CN107474220B - A kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin and preparation method thereof - Google Patents
A kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin and preparation method thereof Download PDFInfo
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- CN107474220B CN107474220B CN201710719780.9A CN201710719780A CN107474220B CN 107474220 B CN107474220 B CN 107474220B CN 201710719780 A CN201710719780 A CN 201710719780A CN 107474220 B CN107474220 B CN 107474220B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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Abstract
The present invention relates to epoxy resin modification technical fields, provide nitrogenous one kind, silicon, chlorine ingrain fireproofing epoxy resin and preparation method thereof；Preparation method includes: the silicon tetrachloride as by-product using production of polysilicon, and first passing through dropwise addition ethylene oxide makes silicon tetrachloride react the relatively low dichlorosilane substituent of generation activity under cryogenic；Then it is reacted at relatively high temperatures with the match gram of nitrogenous flame ratardant using the incidental substitution reaction of silicon-halogen, by the way that match gram is slowly added, controls the reaction of its halogen substitution that mostly occurs greatly；It is finally reacted using the active epoxy group of epoxy resin with a remaining silicon halogen, final synthesis has the epoxy resin of flame retardant property.The synthesis technology of the preparation method is simple, at low cost, and reaction time is short, and reaction efficiency is high.The flame retardant property of ingrain fireproofing epoxy resin prepared by the preparation method is good, and oxygen index (OI) is high, small to the Effect on Mechanical Properties of epoxy resin.
Description
Technical field
The invention belongs to epoxy resin modification technical fields, specifically, being related to a kind of nitrogenous, silicon, chlorine ingrain fireproofing ring
Oxygen resin and preparation method thereof.
Background technique
Epoxy resin due to adhesive strength is high, electrical insulation capability is good, excellent chemical corrosion resistance and it is good plus
Work performance etc. is widely used in the every field of national economy, can be used as coating material, reinforcing material, pouring material and gluing
Agent etc..But since the inflammability of epoxy resin is restricted its application, fire retarding epoxide resin is developed into the weight of epoxy resin
Want research direction.
Mainly start at present from additive flame retardant to the fire-retardant of epoxy resin, but most additive flame retardants and ring
Oxygen system poor compatibility easily influences the use scope of epoxy resin；In addition, the additive amount of additive flame retardant is larger, for example, needing
Add 15%~18% expanded graphite and ammonium polyphosphate or add 15% red phosphorus just epoxy resin UL-94 can be made vertically to fire
It burns grade and reaches V0 rank, this based flame retardant additive amount is larger and the possessed color of this based flame retardant itself will affect asphalt mixtures modified by epoxy resin
The color of rouge itself limits the use scope of epoxy resin instead；For another example, when use ternary intumescent system fire retarding epoxide resin
When, additive amount will reach 25% or more, can be only achieved UL-94 vertical combustion V0 rank, fire retardant usage amount is very big, seriously affects
The mechanical property of epoxy resin reduces the toughness of epoxy resin, impact resistance weakens.
In addition, the method for more common fire retarding epoxide resin is to improve ring after solidification by improving the flame retardant property of curing agent
The flame retardant property of oxygen resin.However, curing efficiency and raising curing agent and asphalt mixtures modified by epoxy resin can be taken into account again reaching flame-retardancy requirements simultaneously
The compatibility of rouge is highly difficult, and this kind of curing agent all only includes a kind of ignition-proof element (nitrogen, phosphorus, silicon, halogen etc.) substantially,
It is few to contain several ignition-proof elements simultaneously, the synergistic effect between ignition-proof element cannot be played well, flame retardant effect is poor,
Only by the amount of raising curing agent come the flame retardant effect of reinforced epoxy, but excessive curing agent not only will affect epoxy
The curing performance of resin and production cost can be greatly improved.
Summary of the invention
For deficiency above-mentioned in the prior art, the first object of the present invention is to provide nitrogenous one kind, silicon, the resistance of chlorine ontology
Epoxy resin is fired, the flame retardant property of the ingrain fireproofing epoxy resin is good, and oxygen index (OI) is high, to the Effect on Mechanical Properties of epoxy resin
It is small.
For deficiency above-mentioned in the prior art, the second object of the present invention is to provide nitrogenous, silicon, chlorine ingrain fireproofing ring
The synthesis technology of the preparation method of oxygen resin, the preparation method is simple, at low cost, and reaction time is short, and reaction efficiency is high, can make
It is standby to obtain the epoxy resin of excellent fireproof performance.
