CN106633188A - Nano silica with sulfonate grafted on surface and preparation method and purpose thereof - Google Patents
Nano silica with sulfonate grafted on surface and preparation method and purpose thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention relates to nano silica with sulfonate grafted on surface and a preparation method and a purpose thereof. The nano silica is characterized in that -C(=O)-R-SO3A groups and -C(=O)-RH groups are grafted on the surface of the nano silica, wherein A is selected from Li, Na or K, and the grafting total amount of the -C(=O)-R-SO3A groups and -C(=O)-RH groups is 2 to 10 weight percent. The nano silica disclosed by the invention can be used as a filling material for preparing polymer composites of polycarbonates and polycarbonate alloys; the nano silica is capable of increasing the dispersity of the nano silica in polycarbonates and polycarbonate alloys and increasing the comprehensive mechanical performance of the polymer materials, and particularly increasing the flame resistance of the polycarbonates.
Description
Technical field
The invention belongs to the nano silicon and its field of nanocomposite materials of organic functional molecular modification, while belonging to
Field of fire-proof technology.
Background technology
Merlon (PC) resin is a kind of thermoplastic engineering plastic of high comprehensive performance, with excellent heat resistance,
Impact resistance and dimensional stability, are one of widely used general engineering plastic kinds of a class, in electric, mechanical, vapour
The industries such as car, illumination and building are widely used.
Due to high request of the field to Flame Retardancy such as electric and office equipment, it is necessary to carry out fire-retardant changing to PC
Property, the fire retardant that PC is usually used at present is divided into two kinds of addition type and response type.And response type is little because of its addition, to performance shadow
Ring little and be more widely applied.
Among these, the Sulfonates fire retardant of sulfur-bearing, such as potassium diphenylsulfone sulfonate (KSS), trichloro-benzenes potassium sulfonate (STB), entirely
Fluorine butyl sulfonic acid potassium (KPFBS) is most widely used and efficiently.
Nanometer inorganic filler such as nano zine oxide, nano titanium oxide, nano montmorillonite, nano silicon etc. are due to tool
There is strong ultravioletlight screening function, and non-migratory is excellent, it is to improve polymer nanocomposite to add them into polymeric material
The important development direction of composite ageing resistace.Nano-particle is because of its distinctive small-size effect, skin effect and quantum
Tunnel-effect, add polymer in, toughness, the rigidity of polymer not only can be improved, it is also possible to obtain excellent translucency,
The features such as barrier, heat resistance, anti-ultraviolet radiation.The performance of Preparing Organic-inorganic Nano Hybrid Material is to a great extent
Chemical constitution, surface finishing status and their dispersion situations in the polymeric material depending on inorganic nano material.
Nano silicon is applied in polymer as a kind of inorganic nano-filler, can improve the comprehensive of polymer
Can, but due to the presence of its surface hydroxyl and unsaturated residual bond, very strong hydrophily is shown, with polymer compound tense compatibility
Difference, it is difficult to dispersed.Therefore have to be surface-treated nano silicon, such as process (beautiful using silane coupler
State patent US 6809149B2), surface grafting process, oligomer and the process of macromolecular cladding etc. so as to which surface exhibits are hydrophobic
Property, solve the consistency problem with polymer.
But how the improvement of the fire resistance that modified manometer silicon dioxide uses it for PC is also rarely reported.
The content of the invention
An object of the present invention is to provide a kind of its dispersiveness in Merlon that not only can improve with comprehensive mechanics
Performance, while improve the modified manometer silicon dioxide of the anti-flammability of Merlon.
The second object of the present invention is to provide a kind of preparation method of above-mentioned modified manometer silicon dioxide.
The third object of the present invention is to provide a kind of polycarbonate compositions containing above-mentioned modified manometer silicon dioxide.
