CN109096493A - A kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof - Google Patents
A kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof Download PDFInfo
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- CN109096493A CN109096493A CN201810970055.3A CN201810970055A CN109096493A CN 109096493 A CN109096493 A CN 109096493A CN 201810970055 A CN201810970055 A CN 201810970055A CN 109096493 A CN109096493 A CN 109096493A
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- fire retardant
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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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The present invention relates to a kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof, belong to Fire Retardant of The Expoxy Resin technical field.Structural formula is:
Description
Technical field
The present invention relates to a kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof, belong to Fire Retardant of The Expoxy Resin
Technical field.
Background technique
In recent years, high molecular material is grown rapidly, and also proposed tightened up requirement to the comprehensive performance of material.Asphalt mixtures modified by epoxy resin
Rouge as a kind of thermosetting resin being most widely used, have adhesion strength height, good stability of the dimension, excellent in mechanical performance,
The advantages that good insulating and chemical property are stablized, has good development prospect and researching value.However, inflammable is asphalt mixtures modified by epoxy resin
One of major defect of rouge above receives many restrictions in application.Therefore, fire retardant preparation resistance is added by substrate of epoxy resin
Combustion epoxy composite material always is the hot spot of research.
A kind of flame-resistant electronic material is disclosed in 107815277 A of Chinese patent application publication number CN, wherein epoxy resin
Fire retardant used contains bromo element, and the virose corrosive gas of tool can be released after burning, is runed counter to environmental protection concept.
A kind of phosphoric epoxy resin flame retardant and its system are disclosed in 103304819 A of Chinese patent application publication number CN
Preparation Method.Although the epoxy resin after addition fire retardant can reach UL-94V-0 rank, additive amount is larger.
Disclosed in 107400194 A of Chinese patent application publication number CN New-type halide-free reaction-type flame-retarding curing agent and its
Preparation method.The flame retardant curing agent molecular weight is low, and additive amount is 15wt% in the epoxy, and UL-94 can be only achieved V-0 grades,
Limit oxygen index is only 27%, and flame retarding efficiency is general.
Summary of the invention
The purpose of the present invention is to solve halogen existing for additive flame retardant, molecular weight is small, additive amount is big and matrix
Compatibility is bad, the easy moisture absorption, the problems such as flame retarding efficiency is not high, and provides a kind of polymerization reaction type Fire Retardant of The Expoxy Resin and its system
Preparation Method.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of polymerization reaction type Fire Retardant of The Expoxy Resin, structural formula is:
Wherein integer of the polymerization degree n between 5-200.
A kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof, the specific steps are as follows:
Step 1: pentaerythrite and distilled phosphorus oxychloride are added in solvent A under the protection of inert gas, first
It mixes at room temperature to stable system, is to slowly warm up to certain temperature, be stirred to react to no hydrogen chloride gas and release, use dichloro
Methane, chloroform or acetone wash product, filter, and dry 12h, obtains intermediate spiral shell in vacuum drying oven 85 DEG C
Cyclic phosphate diacid chloride.
Step 2: P-aminobenzene-sulfonamide is added in solvent B, is stirred to clarify under the protection of inert gas
It is bright, the intermediate spiro-phosphate diacid chloride of step 1 synthesis is added, to system after mixing, acid binding agent is added in stirring,
It is stirred at reflux at 50~60 DEG C 2 hours, is to slowly warm up to 60~80 DEG C and reacts 8~12 hours, with acetone washing, filtered, 80 DEG C
It is dried in vacuo 2h, obtains white powdery solid.
Step 1: inert gas described in step 2 is one of nitrogen, argon gas and helium；
The molar ratio of pentaerythrite described in step 1 and phosphorus oxychloride is 1:(3~7)；
Solvent A described in step 1 is any one of anhydrous acetonitrile, toluene；
Certain temperature described in step 1 corresponds to solvent A, respectively 80 DEG C, 105 DEG C；
Solvent described in step 2 includes anhydrous acetonitrile, tetrahydrofuran, dimethyl sulfoxide.
The molar ratio of spiro-phosphate diacid chloride and P-aminobenzene-sulfonamide described in step 2 is 1:(1.0~1.2)；
Acid binding agent described in step 2 includes triethylamine, pyridine and Anhydrous potassium carbonate；Spiro-phosphate diacid chloride and tie up acid
The molar ratio of agent is 1:1.
Beneficial effect
1, a kind of polymerization reaction type Fire Retardant of The Expoxy Resin provided by the invention, containing ignition-proof elements such as phosphorus, nitrogen, Halogen is low
Poison meets environmental protection concept.
