CN109370157A - A kind of siliceous response type epoxy fire retardant and its application in the epoxy - Google Patents
A kind of siliceous response type epoxy fire retardant and its application in the epoxy Download PDFInfo
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- CN109370157A CN109370157A CN201811236361.0A CN201811236361A CN109370157A CN 109370157 A CN109370157 A CN 109370157A CN 201811236361 A CN201811236361 A CN 201811236361A CN 109370157 A CN109370157 A CN 109370157A
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- siliceous
- fire retardant
- type epoxy
- response type
- epoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
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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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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
Application the invention discloses a kind of siliceous response type epoxy fire retardant and its in the epoxy, the epoxy fire retardant is by 9, bis- (the 4- hydroxyphenyls) -4 of 9-, 5- carboline, chlorosilane dissolve in anhydrous solvent, reaction a period of time in a nitrogen atmosphere, then obtained siliceous intermediate is mixed with epoxychloropropane, phase transfer catalyst, after a period of time of heat preservation at a certain temperature carries out open loop etherificate, sodium hydroxide solution closed loop is added, reaction overnight, then is extracted, and is spin-dried for, vacuum drying, the final fire retardant for obtaining high activity.Obtained flame-retardant agent is added in epoxy resin, the glass transition temperature and thermal stability of material can be improved significantly, had wide practical use in thermosetting material.
Description
Technical field
The invention belongs to functional epoxy resin technology fields, and in particular to a kind of siliceous epoxy fire retardant of novel reaction type
And the preparation method and application thereof method.
Background technique
Epoxy resin is widely used in coating, adhesive, electronics, aerospace etc., however epoxy resin is easy
Combustion property limits its scope of application, the especially application in electronics and microelectronic field.
Traditional halogen containing flame-retardant has very big harm to environment, and therefore, the halogen-free flame retardants of phosphorus system and silicon systems is concerned.
But phosphorus flame retardant is added in epoxy resin, it is also possible to there are problems that thermal stability, glass transition temperature reduce.And silicon
Though the thermal stability and anti-flammability of epoxy resin can be improved in flame retardant, the reduction of glass transition temperature is also resulted in.
Summary of the invention
The purpose of the present invention is to provide a kind of siliceous response type epoxy fire retardants, add it in epoxy resin, can
To significantly improve the glass transition temperature, thermal stability and flame retardant property of epoxy resin.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of siliceous response type epoxy fire retardant, preparation method includes the following steps:
(1) bis- (4- hydroxyphenyl) -4, the 5- carbolines of 9,9- are mixed with chlorosilane, adds anhydrous solvent to dissolve, 50 ~ 80 DEG C, nitrogen
6 ~ 8h of nucleo philic substitution reaction in atmosphere obtains siliceous intermediate；
(2) the siliceous intermediate of gained is mixed with epoxychloropropane, phase transfer catalyst, 3 ~ 5h is kept the temperature at 60 ~ 80 DEG C, then
Sodium hydroxide solution is added dropwise, reaction is overnight；Products therefrom is extracted through ethyl acetate, is spin-dried for, vacuum drying, obtains the resistance of yellow epoxy
Fire agent.
The molar ratio of bis- (4- the hydroxyphenyl) -4,5- carbolines of 9,9- and chlorosilane is (1 ~ 4) in step (1): (0.5 ~
1.5)；Wherein, the chlorosilane is one or both of dimethyldichlorosilane, diphenyl dichlorosilane.
Siliceous intermediate used in step (2), epoxychloropropane, phase transfer catalyst and sodium hydroxide molar ratio be (1
~ 4): (5 ~ 20): (0.1 ~ 0.5): (3 ~ 20)；Wherein, the phase transfer catalyst is tetrabutylammonium bromide, dodecyl front three
One or both of base ammonium bromide.