In order to achieve the above object, the preferred solution that the present invention uses is:
The preparation method of a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin, including following preparation step: (1) low in temperature
Under the conditions of 30 DEG C, dioxane and silicon tetrachloride are mixed to form the first mixed solution by 50ml:4.5g, then mix to first
It is instilled in liquid and forms the second mixed solution with the ethylene oxide of above-mentioned silicon tetrachloride mass ratio 2.2:4.5；(2) by Sai Ke and dioxy
Six rings are mixed to a match gram dissolution by 2-3g:30ml and form third mixed solution, and third mixed solution is mixed with the second of 60-70 DEG C
It closes solution and is mixed to form the 4th mixed solution, carry out condensing reflux reaction；(3) by epoxy resin E44 according to above-mentioned match gram
Mass ratio is that 27-30:2-3 is added to the 5th mixed solution of formation in the 4th mixed solution, condensing reflux reaction is carried out, to the 5th
Mixed solution is rinsed after filtering out six alkane of dioxy in acidity, decompression.
Further, in preferred embodiments of the present invention, epoxy resin E44 is the epoxy resin after 80 DEG C of heating
E44。
Further, in preferred embodiments of the present invention, in step (3) when the pH of the 5th mixed solution is 6~7,
Decompression suction filtration is carried out to the 5th mixed solution.
Further, in preferred embodiments of the present invention, the time being condensed back in step (3) is 1~3h.
Further, in preferred embodiments of the present invention, step (3) further includes using 50% ethanol water as drift
Lotion is rinsed.
It further, further include since the second mixed solution temperature in preferred embodiments of the present invention, in step (1)
60 DEG C are warming up to after being reduced to 30min.
Further, in preferred embodiments of the present invention, the temperature being condensed back in step (2) is 80 DEG C.
Further, in preferred embodiments of the present invention, in step (2) further include: after condensing reflux, the 4th mixing
Solution is cooled to 50 DEG C.
A kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin, by the preparation of above-mentioned nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin
Method is prepared.
One kind provided by the invention is nitrogenous, the beneficial effect of silicon, chlorine ingrain fireproofing epoxy resin is:
(1) nitrogenous, silicon provided in an embodiment of the present invention, chlorine ingrain fireproofing epoxy resin, utilize the by-product of production of polysilicon
Halogenating reaction occurs for object silicon tetrachloride, and utilizes the activity of epoxy resin epoxy base and the activity synthesis of match gram fire retardant hydroxyl
It obtains, flame retardant property is good, and oxygen index (OI) is high, small to the Effect on Mechanical Properties of epoxy resin.
(2) preparation method of nitrogenous, silicon provided in an embodiment of the present invention, chlorine ingrain fireproofing epoxy resin, comprising:
First with the silicon tetrachloride as by-product of production of polysilicon, first passing through dropwise addition ethylene oxide makes silicon tetrachloride in low temperature
Under the conditions of reaction generate the relatively low dichlorosilane substituent of activity；Then existed using the incidental substitution reaction of silicon-halogen
It controls its halogen that mostly occurs greatly by the way that match gram is slowly added with the match gram of nitrogenous flame ratardant reaction under higher temperature and replaces
Reaction；It is finally reacted using the active epoxy group of epoxy resin with a remaining silicon halogen, final synthesis has fire-retardant
The epoxy resin of performance；
Wherein, silicon, the chlorine introduced in reaction process containing the match gram of the fire retardant in nitrogen source and charcoal source and with fire retardation is first
Element can cooperate with the flame retardant effect for improving epoxy resin from different fire retardant mechanism angles；
The additive amount of Sai Ke and epoxy resin be as inventor's creativeness test obtained by, can in the ratio range
The ability of epoxy resin ingrain fireproofing is further increased, also can reach resistance in the case where adding the fire retardant of small amount agent
The effect of combustion, and it is able to maintain the preferable mechanical property of epoxy resin.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Embodiment 1
Present embodiments provide a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method:
(1) in the straight mouth four-necked bottle of 1000ml equipped with blender, thermometer and dimroth's condensing tube, 50ml bis- is added
Six ring of oxygen, 4.5g silicon tetrachloride, control temperature are lower than 30 DEG C, are then slowly dropped into 2.2g ethylene oxide, maintain the temperature at 30 DEG C
Hereinafter, timing starts to warm up after keeping 30min to 60 DEG C after temperature, which starts, to be reduced after being added dropwise to complete；
(2) weigh 20g match gram powder, using 300ml dioxane heating 50 DEG C at a temperature of stirring and dissolving after, slowly
It is added drop-wise in straight mouth four-necked bottle, maintains the temperature at 70 DEG C and be condensed back instead hereinafter, being to slowly warm up to 80 DEG C of stirrings after being added dropwise to complete
After answering 3h, reaction temperature is reduced to 50 DEG C；
(3) it is added at one time the epoxy resin E44 that 300g passes through 80 DEG C of heating, after condensing reflux is stirred to react 1~3h, to
After pH to 6~7 decompression filter out six alkane of dioxy, then using 50% ethanol water rinse epoxy resin surface, obtain it is nitrogenous,
Silicon, chlorine ingrain fireproofing epoxy resin.