For achieving the above object, the present invention provides a kind of nano silicon of surface grafting sulfonate, is in nanometer two
Group shown in the surface grafting formula (1) and formula (2) of silica：
- C (=O)-R-SO3A (1)
- C (=O)-RH (2)
In formula (1), A is selected from Li, Na or K；
In formula (1) and formula (2), R is selected from the group shown in formula (3)：
In formula (3), m takes 0 or 1；R ' is selected from substituted or unsubstituted phenylene；Replacement can be a replacement (R '5), two take
Generation (R '5、R’6), three replacement (R '5、R’6、R’7) or four replacement (R '5、R’6、R’7、R’8)；R1～R4It is identical or different, each other solely
The C1-C22 alkyl on the spot replacing selected from H, C1-C22 alkyl, perfluor or halogen；R’5～R '8It is identical or different, independently of one another
The C1-C22 alkyl replaced selected from C1-C22 alkyl, perfluor or halogen；
Wherein, total grafting amount of formula (1) and group shown in formula (2) is 2wt%～10wt%.
Wherein, R is selected from the group shown in formula (3 ')：
In formula (3 '), m takes 0 or 1；R1～R8It is identical or different, it is independently from each other H, C1-C22 alkyl, perfluor and replaces
C1-C22 alkyl or halogen.
Wherein, the above-mentioned formula of the surface grafting (1) by-OH of silica surface in nano silicon and formula (2) institute
The group for showing.
Wherein, the particle size range of described nano silicon is 1～200nm, its specific surface area can 100～
1000m2Between/g.
Preferably, in formula (3), m takes 0；Preferably, R ' is phenylene.Or, it is preferable that R ' is three substituted phenylenes, is taken
Dai Jiwei halogens, more preferably R ' are three chlorophenylenes.
Preferably, in formula (3), m takes 1；Preferably, R1～R4Identical and selected from H, R ' is phenylene.Or, it is preferable that R1
～R4In have a group for H, the other three is identical or different to be independently from each other halogen, more preferably the other three it is identical and
Selected from chlorine；R ' is three substituted phenylenes, and substituent is halogen, and more preferably R ' is three chlorophenylenes.
Preferably, in formula (3 '), m takes 0；R5～R8It is identical or different, it is independently from each other what H, alkyl, perfluor replaced
Alkyl or halogen.Preferably, R5～R8It is identical and selected from H.Or, it is preferable that R5～R8In have a group for H, the other three
Identical or different to be independently from each other halogen, more preferably the other three is identical and selected from chlorine.
Preferably, in formula (3 '), m takes 1；R1～R8It is identical or different, it is independently from each other what H, alkyl, perfluor replaced
Alkyl or halogen.Preferably, R1～R8It is identical and selected from H.Or, it is preferable that R1～R4In have a group for H, the other three
Identical or different to be independently from each other halogen, more preferably the other three is identical and selected from chlorine；R5～R8In have a group for H,
The other three is identical or different to be independently from each other halogen, and more preferably the other three is identical and selected from chlorine.
The present invention also provides a kind of preparation method of the nano silicon of above-mentioned surface grafting sulfonate, methods described bag
Include following steps：
1) by nano silicon, compound shown in formula (4) and optional catalyst mixing, reaction obtains HR- (C=
O)-O- nano silicons；
HR- (C=O)-X (4)
In formula (4), R is defined as above, and X is halogen or-OR9, R9Selected from C1-4Alkyl；
2) by step 1) HR- (the C=O)-O- nano silicons that obtain carry out sulfonated, into salt, obtain the surface
The nano silicon of grafting sulfonate.
Wherein, methods described specifically includes following steps：
S1, compound shown in heated type (4), obtain its molten mass：
HR- (C=O)-X (4)
In formula (4), R is defined as above, and X is halogen or-OR9, R9Selected from C1-4Alkyl；
Stir in S2, the molten mass for adding step S1 to obtain nano silicon and the first optional catalyst, shape
Disperse suspension into nano silicon；
S3, the suspension for obtaining step S2 stirring reaction under heating and inert gas shielding, obtain HR- (C=O)-
O- nano silicons；
S4, HR- (the C=O)-O- nano silicons for obtaining step S3 further carry out sulfonated, into salt, obtain institute
State the nano silicon of surface grafting sulfonate.
Wherein, in step S1, heating-up temperature is 20 DEG C～150 DEG C, it is therefore preferable to 23 DEG C～140 DEG C.Shown in the formula (1)
The addition of compound be 10～150 weight portions, preferably 30～100 weight portions.