In molar ratio (1 ~ 4) by the siliceous response type epoxy fire retardant and bisphenol A type epoxy resin: after (6 ~ 9) are blended,
In 120 ~ 180 DEG C of 3 ~ 7h of solidification, gained cured product has high glass-transition temperature and high flame resistance.
Remarkable advantage of the invention is:
(1) present invention is introduced into phenodiazine is fluorene structured on the main chain of epoxy resin, provides rigidity double pyridine structures in the molecule,
Epoxy resin high glass-transition temperature, high hot property and thermal oxidation can be assigned；
(2) present invention enters organosilicon structures on the main chain of epoxy resin, and-the Si-O- that pyrolytic generates moves to material
The surface of material can form fine and close protective layer, and effectively barrier heat and oxygen reach material internal, so as to effectively improve epoxy
The thermal stability and flame retardant property of resin；
(3) present invention has synthesized a kind of novel reaction type ring oxygen fire retardant, has preferable compatibility with epoxy resin, can be with ring
Oxygen resin is sufficiently mixed, co-curing；
(4) the raw materials used in the present invention is cheap, process stabilizing, has reached practical and industrialized condition.
Detailed description of the invention
Fig. 1 is the infrared spectrum comparison diagram of embodiment 1 raw materials used, siliceous intermediate and product.
Fig. 2 is the thermogravimetric curve that embodiment 1-3 corresponds to product.
Fig. 3 is the oxygen index (OI) that embodiment 1-3 corresponds to product.
Fig. 4 is fissipation factor-temperature curve that embodiment 1-3 corresponds to product.
Fig. 5 is the load-deformation curve that experimental example 1-3 corresponds to product.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Bis- (4- hydroxyphenyl) -4,5- carbolines of 9,9- used () reference literature
“Highly sensitive and selective fluorescent chemosensor for Ni2+ based on a
New poly (arylene ether) with terpyridine substituent groups " (Analyst 138(23)
7090-7093) prepared.
Embodiment 1
(1) by bis- (4- the hydroxyphenyl) -4,5- carbolines (OH-spiro-DFO) of 9,9- and diphenyl dichlorosilane in molar ratio 1:
0.5 mixing is added anhydrous dimethyl sulphoxide dissolution, is allowed to be sufficiently mixed, then the insulation reaction 6h in 60 DEG C, nitrogen atmosphere,
Obtain siliceous intermediate (DHPFS)；
(2) by the siliceous intermediate of gained, 1:5 is mixed in molar ratio with epoxychloropropane, is warming up to 80 DEG C, then press phase transfer catalysis (PTC)
The molar ratio of agent and siliceous intermediate is that tetrabutylammonium bromide is added in 0.1:1, keeps the temperature 3h, is cooled to room temperature, then by quality point
The sodium hydroxide solution that number is 50% is that 5:1 is added by the molar ratio with siliceous intermediate, and reaction is overnight；Products therefrom is through acetic acid
Ethyl ester extraction, is spin-dried for after liquid separation, is dried in vacuo, obtains yellow solid (DEPFS)；
(3) by gained yellow solid, 1:9 is mixed in molar ratio with E-51, it is to be mixed uniformly after, be added curing agent DDM, at 160 DEG C
Lower solidification 5h, obtains cured product.
Fig. 1 is the infrared spectrum comparison diagram of raw materials used, siliceous intermediate and product.As seen from Figure 1, with raw material (OH-
Spiro-DFO it) compares, siliceous intermediate (DHPFS) is in 1118 cm-1With 1247 cm-1There is typical absorption peak, illustrates two
Diphenyl dichlorosilane is successfully introduced into material frame, and yellow fire retardant (DEPFS) is in 913 cm-1There is typical absorption peak,
Confirm that epoxy resin successfully synthesizes.