Embodiment 2
Present embodiments provide a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method:
(1) in the straight mouth four-necked bottle of 1000ml equipped with blender, thermometer and dimroth's condensing tube, 50ml bis- is added
Six ring of oxygen, 4.5g silicon tetrachloride, control temperature are lower than 30 DEG C, are then slowly dropped into 2.2g ethylene oxide, maintain the temperature at 30 DEG C
Hereinafter, timing starts to warm up after keeping 30min to 60 DEG C after temperature, which starts, to be reduced after being added dropwise to complete；
(2) weigh 20g match gram powder, using 300ml dioxane heating 50 DEG C at a temperature of stirring and dissolving after, slowly
It is added drop-wise in straight mouth four-necked bottle, maintains the temperature at 70 DEG C and be condensed back instead hereinafter, being to slowly warm up to 80 DEG C of stirrings after being added dropwise to complete
After answering 3h, reaction temperature is reduced to 50 DEG C；
(3) it is added at one time the epoxy resin E44 that 280g passes through 80 DEG C of heating, after condensing reflux is stirred to react 1~3h, to
After pH to 6~7 decompression filter out six alkane of dioxy, then using 50% ethanol water rinse epoxy resin surface, obtain it is nitrogenous,
Silicon, chlorine ingrain fireproofing epoxy resin.
Embodiment 3
Present embodiments provide a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method:
(1) in the straight mouth four-necked bottle of 1000ml equipped with blender, thermometer and dimroth's condensing tube, 50ml bis- is added
Six ring of oxygen, 4.5g silicon tetrachloride, control temperature are lower than 30 DEG C, are then slowly dropped into 2.2g ethylene oxide, maintain the temperature at 30 DEG C
Hereinafter, timing starts to warm up after keeping 30min to 60 DEG C after temperature, which starts, to be reduced after being added dropwise to complete；
(2) weigh 20g match gram powder, using 300ml dioxane heating 50 DEG C at a temperature of stirring and dissolving after, slowly
It is added drop-wise in straight mouth four-necked bottle, maintains the temperature at 70 DEG C and be condensed back instead hereinafter, being to slowly warm up to 80 DEG C of stirrings after being added dropwise to complete
After answering 3h, reaction temperature is reduced to 50 DEG C；
(3) it is added at one time the epoxy resin E44 that 270g passes through 80 DEG C of heating, after condensing reflux is stirred to react 1~3h, to
After pH to 6~7 decompression filter out six alkane of dioxy, then using 50% ethanol water rinse epoxy resin surface, obtain it is nitrogenous,
Silicon, chlorine ingrain fireproofing epoxy resin.
Embodiment 4
Present embodiments provide a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method:
(1) in the straight mouth four-necked bottle of 1000ml equipped with blender, thermometer and dimroth's condensing tube, 50ml bis- is added
Six ring of oxygen, 4.5g silicon tetrachloride, control temperature are lower than 30 DEG C, are then slowly dropped into 2.2g ethylene oxide, maintain the temperature at 30 DEG C
Hereinafter, timing starts to warm up after keeping 30min to 60 DEG C after temperature, which starts, to be reduced after being added dropwise to complete；
(2) weigh 30g match gram powder, using 300ml dioxane heating 50 DEG C at a temperature of stirring and dissolving after, slowly
It is added drop-wise in straight mouth four-necked bottle, maintains the temperature at 70 DEG C and be condensed back instead hereinafter, being to slowly warm up to 80 DEG C of stirrings after being added dropwise to complete
After answering 3h, reaction temperature is reduced to 50 DEG C；
(3) it is added at one time the epoxy resin E44 that 300g passes through 80 DEG C of heating, after condensing reflux is stirred to react 1~3h, to
After pH to 6~7 decompression filter out six alkane of dioxy, then using 50% ethanol water rinse epoxy resin surface, obtain it is nitrogenous,
Silicon, chlorine ingrain fireproofing epoxy resin.
