CN104031272B - Amination nano-silica modified PBO polymer and preparation method thereof - Google Patents
Amination nano-silica modified PBO polymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to modified PBO polymers and preparation methods of the modified PBO polymers, in particular to an amination nano-silica modified PBO polymer and a preparation method of the amination nano-silica modified PBO polymer. The technical problem that an existing PBO polymer is poor in ultraviolet resistance is solved. Please find the structural formula of the amination nano-silica modified PBO polymer in the specifications, wherein n and s in the structural formula represent the degree of polymerization, n equals 30-100 and S equals 30-100. The preparation method comprises the first step of performing amination on nano-silica, the second step of precipitating the amination nano-silica through concentrated hydrochloric acid, then adding the precipitated amination nano-silica into a SnCl2 aqueous solution dissolved with 4, 6-diamino resorcinol hydrochloride to obtain a solution A, dissolving terephthalic acid in a NaOH aqueous solution to obtain a solution B, and then dropwise adding the solution B into the solution A to obtain a composite inner salt after reacting, and the third step of adding the composite inner salt into a polyphosphoric acid solution and heating up for polymerization to obtain the amination nano-silica modified PBO polymer.
Description
Technical field
The present invention relates to modified PBO polymer and preparation method thereof.
Background technology
PBO polymer is one of Liquid Crystalline Aromatic Polybenzazoles class representative polymer.Polyphenyl azole fiber is that a class is divided greatly
Lysotropic liquid crystal containing benzothiazole ring, benzoxazole ring, the rigid rod heterocycle structure of benzimidazole ring polymerization on sub- main chain
Fibres, they mostly have the characteristics such as higher mechanical property, high temperature resistant and resistance to chemical attack so as to become the high property of new class
Can fibrous material.Therefore, pbo fiber has huge application prospect as the reinforcement of composite.But pbo fiber is in purple
Outer light irradiation 100h, its intensity only remains original 50%, and UV resistant performance is poor.
Content of the invention
The present invention is to solve the technical problem of existing pbo fiber UV resistant performance difference, and a kind of amination is provided
Nano-silicon dioxide modified PBO polymer and preparation method thereof.
The structural representation of the nano-silicon dioxide modified PBO polymer of the amination of the present invention is：
Wherein n, s represent the degree of polymerization, n=30～100, s=30～100.
The preparation method of the nano-silicon dioxide modified PBO polymer of above-mentioned amination is carried out according to the following steps：
First, the amination of nano silicon is processed：
A, by nano silicon add dry toluene in, stir, obtain silicon dioxide gel,
B, again by this silicon dioxide gel heating in water bath to 80～85 DEG C, be subsequently adding silane coupler, be warming up to boiling
Flow back and maintain the reflux for state 8～12h, then cooling, standing, remove the supernatant, by the product of lower floor successively with ethanol, go
Ionized water eccentric cleaning, lyophilization, obtain amidized nano silicon (NH2-SNPs)；
2nd, the pretreatment of comonomer：
C, by amidized nano silicon (NH2- SNPs) it is dissolved in deionized water, Deca concentrated hydrochloric acid, there is precipitation to produce
Raw, sucking filtration, washing will be precipitated, after lyophilization, obtain amination silicon dioxide hydrochloric acid salt powder；
D, 4,6- diamino resorcin hydrochlorate is dissolved in SnCl2In aqueous solution, add amination silicon dioxide salt
Hydrochlorate powder, stirring and dissolving, obtain solution A；
E, p-phthalic acid (TPA) is dissolved in NaOH aqueous solution, obtains solution B；
F, under nitrogen protection, solution B is added drop-wise in solution A, stirring reaction under conditions of temperature is 90～95 DEG C
0.5～1h, has solid to separate out, and the solid sucking filtration separating out, washing, lyophilization obtain compound inner salt ((DADHB/NH2-
SNPs)-is-TPA)；
3rd, the synthesis of SNPs-PBO complex
G, the configuration of polyphosphoric acids：By P2O5Add mass concentration be in 82%～85% strong phosphoric acid, temperature be 78～
Under conditions of 85 DEG C, stirring reaction 1～1.5h, obtains poly phosphoric acid solution；
H, by compound inner salt ((DADHB/NH2- SNPs)-is-TPA) it is added in poly phosphoric acid solution, add catalyst
The SnCl of amount2·2H2O, stirring reaction 2～3h at a temperature of 76～85 DEG C, then heat to 120 DEG C and stir to system mixing
Uniformly, then 138～145 DEG C of holding reaction 5～5.5h are warming up to the programming rate of 4～5 DEG C/h, then the liter with 4～5 DEG C/h
Warm speed is warming up to 158～165 DEG C of holding reaction 10～10.5h, finally it is warming up to 178 with the programming rate of 4～5 DEG C/h～
185 DEG C of holding reaction 10～10.5h, obtain the nano-silicon dioxide modified PBO polymer of amination.
The course of reaction of the nano-silicon dioxide modified PBO polymer of the amination of the present invention can use following formula table
Show：
Wherein n, s represent the degree of polymerization, n=30～100, s=30～100.