Embodiment 2
(1) by bis- (4- the hydroxyphenyl) -4,5- carbolines (OH-spiro-DFO) of 9,9- and diphenyl dichlorosilane in molar ratio 1:
0.5 mixing is added anhydrous dimethyl sulphoxide dissolution, is allowed to be sufficiently mixed, then the insulation reaction 6h in 60 DEG C, nitrogen atmosphere,
Obtain siliceous intermediate (DHPFS)；
(2) by the siliceous intermediate of gained, 1:10 is mixed in molar ratio with epoxychloropropane, is warming up to 80 DEG C, then press phase transfer catalysis (PTC)
The molar ratio of agent and siliceous intermediate is that tetrabutylammonium bromide is added in 0.2:3, keeps the temperature 3h, is cooled to room temperature, then by quality point
The sodium hydroxide solution that number is 50% is that 10:1 is added by the molar ratio with siliceous intermediate, and reaction is overnight；Products therefrom is through acetic acid
Ethyl ester extraction, is spin-dried for after liquid separation, is dried in vacuo, obtains yellow solid (DEPFS)；
(3) by gained yellow solid, 2:8 is mixed in molar ratio with E-51, it is to be mixed uniformly after, be added curing agent DDM, at 160 DEG C
Lower solidification 5h, obtains cured product.
Embodiment 3
(1) by bis- (4- the hydroxyphenyl) -4,5- carbolines (OH-spiro-DFO) of 9,9- and diphenyl dichlorosilane in molar ratio 1:
0.5 mixing is added anhydrous dimethyl sulphoxide dissolution, is allowed to be sufficiently mixed, then the insulation reaction 6h in 60 DEG C, nitrogen atmosphere,
Obtain siliceous intermediate (DHPFS)；
(2) by the siliceous intermediate of gained, 1:15 is mixed in molar ratio with epoxychloropropane, is warming up to 80 DEG C, then press phase transfer catalysis (PTC)
The molar ratio of agent and siliceous intermediate is that tetrabutylammonium bromide is added in 0.3:4, keeps the temperature 3h, is cooled to room temperature, then by quality point
The sodium hydroxide solution that number is 50% is that 15:1 is added by the molar ratio with siliceous intermediate, and reaction is overnight；Products therefrom is through acetic acid
Ethyl ester extraction, is spin-dried for after liquid separation, is dried in vacuo, obtains yellow solid (DEPFS)；
(3) by gained yellow solid, 3:7 is mixed in molar ratio with E-51, it is to be mixed uniformly after, be added curing agent DDM, at 160 DEG C
Lower solidification 5h, obtains cured product.
Embodiment 4
(1) by bis- (4- the hydroxyphenyl) -4,5- carbolines (OH-spiro-DFO) of 9,9- and diphenyl dichlorosilane in molar ratio 4:
1.5 mixing are added anhydrous dimethyl sulphoxide dissolution, are allowed to be sufficiently mixed, then the insulation reaction 6h in 80 DEG C, nitrogen atmosphere,
Obtain siliceous intermediate (DHPFS)；
(2) by the siliceous intermediate of gained, 1:20 is mixed in molar ratio with epoxychloropropane, is warming up to 60 DEG C, then press phase transfer catalysis (PTC)
The molar ratio of agent and siliceous intermediate is that tetrabutylammonium bromide is added in 0.5:4, keeps the temperature 5h, is cooled to room temperature, then by quality point
The sodium hydroxide solution that number is 50% is that 20:1 is added by the molar ratio with siliceous intermediate, and reaction is overnight；Products therefrom is through acetic acid
Ethyl ester extraction, is spin-dried for after liquid separation, is dried in vacuo, obtains yellow solid (DEPFS)；
(3) by gained yellow solid, 4:6 is mixed in molar ratio with E-51, it is to be mixed uniformly after, be added curing agent DDM, at 180 DEG C
Lower solidification 3h, obtains cured product.
Fig. 2 is the thermogravimetric curve that embodiment 1-3 corresponds to product.It can be seen that being mixed with the increase of DEPFS doping
The thermal stability of resin improves, and carbon left increases under high temperature.At 800 DEG C, modified resin carbon left reaches 30%, and
The carbon left of E-51 is less than 10%, it was demonstrated that phenodiazine is fluorene structured to be introduced into epoxy resin, and the thermostabilization of material can be significantly improved
Property.