2, a kind of polymerization reaction type Fire Retardant of The Expoxy Resin provided by the invention, good with matrix compatibility, molecular weight is higher,
Molecular weight distribution is relatively narrow, and anti-moisture absorption is good, and flame retarding efficiency is high, and in the epoxy, when additive amount is 10%, limit oxygen index reaches
To 30.2%；Vertical burn test grade is up to UL-94V-0 rank.
3, a kind of polymerization reaction type Fire Retardant of The Expoxy Resin provided by the invention, preparation method is simple, reaction condition is mild,
It is easy to control, fire retardant purity is high.
Specific embodiment
Embodiment is provided below in conjunction with experimental result of the present invention with the invention will be further described
Embodiment 1:
A kind of polymerization reaction type Fire Retardant of The Expoxy Resin, structural formula is:
Wherein integer of the polymerization degree n between 5-200.
5.1g (0.0375mol) pentaerythrite is weighed in 250mL four-hole boiling flask, and 17.25g (0.1125mol) is added
Distilled phosphorus oxychloride and 50mL anhydrous acetonitrile, connect thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas.
Under nitrogen atmosphere, it first mixes at room temperature to stable system, is to slowly warm up to 80 DEG C, reaction to no HCl gas releasing is
Only (reaction terminates).It is cooled to room temperature, obtained sediment is filtered, is washed for several times with methylene chloride, acetone or chloroform,
80 DEG C of vacuum drying 12h, obtain white powdery solids intermediate 10.5g, and as spiro-phosphate diacid chloride, yield is
93.6%.
The molar ratio that spiro-phosphate diacid chloride and P-aminobenzene-sulfonamide are pressed to 1:1, weighs P-aminobenzene-sulfonamide
4.306g (0.025mol) is added to four of the 250mL with thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas
In mouthful flask, under the atmosphere of nitrogen, is stirred to clarify in the anhydrous acetonitrile of 50mL transparent, add 7.45g
To system after mixing, three second of 3.5mL (0.025mol) are added in the spiro-phosphate diacid chloride of (0.025mol), stirring
Amine, 50 DEG C of pre-reaction 2h, then 80 DEG C are to slowly warm up to, and stirring 12h reaction terminates, the sediment that reaction obtains filtered,
And with acetone washing, 80 DEG C of vacuum drying oven dry 6h, it is dry after white solid 9.3g, yield 93.3%.
Fire retardant in the present embodiment is applied in bisphenol A type epoxy resin (E-44), 4,4'- diaminodiphenylmethane
As curing agent, fire retarding epoxide resin is prepared.When fire retardant additive amount is 10%, limit oxygen index is up to 30.2%, vertically
Combustion rating is up to UL-94V-0 grades.
Embodiment 2:
A kind of polymerization reaction type Fire Retardant of The Expoxy Resin, structural formula is:
Wherein integer of the polymerization degree n between 5-200.
10.2g (0.075mol) pentaerythrite is weighed in 250mL four-hole boiling flask, and 45.9g (0.3mol) distillation is added
The phosphorus oxychloride and 60mL toluene crossed, connect thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas.In argon atmospher
It under enclosing, first mixes at room temperature to stable system, is to slowly warm up to 105 DEG C, (reaction until reaction to no HCl gas is released
Terminate).It is cooled to room temperature, obtained sediment is filtered, is washed for several times with methylene chloride, acetone or chloroform, 80 DEG C true
The dry 12h of sky, obtains white powdery solids intermediate 21.0g, as spiro-phosphate diacid chloride, yield 93.8%.
The molar ratio that spiro-phosphate diacid chloride and P-aminobenzene-sulfonamide are pressed to 1:1.05, weighs P-aminobenzene-sulfonamide
9.042g (0.0525mol) is added to four of the 250mL with thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas
In mouthful flask, under the atmosphere of argon gas, is stirred to clarify in the dimethyl sulfoxide of 80mL transparent, add 14.9g
The spiro-phosphate diacid chloride of (0.05mol) is stirred to system after mixing, the triethylamine of addition 7mL (0.05mol), 60
DEG C pre-reaction 2h, then 75 DEG C are to slowly warm up to, stirring 10h reaction terminates, and is slowly added dropwise into chloroform, stands, will analyse
Sediment out is filtered, and with acetone washing, 80 DEG C of vacuum drying oven dry 6h, it is dry after white solid 18.6g, yield
93.6%.
Embodiment 3:
A kind of polymerization reaction type Fire Retardant of The Expoxy Resin, structural formula is:
Wherein integer of the polymerization degree n between 5-200.
13.6g (0.1mol) pentaerythrite is weighed in 250mL four-hole boiling flask, and 76.5g (0.5mol) is added and distilled
Phosphorus oxychloride and 100mL toluene, connect thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas.In argon atmosphere
Under, it first mixes at room temperature to stable system, is to slowly warm up to 105 DEG C, (reaction knot until reaction to no HCl gas is released
Beam).It is cooled to room temperature, obtained sediment is filtered, is washed for several times with methylene chloride, acetone or chloroform, 80 DEG C of vacuum
Dry 12h, obtains white powdery solids intermediate 28.0g, as spiro-phosphate diacid chloride, yield 94.0%.
