product carries out hydrosilylation with DDSQ, obtains containing DDSQ and ODOPB structures
Phosphorus silicon linear copolymer fire retardant；
Wherein, ODOPB structural formula is
DDSQ structural formula is：
The synthetic route of above-mentioned technical proposal is as shown in Equation 2：
Specifically, step 1) reaction be the inferior synthetic reaction of William.
Specifically, step 1) carried out under the conditions of lewis base.
Specifically, lewis base is potassium carbonate.
Specifically, step 1) in：
Bromo alkene is 3- bromopropenes；
Bromo alkynes is 3- propargyl bromides.
Specifically, step 1) in：
Under solvent condition carry out, the solvent be acetonitrile, ethanol, acetone, methanol or isopropanol in any one or
A variety of mixing；
The ratio between ODOPB, bromo alkene or bromo alkynes, the amount of material of potassium carbonate are 1：3.0~6.0：4.0~6.0.
Specifically, step 2) in, hydrosilylation is carried out under karstedt catalysts conditions.
Specifically, step 2) in：
Hydrosilylation is carried out under solvent condition, the solvent be THF, toluene, DMF or benzene in any one or
A variety of mixing；
The amount ratio of the material of DDSQ and intermediate product is 1：0.5~2, catalyst is 20/1000000ths of reactant gross mass
~40.
Specifically, preparation process is：
1) by ODOPB, Anhydrous potassium carbonate and solvent are added in the round-bottomed flask with stirrer, add a small amount of 18 crown-
6,6h is stirred at room temperature, adds bromopropene (or propargyl bromide) temperature rising reflux and stays overnight, suction filtration is depressurized after the completion of reaction, filtrate is spin-dried for, two
Chloromethanes Diethyl ether recrystallization obtains white powdery solids a (or b)；
2) white powdery solids a (or b), DDSQ, nitrogen protection are sequentially added in the three-neck flask with stirrer
Lower addition solvent and catalyst, are progressively warming up to the boiling point of solvent, and 18~30h of back flow reaction, rotary evaporation is removed after dereaction
Organic solvent, be down to normal temperature, obtain slightly yellow solid, be containing DDSQ and ODOPB structures phosphorus silicon linear copolymer resistance
Fire agent.
The preparation method of phosphorus silicon linear copolymer fire retardant provided by the present invention containing DDSQ and ODOPB structures passes through
Short synthetic route is that can prepare the phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures.Synthesis condition
Gently, yield is high, and purity is high, it is easy to purify.The fire retardant prepared by this method is environmentally friendly, siliceous phosphorus content
Height, with cooperative flame retardant effect, flame retarding efficiency is high.
Present invention also offers the phosphorus silicon linear copolymer fire retardant provided by the present invention containing DDSQ and ODOPB structures
Application, be applied in PC/ABS as phosphorus silicon synergistic fire retardant.
The phosphorus silicon linear copolymer containing DDSQ and ODOPB structures can be obtained by technical scheme provided by the present invention
Fire retardant, such a fire retardant environmental protection, heat endurance is high, and raw material is simple and easy to get, and preparation method facilitates easy to operate, it is adaptable to
PC/ABS alloys, with excellent anti-flammability.
Embodiment
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to
Limit the scope of the present invention.
Embodiment 1
ODOPB (0.97g, 3mmol), Anhydrous potassium carbonate (2.07g, 15mmol) is added in the mono- neck flasks of 50mL, adds third
Ketone (20mL) and a small amount of crown ether, stirring at normal temperature 6h add bromopropene (1.0mL, 12mmol), and 60 DEG C of backflow 12h are cooled to room
Temperature, suction filtration, filtrate is spin-dried for, and dichloromethane and Diethyl ether recrystallization obtain white solid, and vacuum drying 12h obtains ODOPB derivatives a
(1.09g, 90%).The addition DDSQ (5.0g, 4.35mmol) in the reactor with stirrer, derivative a (1.74g,
4.35mmol), anhydrous THF (30mL), nitrogen protection is lower to be added after 45uL karstedt catalyst, stirring 30min, 60 DEG C of bars
36h is reacted under part makes reaction complete；Vacuum distillation removes solvent after the completion of reaction, and it is formula 3 to be recrystallized to give gray solid
Copolymer I (5.66g, 84%).1H NMR(ppm,CDCl3):0.23(6H,CH3-Si),0.33(4H,-CH2-Si),2.0
(4H ,-CH2-CH2-O-Ph),3.63(4H,-CH2- O-Ph), 6.35-8.0 (m, 96H, phenyl ring)；31P NMR (ppm, CDCl3)：
21.04-23.36；29Si NMR(ppm,CDCl3):- 37.81, -77.73 and -78.69.