Fig. 3 is the oxygen index (OI) that embodiment 1-3 corresponds to product.It can be seen that with the increase of DEPFS doping, oxygen refers to
Number is gradually increased, and flame retardant property steps up.When doping reaches 20%, the single fire retardant of gained just has excellent fire-retardant
Performance (traditional fire retardant is all much the composite flame-retardant agents such as phosphorus silicon systems, phosphorus nitrogen system and phosphorus silicon nitrogen system) illustrates using phenodiazine
The fluorene structured single fire retardant that preparation is combined with organosilicon structures can significantly improve the flame retardant property of material.
Fig. 4 is fissipation factor-temperature curve that embodiment 1-3 corresponds to product.It can be seen that with DEPFS doping
Increase, glass transition temperature is gradually increased, and single peak is presented always, it was demonstrated that DEPFS has good phase with epoxy resin
Capacitive.
Fig. 5 is the load-deformation curve that experimental example 1-3 corresponds to product.It can be seen that with the increasing of DEPFS doping
Add, the intensity and toughness of modified epoxy resin all improve a lot, and illustrate that the linear response type fire retardant of synthesis can be right
Epoxy resin plays the role of activeness and quietness.
Existing organic silicon fibre retardant is to be incorporated into epoxy resin with polysiloxanes to be modified branch mostly, but organic
The poor compatibility of silicon fire retardant and epoxy resin, glass transition temperature are low.For example, " Synthesis and thermal
Characterization of phosphorus containing siliconized epoxy resins " (European
Polymer Journal 42 (10), 2419-2429) in, though adding the oxygen index (OI) of the epoxy resin of organosilicon can achieve
32%, but its glass transition temperature is only 123 DEG C.And in the present invention, the oxygen index (OI) for being added to the epoxy resin of 30% DEPFS is reachable
30.1%, and up to 187 DEG C of glass transition temperature, it is comprehensive much higher than the epoxy resin for being added to organosilicon.Present invention reaction
On the one hand type organic silicon fibre retardant introduces upper a large amount of Si-O on main chain, make single fire retardant that can reach fire-retardant well
Effect；On the other hand, there is good compatibility with epoxy resin, and there is great crosslink density, therefore can be in vitrifying temperature
Degree does not affect the mechanical properties while raising.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. a kind of siliceous response type epoxy fire retardant, it is characterised in that: preparation method includes the following steps:
(1) bis- (4- hydroxyphenyl) -4, the 5- carbolines of 9,9- are mixed with chlorosilane, adds anhydrous solvent to dissolve, in certain temperature, nitrogen
A period of time is reacted in gas atmosphere, obtains siliceous intermediate；
(2) siliceous intermediate is mixed with epoxychloropropane, phase transfer catalyst, at a certain temperature heat preservation a period of time, so
After be added dropwise sodium hydroxide solution, reaction is overnight；Products therefrom is extracted through ethyl acetate, is spin-dried for, and vacuum drying obtains yellow epoxy
Fire retardant.
2. siliceous response type epoxy fire retardant according to claim 1, it is characterised in that: bis- (the 4- oxybenzenes of 9,9- in step (1)
Base) molar ratio of -4,5- carboline and chlorosilane is (1 ~ 4): (0.5 ~ 1.5)；
The chlorosilane is one or both of dimethyldichlorosilane, diphenyl dichlorosilane.
3. siliceous response type epoxy fire retardant according to claim 1, it is characterised in that: the temperature of reaction described in step (1)
Degree is 50 ~ 80 DEG C, and the time is 6 ~ 8h.