Wherein, in step S2, nano silicon is 1 weight portion with the weight ratio of compound shown in formula (4):(10
～150) weight portion, preferably 1 weight portion:(30～100) weight portion；The weight portion of first catalyst and nano silicon
Ratio be (0.45～0.65) weight portion:1 weight portion.
Wherein, in step S2, when X is halogen, without adding first catalyst；When X is-OR9When, add first to urge
Agent, first catalyst is the catalyst for ester exchange reaction, for example：Selected from sodium methoxide, potassium tert-butoxide, Carbon Dioxide
One kind in potassium, nano magnalium hydrotalcite, p-methyl benzenesulfonic acid, Dibutyltin oxide, dioctyl tin oxide.
Wherein, in step S3, suspension stirring reaction in the case where temperature is 110～200 DEG C and inert gas shielding；It is preferred that
Ground, the reaction time be 2-10 hours, preferred 3-5 hours.
Wherein, in step S3, after reaction terminates, also including post-processing step, including：Filter, filter cake is washed with cleaning solvent
Wash, remove compound shown in unreacted formula (4), obtain the nano silicon of HR- (C=O)-grafting.
Wherein, in step S4, the sulfonated process is specially：The nano silicon of the grafting that step S3 is obtained
In being dispersed in organic solution, excessive halosulfonic acid and the second catalyst, the stirring reaction under inert gas shielding, question response knot are added
Filter after beam, filter cake is washed with solvent, remove unreacted halosulfonic acid.
Wherein, in step S4, the process into salt is specially：Sulfonated nano silicon carbon after by washing
Sour lithium or sodium carbonate or solution of potassium carbonate are processed, and form sulfonate.It further includes following post-processing step：Deionization is washed
Wash, the modified manometer silicon dioxide after washing is dried in vacuum drying chamber.
The present invention further provides a kind of polycarbonate compositions, it includes Merlon and above-mentioned surface grafting sulfonic acid
The nano silicon of salt.
Preferably, the addition of the nano silicon of the surface grafting sulfonate is 2wt%～5wt%.
Preferably, glass fibre is also included in the composition.
Preferably, impact modifier is also included in the composition.
The present invention further provides a kind of composite, it passes through above-mentioned polycarbonate compositions processing and is obtained.
Preferably, above-mentioned polycarbonate compositions Jing double screw extruder melting extrusions are obtained the composite.
Beneficial effects of the present invention：
The present invention is sulfonate in the structure of nano-silica surface grafting, it turned out that have catalysis resistance to Merlon
Combustion is acted on, and in Merlon combustion process carbon is catalyzed into, and has certain insulating effect to heat, oxygen, can be prevented
Resin further burns.Selected polycarbonate system can be Merlon, and Merlon glass fibre filling, Merlon resists
Punching is modified to wait formula.R group structure in the sulfonate of surface grafting, improves nano silicon compatible with Merlon
Property, improve dispersiveness of the nano silicon in polycarbonate system.It can be seen that, the present invention is by the design nano-silica
The structure of the graft of SiClx, not only improves the comprehensive mechanical property of its dispersiveness and Merlon in Merlon, together
When improve the anti-flammability of Merlon.
The present invention also provides a kind of preparation method of the nano silicon of above-mentioned surface grafting sulfonate, is a kind of economical
Efficient method, merely through three-step reaction the nano silicon of the surface modification has been obtained.
Description of the drawings：
Fig. 1 is a kind of course of reaction schematic diagram of the present invention.
Specific embodiment
As described above, the invention discloses a kind of nano silicon of surface grafting sulfonate, is in nanometer titanium dioxide
Group shown in the above-mentioned formula of the surface grafting (1) and formula (2) of silicon.
Total grafting amount of the formula (1) and formula (2) group is 2wt%～10wt%.The grafting amount passes through thermogravimetry table
Levy, i.e. the weight of the group in grafting accounts for the percentage of the nano silicon weight of surface grafting sulfonate.
Further, the present invention is titrated by the aqueous sodium carbonate of the nano silicon to the graft modification
Detection, in being calculated the nano silicon of the graft modification, group shown in formula (1) accounts for formula (1) and group shown in formula (2)
Summation percentage between 10-90%, i.e., sulphonation rate be 10-90%.Preferably, between 30-90%.