Comparative example 1
This comparative example provides a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method:
(1) in the straight mouth four-necked bottle of 1000ml equipped with blender, thermometer and dimroth's condensing tube, 50ml bis- is added
Six ring of oxygen, 4.5g silicon tetrachloride, control temperature are lower than 30 DEG C, are then slowly dropped into 2.2g ethylene oxide, maintain the temperature at 30 DEG C
Hereinafter, timing starts to warm up after keeping 30min to 60 DEG C after temperature, which starts, to be reduced after being added dropwise to complete；
(2) weigh 35g match gram powder, using 300ml dioxane heating 50 DEG C at a temperature of stirring and dissolving after, slowly
It is added drop-wise in straight mouth four-necked bottle, maintains the temperature at 70 DEG C and be condensed back instead hereinafter, being to slowly warm up to 80 DEG C of stirrings after being added dropwise to complete
After answering 3h, reaction temperature is reduced to 50 DEG C；
(3) it is added at one time the epoxy resin E44 that 300g passes through 80 DEG C of heating, after condensing reflux is stirred to react 1~3h, to
After pH to 6~7 decompression filter out six alkane of dioxy, then using 50% ethanol water rinse epoxy resin surface, obtain it is nitrogenous,
Silicon, chlorine ingrain fireproofing epoxy resin.
Comparative example 2
This comparative example provides a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method:
(1) in the straight mouth four-necked bottle of 1000ml equipped with blender, thermometer and dimroth's condensing tube, 50ml bis- is added
Six ring of oxygen, 4.5g silicon tetrachloride, control temperature are lower than 30 DEG C, are then slowly dropped into 2.2g ethylene oxide, maintain the temperature at 30 DEG C
Hereinafter, timing starts to warm up after keeping 30min to 60 DEG C after temperature, which starts, to be reduced after being added dropwise to complete；
(2) weigh 19g match gram powder, using 300ml dioxane heating 50 DEG C at a temperature of stirring and dissolving after, slowly
It is added drop-wise in straight mouth four-necked bottle, maintains the temperature at 70 DEG C and be condensed back instead hereinafter, being to slowly warm up to 80 DEG C of stirrings after being added dropwise to complete
After answering 3h, reaction temperature is reduced to 50 DEG C；
(3) it is added at one time the epoxy resin E44 that 300g passes through 80 DEG C of heating, after condensing reflux is stirred to react 1~3h, to
After pH to 6~7 decompression filter out six alkane of dioxy, then using 50% ethanol water rinse epoxy resin surface, obtain it is nitrogenous,
Silicon, chlorine ingrain fireproofing epoxy resin.
Comparative example 3
This comparative example provides a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method:
(1) in the straight mouth four-necked bottle of 1000ml equipped with blender, thermometer and dimroth's condensing tube, 50ml bis- is added
Six ring of oxygen, 4.5g silicon tetrachloride, control temperature are lower than 30 DEG C, are then slowly dropped into 2.2g ethylene oxide, maintain the temperature at 30 DEG C
Hereinafter, timing starts to warm up after keeping 30min to 60 DEG C after temperature, which starts, to be reduced after being added dropwise to complete；
(2) weigh 20g match gram powder, using 300ml dioxane heating 50 DEG C at a temperature of stirring and dissolving after, slowly
It is added drop-wise in straight mouth four-necked bottle, maintains the temperature at 70 DEG C and be condensed back instead hereinafter, being to slowly warm up to 80 DEG C of stirrings after being added dropwise to complete
After answering 3h, reaction temperature is reduced to 50 DEG C；
(3) it is added at one time the epoxy resin E44 that 320g passes through 80 DEG C of heating, after condensing reflux is stirred to react 1~3h, to
After pH to 6~7 decompression filter out six alkane of dioxy, then using 50% ethanol water rinse epoxy resin surface, obtain it is nitrogenous,
Silicon, chlorine ingrain fireproofing epoxy resin.