The molar ratio that spiro-phosphate diacid chloride and P-aminobenzene-sulfonamide are pressed to 1:1.1, weighs P-aminobenzene-sulfonamide
18.95g (0.11mol) is added to four mouthfuls of the 250mL with thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas
In flask, under the atmosphere of argon gas, is stirred to clarify in the tetrahydrofuran of 100mL transparent, add 29.8g's (0.1mol)
To system after mixing, the Anhydrous potassium carbonate of 13.8g (0.1mol) is added in spiro-phosphate diacid chloride, stirring, and 60 DEG C pre- anti-
2h is answered, then is to slowly warm up to 70 DEG C, stirring 12h reaction terminates, and the sediment that reaction obtains is filtered, and is washed with acetone
It washs, 80 DEG C of vacuum drying oven dry 6h, obtains white solid 37.2g, yield 93.7% after dry.
Embodiment 4:
A kind of polymerization reaction type Fire Retardant of The Expoxy Resin, structural formula is:
Wherein integer of the polymerization degree n between 5-200.
17g (0.125mol) pentaerythrite is weighed in 500mL four-hole boiling flask, and 114.75g (0.75mol) distillation is added
The phosphorus oxychloride and 100mL acetonitrile crossed, connect thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas.In helium-atmosphere
It under enclosing, first mixes at room temperature to stable system, is to slowly warm up to 80 DEG C, (reaction knot until reaction to no HCl gas is released
Beam).It is cooled to room temperature, obtained sediment is filtered, is washed for several times with methylene chloride, acetone or chloroform, 80 DEG C of vacuum
Dry 12h, obtains white powdery solids intermediate 35.1g, as spiro-phosphate diacid chloride, yield 94.1%.
The molar ratio that spiro-phosphate diacid chloride and P-aminobenzene-sulfonamide are pressed to 1:1.15, weighs P-aminobenzene-sulfonamide
24.76g (0.11mol) is added to four mouthfuls of the 250mL with thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas
In flask, under the atmosphere of helium, is stirred to clarify in the tetrahydrofuran of 100mL transparent, add 37.25g
The spiro-phosphate diacid chloride of (0.125mol) is stirred to system after mixing, the pyridine of addition 9.9g (0.125mol), 50
DEG C pre-reaction 2h, then be to slowly warm up to 80 DEG C, stirring 10h reaction terminates, and sediment that reaction obtains is filtered, and with third
Ketone washing, 80 DEG C of vacuum drying oven dry 6h obtain white solid 46.5g, yield 93.7% after dry.
Embodiment 5:
A kind of polymerization reaction type Fire Retardant of The Expoxy Resin, structural formula is:
Wherein integer of the polymerization degree n between 5-200.
20.4g (0.15mol) pentaerythrite is weighed in 500mL four-hole boiling flask, and 160.7g (1.05mol) distillation is added
The phosphorus oxychloride and 150mL toluene crossed, connect thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas.In helium-atmosphere
It under enclosing, first mixes at room temperature to stable system, is to slowly warm up to 105 DEG C, (reaction until reaction to no HCl gas is released
Terminate).It is cooled to room temperature, obtained sediment is filtered, is washed for several times with methylene chloride, acetone or chloroform, 80 DEG C true
The dry 12h of sky, obtains white powdery solids intermediate 42.3g, as spiro-phosphate diacid chloride, yield 94.6%.
The molar ratio that spiro-phosphate diacid chloride and P-aminobenzene-sulfonamide are pressed to 1:1.2, weighs P-aminobenzene-sulfonamide
31.00g (0.18mol) is added to four mouthfuls of the 500mL with thermometer, mechanical agitator, condenser pipe and device for absorbing tail gas
In flask, under the atmosphere of helium, is stirred to clarify in the acetonitrile of 150mL transparent, add the spiral shell of 44.7g (0.15mol)
Cyclic phosphate diacid chloride is stirred to system after mixing, the triethylamine of addition 21mL (0.15mol), 60 DEG C of pre-reaction 2h, then
It is to slowly warm up to 65 DEG C, stirring 12h reaction terminates, and sediment that reaction obtains is filtered, and use acetone washing, vacuum baking
80 DEG C of case dry 6h obtain white solid 55.7g, yield 93.6% after dry.
Above-described specific descriptions have carried out further specifically the purpose of invention, technical scheme and beneficial effects
It is bright, it should be understood that the above is only a specific embodiment of the present invention, the protection model being not intended to limit the present invention
It encloses, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection scope within.