As described above, the nano silicon of the surface grafting sulfonate can make an addition in Merlon and obtain poly- carbon
Acid ester composite, and further prepare a kind of composite.
In the composition, polycarbonate resin is prepared by known methods and obtains, be such as obtained by phosgenation or
Person is obtained by ester-interchange method.In phosgenation, for example, prepared with various dihydroxy diaryl compounds and phosgene reaction.Ester exchange
In method, such as with dihydroxy diaryl compound and carbonic ester (such as diaryl carbonate, concrete such as diphenyl carbonate) reaction system
It is standby.The dihydroxy diaryl compound is, for example, that two (hydroxyaryl) alkane, two (hydroxyaryl) cycloalkane, dihydroxy two are fragrant
Base ether, dihydroxy diaryl thioether, dihydroxy diaryl sulfoxide or dihydroxy diaryl sulfone.Described two (hydroxyaryl) alkane example
In this way 2,2- bis- (4- hydroxy phenyls) propane (bisphenol-A), two (4- hydroxy phenyls) methane, 1,1- bis- (4- hydroxy phenyls) ethane,
2,2- bis- (4- hydroxy phenyls) butane, 2,2- bis- (4- hydroxy phenyls) octane, two (4- hydroxy phenyls) phenylmethanes, 2,2- bis-
(4- hydroxy phenyl -3- aminomethyl phenyls) propane, 1,1- bis- (4- hydroxyl -3- tert-butyl-phenyls) the propane, (4- hydroxyl -3- of 2,2- bis-
Bromophenyl) propane, (4- hydroxyl -3,5- dibromo phenyls) propane of 2,2- bis- or 2,2- bis- (4- hydroxyl -3,5- dichlorophenyls) propane.
Described two (hydroxyaryl) cycloalkane is, for example, (4- hydroxy phenyls) pentamethylene of 1,1- bis- or 1,1- bis- (4- hydroxy phenyls) hexamethylene
Alkane.The dihydroxy diaryl ether is, for example, 4,4'- dihydroxydiphenyl ethers or 4,4'- dihydroxy -3,3'- dimethyl diphenyls
Ether.The dihydroxy diaryl thioether is, for example, 4,4'- dihydroxydiphenyl thioethers.The dihydroxy diaryl sulfoxide is, for example,
4,4'- dihydroxydiphenyls sulfoxide or 4,4'- dihydroxy -3,3'- dimethyl diphenyl sulfoxides.The dihydroxy diaryl sulfone example
4,4'- dihydroxy-diphenyl sulfones or 4,4'- dihydroxy -- 3,3'- dimethyl diphenyl sulfones in this way.
The polycarbonate resin can be used alone or two or more be used in mixed way.The weight of the polycarbonate resin
Average molecular weight is, for example, 10000-100000, preferably 15000-80000.
The addition of the nano silicon of the surface grafting sulfonate is 2wt%-5wt%, if being less than the content,
Effective flame retardant effect can not then be played；If being higher than the content, dispersiveness can be reduced, and be unfavorable for that the nano silicon exists
It is dispersed in the composition, cause processing difficulties.
In an embodiment of the invention, glass fibre can also be added in the composition.The glass fibre
E.g. short glass fiber, puts down fibre, long glass fibres, hollow glass fibre etc..Its addition be, for example, 5wt%～
40wt%.
In an embodiment of the invention, impact modifier can also be added in the composition.The anti-impact changes
Property agent is, for example, MBS, ABS, ASA, siliceous class core shell structure impact modifier etc..Its addition be, for example, 0.5wt%～
10wt%.
In an embodiment of the invention, can also add in polycarbonate compositions in the composition routinely makes
Additive, such as antioxidant and anti-dripping agent.The antioxidant can be that one-component (primary antioxidant), or master are anti-
Oxygen agent and the mixture of auxiliary antioxidant.The primary antioxidant is generally phenols and/or amine, e.g. preferred phenols, antioxygen
One or more in agent 1010, antioxidant 1076, antioxidant 1098, antioxidant 245 or antioxidant 2246.The auxiliary antioxygen
Agent is phosphinate kind antioxidant and/or sulphur ester antioxidant, the phosphiinic acid ester antioxidant include irgasfos 168, TPP,
One or more in PEP-36, P-EPQ or S9288, the sulphur ester antioxidant includes antioxidant 1035, DLTDP, DSTDP
Or one or more in 412S.The addition of the antioxidant is, for example, 0.01wt%～1wt%.