The present invention first adopts silane coupler to process nano silicon, obtains with amido modified nano silicon
Then aminosilica after processing is made terephthalate by particle, then with 4,6-diaminoresorcinol and right
Phthalic acid copolycondensation, obtains the nano-silicon dioxide modified PBO polymer of amination, and nano silicon has small size effect
Should and macro quanta tunnel effect, silicon dioxide is connected near the unsaturated bond of macromolecular chain, and and unsaturated bond electronics
Cloud is had an effect, and improves heat, light stability and the chemical stability of macromolecular material, thus improving anti-ultraviolet aging, heat
Ageing properties and chemical-resistance.The nano-silicon dioxide modified PBO polymer of amination in ultraviolet light 100h, its intensity
Only reduce by 8%～14%, modulus reduces by 15%～20%, compared with PBO, the stability under ultraviolet irradiates significantly improves.
Brief description
Fig. 1 is the fourier infrared absorbing light of the nano silicon in a in test 1 and amidized nano silicon
Spectrogram；
Fig. 2 is the FT-IR spectrum figure of nano silicon and amidized nano silicon in test 2；
Specific embodiment
Specific embodiment one：The structural table of the nano-silicon dioxide modified PBO polymer of the amination of present embodiment
Show that formula is：
Wherein n, s represent the degree of polymerization, n=30～100, s=30～100.
Specific embodiment two：The nano-silicon dioxide modified PBO polymer of amination described in specific embodiment one
Preparation method, carry out according to the following steps：
First, the amination of nano silicon is processed：
A, by nano silicon add dry toluene in, stir, obtain silicon dioxide gel,
B, again by this silicon dioxide gel heating in water bath to 80～85 DEG C, be subsequently adding silane coupler, be warming up to boiling
Flow back and maintain the reflux for state 8～12h, then cooling, standing, remove the supernatant, by the product of lower floor successively with ethanol, go
Ionized water eccentric cleaning, lyophilization, obtain amidized nano silicon (NH2-SNPs)；
2nd, the pretreatment of comonomer：
C, by amidized nano silicon (NH2- SNPs) it is dissolved in deionized water, Deca concentrated hydrochloric acid, there is precipitation to produce
Raw, sucking filtration, washing will be precipitated, after lyophilization, obtain amination silicon dioxide hydrochloric acid salt powder；
D, 4,6- diamino resorcin hydrochlorate is dissolved in SnCl2In aqueous solution, add amination silicon dioxide salt
Hydrochlorate powder, stirring and dissolving, obtain solution A；
E, p-phthalic acid (TPA) is dissolved in NaOH aqueous solution, obtains solution B；
F, under nitrogen protection, solution B is added drop-wise in solution A, stirring reaction under conditions of temperature is 90～95 DEG C
0.5～1h, has solid to separate out, and the solid sucking filtration separating out, washing, lyophilization obtain compound inner salt ((DADHB/NH2-
SNPs)-is-TPA)；
3rd, the synthesis of SNPs-PBO complex
G, the configuration of polyphosphoric acids：By P2O5Add mass concentration be in 82%～85% strong phosphoric acid, temperature be 78～
Under conditions of 85 DEG C, stirring reaction 1～1.5h, obtains poly phosphoric acid solution；
H, by compound inner salt ((DADHB/NH2- SNPs)-is-TPA) it is added in poly phosphoric acid solution, add catalyst
The SnCl of amount2·2H2O, stirring reaction 2～3h at a temperature of 76～85 DEG C, then heat to 120 DEG C and stir to system mixing
Uniformly, then 138～145 DEG C of holding reaction 5～5.5h are warming up to the programming rate of 4～5 DEG C/h, then the liter with 4～5 DEG C/h
Warm speed is warming up to 158～165 DEG C of holding reaction 10～10.5h, finally it is warming up to 178 with the programming rate of 4～5 DEG C/h～
185 DEG C of holding reaction 10～10.5h, obtain the nano-silicon dioxide modified PBO polymer of amination.
Specific embodiment three：Present embodiment and nano silicon in step a unlike specific embodiment two
The ratio of quality and the volume of silane coupler in step b be 1g：(4～5) mL.Other identical with specific embodiment two.
Specific embodiment four：Present embodiment is silane coupled from step b unlike specific embodiment two or three
Agent is Silane coupling agent KH550, KH540 or KH792.Other identical with specific embodiment two or three.