Embodiment 2
ODOPB (0.97g, 3mmol), Anhydrous potassium carbonate (1.66g, 12mmol) is added in the mono- neck flasks of 50mL, adds third
Ketone (20mL) and a small amount of crown ether, stirring at normal temperature 6h add bromopropene (1.0mL, 12mmol), and 60 DEG C of backflow 12h are cooled to room
Temperature, suction filtration, filtrate is spin-dried for, and dichloromethane and Diethyl ether recrystallization obtain white solid, and vacuum drying 12h obtains ODOPB derivatives a
(1.02g, 85%).The addition DDSQ (5.0g, 4.35mmol) in the reactor with stirrer, derivative a (1.74g,
4.35mmol), dry toluene (30mL), nitrogen protection is lower to be added after 45uL karstedt catalyst, stirring 30min, 110 DEG C
Under the conditions of reaction 36h make reaction complete；Vacuum distillation removes solvent after the completion of reaction, and it is formula 3 to be recrystallized to give gray solid
Copolymer I (4.58g, 68%).
Embodiment 3
ODOPB (0.97g, 3mmol), Anhydrous potassium carbonate (1.66g, 12mmol) is added in the mono- neck flasks of 50mL, adds third
Ketone (20mL) and a small amount of crown ether, stirring at normal temperature 6h add propargyl bromide (1.0mL, 12mmol), and 60 DEG C of backflow 12h are cooled to room
Temperature, suction filtration, filtrate is spin-dried for, and dichloromethane and Diethyl ether recrystallization obtain white solid, and vacuum drying 12h obtains ODOPB derivatives b
(1.02g, 85%).The addition DDSQ (5.0g, 4.35mmol) in the reactor with stirrer, derivative b (1.76g,
4.35mmol), anhydrous THF (30mL), nitrogen protection is lower to be added after 45uL karstedt catalyst, stirring 30min, 60 DEG C of bars
36h is reacted under part makes reaction complete；Vacuum distillation removes solvent after the completion of reaction, and it is formula 4 to be recrystallized to give gray solid
Copolymers II (5.95g, 88%).1H NMR(ppm,CDCl3):0.23(6H,CH3-Si),0.33(4H,-CH2-Si),4.23
(4H,-CH2- O-Ph), 5.56 (2H ,-CH=CH-O-Ph), 6.35-8.0 (m, 96H, phenyl ring)；31P NMR (ppm, CDCl3)：
21.35-24.44；29Si NMR(ppm,CDCl3):- 46.81, -77.73 and -78.82.
Embodiment 4
ODOPB (0.97g, 3mmol), Anhydrous potassium carbonate (2.07g, 15mmol) is added in the mono- neck flasks of 50mL, adds third
Ketone (20mL) and a small amount of crown ether, stirring at normal temperature 6h add propargyl bromide (1.25mL, 15mmol), and 60 DEG C of backflow 12h are cooled to room
Temperature, suction filtration, filtrate is spin-dried for, and dichloromethane and Diethyl ether recrystallization obtain white solid, and vacuum drying 12h obtains ODOPB derivatives b
(1.12g, 92%).The addition DDSQ (5.0g, 4.35mmol) in the reactor with stirrer, derivative b (1.76g,
4.35mmol), dry toluene (30mL), nitrogen protection is lower to be added after 45uL karstedt catalyst, stirring 30min, 110 DEG C
Under the conditions of reaction 36h make reaction complete；Vacuum distillation removes solvent after the completion of reaction, and it is formula 4 to be recrystallized to give gray solid
Copolymers II (4.78g, 71%).
Effect example
The phosphorus silicon fire retardant that the present invention is provided is added in PC/ABS alloys using as follows：
Flame retardant test uses Vertical combustion instrument and limited oxygen index instrument, is tested according to respective standard.
Shown in fire resistance test data table 1 below：
From upper table it will be seen that using phosphorus silicon linear copolymer fire retardant provided by the present invention, alloy anti-flammability
Can more preferably, also, fire retardant II is slightly stronger than the effect of fire retardant I.The amount of fire retardant can influence the anti-flammability of PC/ABS alloys simultaneously
Can, with the increase of phosphorus silicon flame retardant amount, flame retardant effect is better, when flame retardant amount reaches 10%, fire retardation PC/ABS LOI values
26.8%, more than 27.0%, UL-94 can be increased to and reach V0 grades, PC/ABS application needs are met.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures, it is characterised in that its general structure such as formula
Shown in 1：
Wherein, R=-CH2-CH2-CH2- or-CH=CH-CH2-, n is 8~10 integer.