The anti-dripping agent is the fluoropolymer with fiberizability, and its effect is to prevent fused mass in combustion process
Middle generation drip effect.The anti-dripping agent is, for example, polytetrafluoroethylene (PTFE) or Kynoar.The addition of the anti-dripping agent
E.g. 0.1wt%～1wt%.
Embodiments of the present invention are illustrated below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands easily other advantages and effect of the present invention.The present invention can also be by different specific embodiment parties
Formula is carried out or applies, and the every details in this specification can also be based on the application of different aspect, without departing from this
Various modifications and changes are carried out under bright spirit.
Embodiment 1
The nano silicon for using is Degussa A-200, is prepared using vapor phase method, primary particle diameter 12nm, specific surface area
200±25m2/g.Hydroxyl and unsaturated residual bond are contained in surface, and hydrophily is stronger.
Chlorobenzoyl chloride 30g is weighed, is stirred at room temperature under nitrogen protection, be subsequently adding above-mentioned 1g nano silicons stirring,
Form nano silicon dispersion suspension；By suspension under nitrogen protection, filter after heating stirring is reacted 3 hours, and will
Respectively washing three times of gained filter cake ethanol and methyl alcohol, each cleaning solvent consumption 200ml after filtration.By the modified Nano after washing
Silica is put into vacuum drying oven, is dried 6 hours in the case where temperature is for 105 DEG C.By the improved silica for obtaining and excess chlorine
Sulfonic acid reacts, and makes the phenyl sulfonation in the benzoyl being grafted on silica, and the product after sulfonation is filtered, and adds carbonic acid
Stir 3 hours in aqueous solutions of potassium.Filter, be washed with deionized three times, each 200ml, by the modified nano-silica after washing
SiClx is placed into vacuum drying oven, is dried 6 hours in the case where temperature is for 105 DEG C, obtains the nano-silica of surface grafting benzene sulfonic acid potassium
SiClx (its reaction schematic diagram is as shown in Figure 1).
It is 5wt%～7wt% that thermal weight loss characterizes grafting amount.
Jing carries out titration detection to aqueous sodium carbonate, is calculated the benzoyl that wherein silica surface is grafted
Sulphonation rate is 85%.
Embodiment 2
The nano silicon for using is Degussa A-200, is prepared using vapor phase method, primary particle diameter 12nm, specific surface area
200±25m2/g.Hydroxyl and unsaturated residual bond are contained in surface, and hydrophily is stronger.
Chlorobenzoyl chloride 30g is weighed, is stirred at room temperature under nitrogen protection, be subsequently adding above-mentioned 1g nano silicons stirring,
Form nano silicon dispersion suspension；By suspension under nitrogen protection, filter after heating stirring is reacted 3 hours, and will
Respectively washing three times of gained filter cake ethanol and methyl alcohol, each cleaning solvent consumption 200ml after filtration.By the modified Nano after washing
Silica is put into vacuum drying oven, is dried 6 hours in the case where temperature is for 105 DEG C.By the improved silica for obtaining and excess chlorine
Sulfonic acid reacts, the benzoic acid sulfonation being grafted on silica, and the product after sulfonation is filtered, and adds and is stirred in aqueous sodium carbonate
Mix 3 hours.Filter, be washed with deionized three times, each 200ml places into the modified manometer silicon dioxide after washing very
In empty baking oven, dry 6 hours in the case where temperature is for 105 DEG C, obtain the nano silicon of surface grafting benzene sulfonic acid sodium salt.
It is 5wt%～7wt% that thermal weight loss characterizes grafting amount.
Titration detection is carried out to aqueous sodium carbonate, the sulphur of the wherein benzoyl of silica surface grafting is calculated
Rate is 90%.