4. siliceous response type epoxy fire retardant according to claim 1, it is characterised in that: siliceous centre used in step (2)
Body, epoxychloropropane, phase transfer catalyst and sodium hydroxide molar ratio be (1 ~ 4): (5 ~ 20): (0.1 ~ 0.5): (3 ~ 20)；
The phase transfer catalyst is one or both of tetrabutylammonium bromide, dodecyl trimethyl ammonium bromide.
5. siliceous response type epoxy fire retardant according to claim 1, it is characterised in that: holding temperature is 60 in step (2)
~ 80 DEG C, the time is 3 ~ 5h.
6. a kind of application method of siliceous response type epoxy fire retardant in the epoxy, feature as described in claim 1 exist
In: in molar ratio (1 ~ 4) by the epoxy fire retardant and bisphenol A type epoxy resin: after (6 ~ 9) are blended, solidifying in 120 ~ 180 DEG C
3~7h。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811236361.0A CN109370157B (en) | 2018-10-23 | 2018-10-23 | Silicon-containing reactive epoxy flame retardant and application thereof in epoxy resin |
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| CN201811236361.0A CN109370157B (en) | 2018-10-23 | 2018-10-23 | Silicon-containing reactive epoxy flame retardant and application thereof in epoxy resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979921A (en) * | 2021-02-25 | 2021-06-18 | 中国船舶重工集团公司第七二五研究所 | In-situ response corrosion-inhibition type epoxy resin and preparation method and application thereof |
| CN115466371A (en) * | 2022-09-09 | 2022-12-13 | 中国船舶重工集团公司第七二五研究所 | Intermediate of high-shielding self-corrosion-inhibition material, preparation method of intermediate, preparation method of high-shielding self-corrosion-inhibition material and application of intermediate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3414494A1 (en) * | 1984-04-17 | 1985-10-24 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of halogenated arylsiloxanes |
| CN103130982A (en) * | 2012-11-08 | 2013-06-05 | 桂林理工大学 | Composite method and solidifying method of fluorine-containing high temperature resisting organosilicon epoxy resin |
| CN103360417A (en) * | 2013-07-16 | 2013-10-23 | 苏州科技学院 | Flame retardant tri(dichloropropyl)tribromophenylsilicate compound and preparation method thereof |
| CN104710470A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Sencorer triester(dimethyl dihalogen propoxy silicon acid ) compound serving as fire retardant and preparation method of sencorer triester(dimethyl dihalogen propoxy silicon acid ) compound |
-
2018
- 2018-10-23 CN CN201811236361.0A patent/CN109370157B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3414494A1 (en) * | 1984-04-17 | 1985-10-24 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of halogenated arylsiloxanes |
| CN103130982A (en) * | 2012-11-08 | 2013-06-05 | 桂林理工大学 | Composite method and solidifying method of fluorine-containing high temperature resisting organosilicon epoxy resin |
| CN103360417A (en) * | 2013-07-16 | 2013-10-23 | 苏州科技学院 | Flame retardant tri(dichloropropyl)tribromophenylsilicate compound and preparation method thereof |
| CN104710470A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Sencorer triester(dimethyl dihalogen propoxy silicon acid ) compound serving as fire retardant and preparation method of sencorer triester(dimethyl dihalogen propoxy silicon acid ) compound |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979921A (en) * | 2021-02-25 | 2021-06-18 | 中国船舶重工集团公司第七二五研究所 | In-situ response corrosion-inhibition type epoxy resin and preparation method and application thereof |
| CN115466371A (en) * | 2022-09-09 | 2022-12-13 | 中国船舶重工集团公司第七二五研究所 | Intermediate of high-shielding self-corrosion-inhibition material, preparation method of intermediate, preparation method of high-shielding self-corrosion-inhibition material and application of intermediate |
| CN115466371B (en) * | 2022-09-09 | 2023-09-29 | 中国船舶重工集团公司第七二五研究所 | Intermediate of high-shielding self-corrosion-inhibition material, preparation method of intermediate, preparation method and application of high-shielding self-corrosion-inhibition material |
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