Claims (7)
1. a kind of polymerization reaction type Fire Retardant of The Expoxy Resin, it is characterised in that: structural formula is:
Wherein integer of the polymerization degree n between 5-200.
2. a kind of preparation method of polymerization reaction type Fire Retardant of The Expoxy Resin, it is characterised in that: specific step is as follows:
Step 1: pentaerythrite and distilled phosphorus oxychloride are added in solvent A under the protection of inert gas, first in room
It mixes under temperature to stable system, is to slowly warm up to certain temperature, be stirred to react to no hydrogen chloride gas and release, use dichloromethane
Alkane, chloroform or acetone wash product, filter, and dry 12h, obtains intermediate loop coil in vacuum drying oven 85 DEG C
Phosphate diacid chloride；
Step 2: P-aminobenzene-sulfonamide is added in solvent B under the protection of inert gas, stir to clarify it is transparent, then
The intermediate spiro-phosphate diacid chloride of step 1 synthesis is added, to system after mixing, acid binding agent is added in stirring, 50~
60 DEG C are stirred at reflux 2 hours, are to slowly warm up to 60~80 DEG C and react 8~12 hours, with acetone washing, filter, and 80 DEG C of vacuum are dry
Dry 2h obtains white powdery solid to get polymerization reaction type Fire Retardant of The Expoxy Resin is arrived.
3. a kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof as claimed in claim 2, it is characterised in that: described
Inert gas be one of nitrogen, argon gas and helium.
4. a kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof as claimed in claim 2, it is characterised in that: step
The molar ratio of pentaerythrite described in one and phosphorus oxychloride is 1:(3~7)；Spiro-phosphate diacid chloride described in step 2 with it is right
The molar ratio of aminobenzene sulfonamide is 1:(1.0~1.2).
5. a kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof as claimed in claim 2, it is characterised in that: step
Solvent A described in one is anhydrous acetonitrile or toluene；Solvent described in step 2 includes that anhydrous acetonitrile, tetrahydrofuran or dimethyl are sub-
Sulfone.
6. a kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof as claimed in claim 2, it is characterised in that: step
Certain temperature described in one is 80 DEG C, 105 DEG C；When solvent A selects anhydrous acetonitrile, temperature is 80 DEG C；When solvent A selects toluene
When, temperature is 105 DEG C.
7. a kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof as claimed in claim 2, it is characterised in that: step
Acid binding agent described in two includes triethylamine, pyridine and Anhydrous potassium carbonate；The molar ratio of spiro-phosphate diacid chloride and acid binding agent is
1:1。
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| CN201810970055.3A CN109096493A (en) | 2018-08-24 | 2018-08-24 | A kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183684A (en) * | 2019-06-13 | 2019-08-30 | 西北师范大学 | A kind of modified oil shale semicoke and preparation method thereof and the application in high molecular material |
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| GB2352447B (en) * | 1999-07-28 | 2003-10-15 | Bolton Inst Higher Education | Flame retardancy treatment of polymeric material |
| CN101613605A (en) * | 2009-07-21 | 2009-12-30 | 东北林业大学 | Spiro-phosphorus phenone polyesteramide intumescent fire retardant and synthetic method thereof |
| CN106397778A (en) * | 2016-09-05 | 2017-02-15 | 北京理工大学 | Method for increasing yield and polymerization degree of polymeric phosphorus-nitrogen intumescent flame retardant |
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2018
- 2018-08-24 CN CN201810970055.3A patent/CN109096493A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2352447B (en) * | 1999-07-28 | 2003-10-15 | Bolton Inst Higher Education | Flame retardancy treatment of polymeric material |
| CN101613605A (en) * | 2009-07-21 | 2009-12-30 | 东北林业大学 | Spiro-phosphorus phenone polyesteramide intumescent fire retardant and synthetic method thereof |
| CN106397778A (en) * | 2016-09-05 | 2017-02-15 | 北京理工大学 | Method for increasing yield and polymerization degree of polymeric phosphorus-nitrogen intumescent flame retardant |
Non-Patent Citations (2)
| Title |
|---|
| GUI-HONG CHEN，等: "A Novel Flame Retardant of Spirocyclic Pentaerythritol Bisphosphorate for Epoxy Resins", 《APPLIED POLYMER SCIENCE》 * |
| 欧育湘，等: "《阻燃剂》", 30 September 2009, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183684A (en) * | 2019-06-13 | 2019-08-30 | 西北师范大学 | A kind of modified oil shale semicoke and preparation method thereof and the application in high molecular material |
| CN110183684B (en) * | 2019-06-13 | 2021-10-15 | 烟台佳合高分子材料有限公司 | Modified oil shale semicoke, preparation method thereof and application thereof in high polymer material |
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Application publication date: 20181228 |