Embodiment 3
The nano silicon for using is Degussa A-200, is prepared using vapor phase method, primary particle diameter 12nm, specific surface area
200±25m2/g.Hydroxyl and unsaturated residual bond are contained in surface, and hydrophily is stronger.
Methyl benzoate 30g is weighed, is stirred at room temperature, be subsequently adding above-mentioned 1g nano silicons and 0.45g sodium methoxides, stirred
Mix, form nano silicon dispersion suspension；By suspension under nitrogen protection, filter after heating stirring is reacted 3 hours, and
Respectively washing three times of gained filter cake ethanol and methyl alcohol, each cleaning solvent consumption 200ml after filtering.Modified after by washing receives
Rice silica is put into vacuum drying oven, is dried 6 hours in the case where temperature is for 105 DEG C.By the improved silica for obtaining and excess
Chlorosulfonic acid reacts, the benzoic acid sulfonation being grafted on silica, and the product after sulfonation is filtered, in adding wet chemical
Stirring 3 hours.Filter, be washed with deionized three times, each 200ml places into the modified manometer silicon dioxide after washing
In vacuum drying oven, dry 6 hours in the case where temperature is for 105 DEG C, obtain the nano silicon of surface grafting benzene sulfonic acid potassium.
It is 6wt%～8wt% that thermal weight loss characterizes grafting amount.
Embodiment 4
The nano silicon for using is Degussa A-200, is prepared using vapor phase method, primary particle diameter 12nm, specific surface area
200±25m2/g.Hydroxyl and unsaturated residual bond are contained in surface, and hydrophily is stronger.
Ethyl benzoate 30g is weighed, is stirred at room temperature, be subsequently adding above-mentioned 1g nano silicons and 0.45g sodium methoxides, stirred
Mix, form nano silicon dispersion suspension；By suspension under nitrogen protection, filter after heating stirring is reacted 3 hours, and
Respectively washing three times of gained filter cake ethanol and methyl alcohol, each cleaning solvent consumption 200ml after filtering.Modified after by washing receives
Rice silica is put into vacuum drying oven, is dried 6 hours in the case where temperature is for 105 DEG C.By the improved silica for obtaining and excess
Chlorosulfonic acid reacts, the benzoic acid sulfonation being grafted on silica, and the product after sulfonation is filtered, in adding wet chemical
Stirring 3 hours.Filter, be washed with deionized three times, each 200ml places into the modified manometer silicon dioxide after washing
In vacuum drying oven, dry 6 hours in the case where temperature is for 105 DEG C, obtain the nano silicon of surface grafting benzene sulfonic acid potassium.
It is 2wt%～3wt% that thermal weight loss characterizes grafting amount.
Embodiment 5
The surface modified silicon dioxide that embodiment 1 is obtained is granulated with the melting extrusion of Merlon double screw extruder, is surveyed
Its fire resistance is tried, material, formula and result are as shown in table 1.Combustibility test is according to Underwriter ' s Laboratory
The method of Bulletin 94 entitled " plastics flammability test, UL94 " is carried out.
Table 1
Following facts can be illustrated by embodiment 5, add the nano silicon of benzene sulfonate of surface grafting to poly- carbon
The fire resistance of acid esters has greatly lifting, and it can be applied to the fire-retardant of Merlon as a kind of efficient flame-proof modifier
It is modified.
Embodiment 6
Using method same as Example 1, simply chlorobenzoyl chloride therein is replaced with into p- (Ph-SO2)-Ph-COCl。
It is 5wt%～7wt% that thermal weight loss characterizes grafting amount.
Embodiment 7
By in the nano silicon alternative embodiment 1 of the benzene sulfonate of the surface grafting in embodiment 6, obtain and reality
Apply example 5 and constitute the polycarbonate compositions similar with content, its performance test results is as follows：
Table 2
Claims (10)
1. a kind of nano silicon of surface grafting sulfonate, it is characterised in that the nanometer two of the surface grafting sulfonate
Silica is the group shown in surface grafting formula (1) and formula (2) in nano silicon and obtains：
- C (=O)-R-SO3A (1)
- C (=O)-RH (2)
In formula (1), A is selected from Li, Na or K；
In formula (1) and formula (2), R is selected from the group shown in formula (3)：
In formula (3), m takes 0 or 1；R ' is selected from substituted or unsubstituted phenylene；Replacement can be a replacement (R '5), two replacements
(R’5、R’6), three replacement (R '5、R’6、R’7) or four replacement (R '5、R’6、R’7、R’8)；R1～R4It is identical or different, independently of one another
C1-C22 alkyl or halogen that ground replaces selected from H, C1-C22 alkyl, perfluor；R’5～R '8It is identical or different, select independently of one another
The C1-C22 alkyl replaced from C1-C22 alkyl, perfluor or halogen；
Wherein, total grafting amount of formula (1) and group shown in formula (2) is 2wt%～10wt%.