2. a kind of preparation method of the phosphorus silicon linear copolymer fire retardant containing DDSQ and ODOPB structures, it is characterised in that including
Following steps：
1) ODOPB reacts with bromo alkene or bromo alkynes, obtains intermediate product；
2) step 1) obtained intermediate product carries out hydrosilylation with DDSQ, obtains the phosphorus containing DDSQ and ODOPB structures
Silicon linear copolymer fire retardant；
Wherein, ODOPB structural formula is
DDSQ structural formula is：
3. the preparation method of the phosphorus silicon linear copolymer fire retardant according to claim 2 containing DDSQ and ODOPB structures,
It is characterized in that：Step 1) reaction be the inferior synthetic reaction of William.
4. the preparation method of the phosphorus silicon linear copolymer fire retardant according to claim 3 containing DDSQ and ODOPB structures,
It is characterized in that：Step 1) carried out under the conditions of lewis base.
5. the preparation method of the phosphorus silicon linear copolymer fire retardant according to claim 4 containing DDSQ and ODOPB structures,
It is characterized in that：Lewis base is potassium carbonate.
6. the preparation method of the phosphorus silicon linear copolymer fire retardant according to claim 5 containing DDSQ and ODOPB structures,
Characterized in that, step 1) in：
Bromo alkene is 3- bromopropenes；
Bromo alkynes is 3- propargyl bromides.
7. the preparation method of the phosphorus silicon linear copolymer fire retardant according to claim 6 containing DDSQ and ODOPB structures,
Characterized in that, step 1) in：
Reaction under solvent condition carry out, the solvent be acetonitrile, ethanol, acetone, methanol or isopropanol in any one or
A variety of mixing；
The ratio between ODOPB, bromo alkene or bromo alkynes, the amount of material of potassium carbonate are 1：3.0~6.0：4.0~6.0.
8. the preparation method of the phosphorus silicon linear copolymer fire retardant according to claim 2 containing DDSQ and ODOPB structures,
It is characterized in that：Step 2) in, hydrosilylation is carried out under karstedt catalysts conditions.
9. the preparation method of the phosphorus silicon linear copolymer fire retardant according to claim 8 containing DDSQ and ODOPB structures,
Characterized in that, step 2) in：
Hydrosilylation is carried out under solvent condition, and the solvent is any one or more in THF, toluene, DMF or benzene
Mixing；
The amount ratio of the material of DDSQ and intermediate product is 1：0.5~2, karstedt catalyst are million points of reactant gross mass
20~40.
10. a kind of phosphorus silicon linear copolymer fire retardant according to claim 1 containing DDSQ and ODOPB structures should
With, it is characterised in that：It is applied in PC/ABS as phosphorus silicon synergistic fire retardant.
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Cited By (3)
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| 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 |
| CN110734551A (en) * | 2019-09-25 | 2020-01-31 | 锦西化工研究院有限公司 | high-strength high-heat-resistant flame-retardant transparent polycarbonate resin and preparation method thereof |
| CN112795019A (en) * | 2020-12-31 | 2021-05-14 | 常州大学 | Phenyl sulfonic acid silicone oil ester flame retardant and preparation method thereof |
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| US6441067B1 (en) * | 2001-08-23 | 2002-08-27 | Chung-Shan Institute Of Science & Technology | Phosphorus-containing compounds and their use in flame retardance |
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2017
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| US6441067B1 (en) * | 2001-08-23 | 2002-08-27 | Chung-Shan Institute Of Science & Technology | Phosphorus-containing compounds and their use in flame retardance |
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| CN104558683A (en) * | 2015-01-21 | 2015-04-29 | 三峡大学 | DOPO-containing cyclic phosphate flame retardant as well as preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110734551A (en) * | 2019-09-25 | 2020-01-31 | 锦西化工研究院有限公司 | high-strength high-heat-resistant flame-retardant transparent polycarbonate resin and preparation method thereof |
| CN110734551B (en) * | 2019-09-25 | 2022-05-13 | 锦西化工研究院有限公司 | High-strength high-heat-resistance flame-retardant transparent polycarbonate resin and preparation method thereof |
| CN112795019A (en) * | 2020-12-31 | 2021-05-14 | 常州大学 | Phenyl sulfonic acid silicone oil ester flame retardant and preparation method thereof |
| CN112795019B (en) * | 2020-12-31 | 2022-05-31 | 常州大学 | Phenyl sulfonic acid silicone oil ester flame retardant and preparation method thereof |
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Application publication date: 20170829 |