Comparative example 4
This comparative example provides a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method:
(1) in the straight mouth four-necked bottle of 1000ml equipped with blender, thermometer and dimroth's condensing tube, 50ml bis- is added
Six ring of oxygen, 4.5g silicon tetrachloride, control temperature are lower than 30 DEG C, are then slowly dropped into 2.2g ethylene oxide, maintain the temperature at 30 DEG C
Hereinafter, timing starts to warm up after keeping 30min to 60 DEG C after temperature, which starts, to be reduced after being added dropwise to complete；
(2) weigh 20g match gram powder, using 300ml dioxane heating 50 DEG C at a temperature of stirring and dissolving after, slowly
It is added drop-wise in straight mouth four-necked bottle, maintains the temperature at 70 DEG C and be condensed back instead hereinafter, being to slowly warm up to 80 DEG C of stirrings after being added dropwise to complete
After answering 3h, reaction temperature is reduced to 50 DEG C；
(3) it is added at one time the epoxy resin E44 that 330g passes through 80 DEG C of heating, after condensing reflux is stirred to react 1~3h, to
After pH to 6~7 decompression filter out six alkane of dioxy, then using 50% ethanol water rinse epoxy resin surface, obtain it is nitrogenous,
Silicon, chlorine ingrain fireproofing epoxy resin.
Experimental example 1
The fire retarding epoxide resin and epoxy resin E44 for taking same amount of embodiment 1-4 and comparative example 1-4 to be prepared,
It is set as experimental group 1-9；The sample in 92g experimental group 1-9 is weighed, after 80 DEG C of heating, is separately added into 8g curing agent isophthalic two
Amine, after uniform stirring, vacuumize process 30min in vacuum oven in an oven, after removing the bubble in sample, selection is corresponding
Template carries out clamp operation, by 80 DEG C of heating 1h, 100 DEG C of heating 2h, and 120 DEG C of modes for heating 2h successively elevated cure.
Carry out fire-retardant Mechanics Performance Testing and epoxide equivalent measurement respectively to experimental group 1-9.
Vertical burn test is carried out by national standard GB-T 2408-2008, batten specification is 130 × 13 × 3.2mm；By national standard
GB-T 2406.2-2009 determination limit oxygen index (OI), batten standard are 130 × 6.5 × 3.2mm；By national standard GB/T1843-2008
Plastics toughness is measured using cylinder strutbeam combination shock machine, batten specification is 80 × 10 × 4mm, and test result is shown in Table 1 and table
2:
The fire-retardant Mechanics Performance Testing parameter comparison of 1 experimental group 1-9 of table
The epoxide equivalent parameter comparison of 2 experimental group 1-9 of table
By the result of Tables 1 and 2 it is found that the flame retardant effect of embodiment 1-4 and comparative example 1-4 are superior to experimental group 9, the knot
Fruit shows that the epoxy resin being prepared using preparation method of the invention has excellent flame retardant effect, this has benefited from the present invention
Halogenating reaction occurs using the silicon tetrachloride as by-product of production of polysilicon, introduces in reaction process fire-retardant containing nitrogen source and charcoal source
Agent match gram and the silicon with fire retardation, chlorine element, can cooperate with the resistance for improving epoxy resin from different fire retardant mechanism angles
Fuel efficiency fruit.
The additive amount and reaction condition of each reactant of the step of embodiment 1-3 and comparative example 3-4 (1) and step (2)
Control is the same, and the main distinction is epoxy resin E in step (3)44Additive amount it is different, make the flame retardant epoxy tree of synthesis
The flame retardant effect of rouge is different, it can be found that under conditions of the experimental amount, when epoxy resin additive amount is the mass ratio with match gram
When for 27-30:2-3, the fire retarding epoxide resin being prepared can obtain preferable flame retardant effect, be attained by V0 rank.
When epoxy resin content is identical with reaction condition in the step of embodiment 1 and 4, comparative example 1-2 (3), change step
Suddenly the additive amount of (2) middle match gram, discovery dissolution when reacting when match gram content improves is difficult, when content is reduced in anti-flammability
Can be bad, therefore be 2-3:27-30 matching gram additive amount as the mass ratio with epoxy resin: when, it can obtain preferable fire-retardant
Effect.
Table 2 statistics indicate that, the epoxide number of the sample of experimental group 1-8 is lower than test group 9, should the result shows that, by passing through this hair
The epoxy group of the fire retarding epoxide resin that bright experimental procedure and technological parameter are made compared with the prior art in epoxy resin
There are more epoxy groups to participate in reaction.