Preferably, R is selected from the group shown in formula (3 ')：
In formula (3 '), m takes 0 or 1；R1～R8It is identical or different, it is independently from each other the C1- that H, C1-C22 alkyl, perfluor replace
C22 alkyl or halogen.
2. nano silicon according to claim 1 the, it is characterised in that by-OH of silica surface in nanometer
Group shown in the above-mentioned formula of the surface grafting (1) and formula (2) of silica.
Preferably, the particle size range of described nano silicon is 1～200nm, and its specific surface area is 100～1000m2/g。
3. nano silicon according to claim 1 and 2, it is characterised in that in formula (3), m takes 0；Preferably, R ' is
Phenylene.Or, it is preferable that R ' is three substituted phenylenes, and substituent is halogen, and more preferably R ' is three chlorophenylenes.
Preferably, in formula (3), m takes 1；Preferably, R1～R4Identical and selected from H, R ' is phenylene.Or, it is preferable that R1～R4
In have a group for H, the other three is identical or different to be independently from each other halogen, and more preferably the other three is identical and is selected from
Chlorine；R ' is three substituted phenylenes, and substituent is halogen, and more preferably R ' is three chlorophenylenes.
Preferably, in formula (3 '), m takes 0；R5～R8It is identical or different, it is independently from each other the alkyl that H, alkyl, perfluor replace
Or halogen.Preferably, R5～R8It is identical and selected from H.Or, it is preferable that R5～R8In have a group for H, the other three is identical
Or difference is independently from each other halogen, more preferably the other three is identical and selected from chlorine.
Preferably, in formula (3 '), m takes 1；R1～R8It is identical or different, it is independently from each other the alkyl that H, alkyl, perfluor replace
Or halogen.Preferably, R1～R8It is identical and selected from H.Or, it is preferable that R1～R4In have a group for H, the other three is identical
Or difference is independently from each other halogen, more preferably the other three is identical and selected from chlorine；R5～R8In have a group for H, in addition
Three identical or different to be independently from each other halogen, and more preferably the other three is identical and selected from chlorine.
4. the preparation method of the nano silicon of surface grafting sulfonate described in a kind of any one of claim 1-3, its feature
It is to the method comprising the steps of：
1) by nano silicon, compound shown in formula (4) and optional catalyst mixing, reaction obtains HR- (C=O)-O-
Nano silicon；
HR- (C=O)-X (4)
In formula (4), R is defined as above, and X is halogen or-OR9, R9Selected from C1-4Alkyl；
2) by step 1) HR- (the C=O)-O- nano silicons that obtain carry out sulfonated, into salt, obtain the surface grafting
The nano silicon of sulfonate.
Preferably, methods described specifically includes following steps：
S1, compound shown in heated type (4), obtain its molten mass：
HR- (C=O)-X (4)
In formula (4), R is defined as above, and X is halogen or-OR9, R9Selected from C1-4Alkyl；
Stir in S2, the molten mass for adding step S1 to obtain nano silicon and the first optional catalyst, formation is received
Rice silica dispersion suspension；
S3, the suspension for obtaining step S2 stirring reaction under heating and inert gas shielding, obtain HR- (C=O)-O- and receive
Rice silica；
S4, HR- (the C=O)-O- nano silicons for obtaining step S3 further carry out sulfonated, into salt, obtain the table
Face is grafted the nano silicon of sulfonate.
5. preparation method according to claim 4, it is characterised in that in step S1, heating-up temperature is 20 DEG C～150 DEG C,
Preferably 23 DEG C～140 DEG C.The addition of compound shown in the formula (1) be 10～150 weight portions, preferably 30～100 weights
Amount part.
Preferably, in step S2, nano silicon is 1 weight portion with the weight ratio of compound shown in formula (4):(10～
150) weight portion, preferably 1 weight portion:(30～100) weight portion；The weight portion of first catalyst and nano silicon it
Than for (0.45～0.65) weight portion:1 weight portion.
Preferably, in step S2, when X is halogen, without adding first catalyst；When X is-OR9When, add first to be catalyzed
Agent, first catalyst is the catalyst for ester exchange reaction, selected from sodium methoxide, potassium tert-butoxide, Anhydrous potassium carbonate, nanometer
One kind in magnalium hydrotalcite, p-methyl benzenesulfonic acid, Dibutyltin oxide, dioctyl tin oxide.
6. the preparation method according to claim 4 or 5, it is characterised in that in step S3, suspension temperature be 110～
Stirring reaction under 200 DEG C and inert gas shielding；Preferably, the reaction time be 2-10 hours, preferred 3-5 hours.
Preferably, in step S3, after reaction terminates, also including post-processing step, including：Filter, filter cake is washed with cleaning solvent,
Compound shown in unreacted formula (4) is removed, the nano silicon of HR- (C=O)-grafting is obtained.
7. the preparation method according to any one of claim 4-6, it is characterised in that in step S4, the sulfonated mistake
Journey is specially：The nano silicon of the grafting that step S3 is obtained is dispersed in organic solution, adds excessive halosulfonic acid and the
Two catalyst, the stirring reaction under inert gas shielding, question response is filtered after terminating, and filter cake is washed with solvent, removes unreacted
Halosulfonic acid.
Preferably, in step S4, the process into salt is specially：Sulfonated nano silicon carbonic acid after by washing
Lithium or sodium carbonate or solution of potassium carbonate are processed, and form sulfonate.It further includes following post-processing step：Deionization is washed
Wash, the modified manometer silicon dioxide after washing is dried in vacuum drying chamber.
8. a kind of polycarbonate compositions, it includes Merlon and the surface grafting sulfonic acid described in any one of claim 1-3
The nano silicon of salt.
Preferably, the addition of the nano silicon of the surface grafting sulfonate is 2wt%～5wt%.
9. polycarbonate compositions according to claim 8, it is characterised in that also include glass fibers in the composition
Dimension.
Preferably, impact modifier is also included in the composition.
10. a kind of composite, it passes through the polycarbonate compositions processing described in claim 8 or 9 and is obtained.
Preferably, above-mentioned polycarbonate compositions Jing double screw extruder melting extrusions are obtained the composite.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004059690A (en) * | 2002-07-26 | 2004-02-26 | Asahi Kasei Chemicals Corp | Aromatic polycarbonate-based colored flame-retardant resin composition and molding |
| CN102417708A (en) * | 2011-11-23 | 2012-04-18 | 金发科技股份有限公司 | Halogen-free flame-retardant polycarbonate composition for LED lampshade and preparation method and application thereof |
| CN103849165A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院化学研究所 | Functionalized nanometer silica with ultraviolet ray absorption function group grafted on surface, and preparation method thereof |
| CN104893272A (en) * | 2015-06-09 | 2015-09-09 | 傅兴琴 | Preparation method of micro-capsular sulfonate fire retardant for polycarbonate material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004059690A (en) * | 2002-07-26 | 2004-02-26 | Asahi Kasei Chemicals Corp | Aromatic polycarbonate-based colored flame-retardant resin composition and molding |
| CN102417708A (en) * | 2011-11-23 | 2012-04-18 | 金发科技股份有限公司 | Halogen-free flame-retardant polycarbonate composition for LED lampshade and preparation method and application thereof |
| CN103849165A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院化学研究所 | Functionalized nanometer silica with ultraviolet ray absorption function group grafted on surface, and preparation method thereof |
| CN104893272A (en) * | 2015-06-09 | 2015-09-09 | 傅兴琴 | Preparation method of micro-capsular sulfonate fire retardant for polycarbonate material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539814A (en) * | 2022-02-26 | 2022-05-27 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion white carbon black |
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