In conclusion nitrogenous, silicon provided in an embodiment of the present invention, chlorine ingrain fireproofing epoxy resin, flame retardant property is good, oxygen
Index is high, small to the Effect on Mechanical Properties of epoxy resin；Nitrogenous, silicon provided in an embodiment of the present invention, chlorine ingrain fireproofing asphalt mixtures modified by epoxy resin
The synthesis technology of the preparation method of rouge, preparation method is simple, at low cost, and reaction time is short, and reaction efficiency is high, can be prepared into
To the epoxy resin of excellent fireproof performance.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin preparation method, which is characterized in that including following preparation step:
(1) under the conditions of temperature is lower than 30 DEG C, by dioxane and silicon tetrachloride by 50ml:4.5g be mixed to form first mix it is molten
Liquid, then instill into first mixed liquor and mixed with above-mentioned silicon tetrachloride mass ratio for the ethylene oxide formation second of 2.2:4.5
Close solution；
(2) Sai Ke is mixed by 2-3g:30ml to a match gram dissolution with dioxane and forms third mixed solution, the third is mixed
Second mixed solution that solution is closed with 60-70 DEG C is mixed to form the 4th mixed solution, carries out condensing reflux reaction；
It (3) is that 27-30:2-3 is added in the 4th mixed solution according to the mass ratio of above-mentioned match gram by epoxy resin E44
The 5th mixed solution is formed, condensing reflux reaction is carried out, to the 5th mixed solution in acidity, decompression filters out six alkane of dioxy
After rinsed.
2. the preparation method of nitrogenous, silicon according to claim 1, chlorine ingrain fireproofing epoxy resin, which is characterized in that described
Epoxy resin E44 is the epoxy resin E44 after 80 DEG C of heating.
3. the preparation method of nitrogenous, silicon according to claim 2, chlorine ingrain fireproofing epoxy resin, which is characterized in that step
(3) in when the pH of the 5th mixed solution is 6~7, decompression suction filtration is carried out to the 5th mixed solution.
4. the preparation method of nitrogenous, silicon according to claim 3, chlorine ingrain fireproofing epoxy resin, which is characterized in that step
(3) time being condensed back in is 1~3h.
5. the preparation method of nitrogenous, silicon according to claim 1, chlorine ingrain fireproofing epoxy resin, which is characterized in that step
It (3) further include being rinsed using 50% ethanol water as purificant.
6. the preparation method of nitrogenous, silicon according to claim 1, chlorine ingrain fireproofing epoxy resin, which is characterized in that step
It (1) further include being warming up to 60 DEG C after being reduced to 30min since the second mixed solution temperature in.
7. the preparation method of nitrogenous, silicon according to claim 1, chlorine ingrain fireproofing epoxy resin, which is characterized in that step
(2) temperature being condensed back in is 80 DEG C.
8. the preparation method of nitrogenous, silicon according to claim 7, chlorine ingrain fireproofing epoxy resin, which is characterized in that step
(2) in further include: after condensing reflux, the 4th mixed solution is cooled to 50 DEG C.
9. a kind of nitrogenous, silicon, chlorine ingrain fireproofing epoxy resin, which is characterized in that contain as described in claim 1-8 any one
Nitrogen, silicon, chlorine ingrain fireproofing epoxy resin preparation method be prepared.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731550A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Triazinetrichloropropyl silicate compound and preparation method thereof |
| CN102731545A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Isocyanurate chloropropyl chloroethyl silicate and preparation method thereof |
| CN103524545A (en) * | 2013-11-08 | 2014-01-22 | 苏州科技学院相城研究院 | Fire retardant1,3,5-tris(2-hydroxyethyl)isocyanurate 3-silicate-chloride propyl ester compound and preparation method thereof |
| CN104710458A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Tri(2-dimethylethyoxylacyloxyethyl)isocyanurate compound and preparation method thereof |
| CN104710457A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Tri[(2-dimethylchloridepropoxysiliconacyloxy)ethyl] isocyanurate compound and preparation method thereof |
-
2017
- 2017-08-21 CN CN201710719780.9A patent/CN107474220B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731550A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Triazinetrichloropropyl silicate compound and preparation method thereof |
| CN102731545A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Isocyanurate chloropropyl chloroethyl silicate and preparation method thereof |
| CN103524545A (en) * | 2013-11-08 | 2014-01-22 | 苏州科技学院相城研究院 | Fire retardant1,3,5-tris(2-hydroxyethyl)isocyanurate 3-silicate-chloride propyl ester compound and preparation method thereof |
| CN104710458A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Tri(2-dimethylethyoxylacyloxyethyl)isocyanurate compound and preparation method thereof |
| CN104710457A (en) * | 2015-03-06 | 2015-06-17 | 苏州阳桥化工科技有限公司 | Tri[(2-dimethylchloridepropoxysiliconacyloxy)ethyl] isocyanurate compound and preparation method thereof |
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