Specific embodiment five：Amino in step c unlike one of present embodiment and specific embodiment two to four
The quality of nano silicon changed is 1g with the ratio of the volume of deionized water：(150～200) mL.Other and specific embodiment party
One of formula two to four is identical.
Specific embodiment six：SnCl in step d unlike one of present embodiment and specific embodiment two to five2
The mass percentage concentration of aqueous solution is 0.01%～0.05%, the quality of 4,6-diaminoresorcinol hydrochlorate and SnCl2Water
SnCl in solution2Quality ratio be 250～300)：1.Other identical one of with specific embodiment two to five.
Specific embodiment seven：4,6- in step d unlike one of present embodiment and specific embodiment two to six
Diamino resorcin hydrochlorate is (100～200) with the mass ratio of amination silicon dioxide hydrochlorate：1.Other with concrete reality
Apply one of mode two to six identical.
Specific embodiment eight：4,6- in step d unlike one of present embodiment and specific embodiment two to seven
The preparation method of diamino resorcin hydrochlorate is as follows：4,6-diaminoresorcinol (DAR) is dissolved in deionized water, so
Deca concentrated hydrochloric acid afterwards, has white crystal to separate out, crystal is filtered out, is washed with concentrated hydrochloric acid, and re-dry obtains white 4,6- bis-
Aminoresorcinol hydrochlorate (DADHB).Other identical one of with specific embodiment two to seven.
Specific embodiment nine：NaOH in step e unlike one of present embodiment and specific embodiment two to eight
The concentration of aqueous solution is 0.1～0.12mol/L.Other identical one of with specific embodiment two to eight.
Specific embodiment ten：To benzene in step e unlike one of present embodiment and specific embodiment two to nine
The quality of dioctyl phthalate (TPA) and the ratio of the volume of NaOH aqueous solution are 1g：(40～50) mL.Other with specific embodiment two to
One of nine is identical.
Specific embodiment 11：Molten in step f unlike one of present embodiment and specific embodiment two to ten
In liquid A, 4,6- diamino resorcin hydrochlorate and the mass ratio of p-phthalic acid in solution B are 1：(0.8～1.5).Other with
One of specific embodiment two to ten is identical.
Specific embodiment 12：In step g unlike one of present embodiment and specific embodiment two to ten one
P2O5The mass ratio of the strong phosphoric acid being 82%～85% with mass concentration is 1：(1～2).Other and specific embodiment two to ten
One of one is identical.
Specific embodiment 13：In step h unlike one of present embodiment and specific embodiment two to ten two
Compound inner salt ((DADHB/NH2- SNPs)-is-TPA) it is 1 with the mass ratio of poly phosphoric acid solution：(5～6), compound inner salt
((DADHB/NH2- SNPs)-is-TPA) and SnCl2·2H2The mass ratio of O is (48～150)：1.Other and specific embodiment
One of two to ten two is identical.
Specific embodiment 14：In step c unlike one of present embodiment and specific embodiment two to ten three
The mass percentage concentration of concentrated hydrochloric acid is 36.5～37%.Other identical one of with specific embodiment two to ten three.
Specific embodiment 15：In step b unlike one of present embodiment and specific embodiment two to ten four
Rotating speed during deionized water eccentric cleaning is 5000～10000 revs/min.Other and one of specific embodiment two to ten four phase
With.
With following verification experimental verification beneficial effects of the present invention：
Test 1：The preparation method of the nano-silicon dioxide modified PBO polymer of the amination of this test is entered according to the following steps
OK：
First, the amination of nano silicon is processed：
A, by 5g nano silicon add 100ml dry toluene in, stir, obtain silicon dioxide gel, transfer
To in 250ml there-necked flask；
B, again by this silicon dioxide gel heating in water bath to 85 DEG C, be subsequently adding 20ml Silane coupling agent KH550, be warming up to
Boiling reflux simultaneously maintains the reflux for state 8h, then cooling, standing, removes the supernatant, and the product of lower floor is clear with ethanol successively
Wash 3 times, deionized water eccentric cleaning 3 times, lyophilization under conditions of rotating speed is 10000 revs/min, obtain amidized nanometer
Silicon dioxide (NH2-SNPs)；
2nd, the pretreatment of comonomer：
C, by amidized for 5g nano silicon (NH2- SNPs) it is dissolved in 500ml deionized water, Deca percent mass
Concentration is 37% concentrated hydrochloric acid, has precipitation to produce, and will precipitate sucking filtration, washing, after lyophilization, obtain amination silicon dioxide hydrochloric acid
Salt powder；
D, by 30g4,6- diamino resorcin (DAR) is dissolved in 600ml deionized water, and then Deca percent mass is dense
Spend the concentrated hydrochloric acid for 37%, have white crystal to separate out, filter out crystal, washed with the concentrated hydrochloric acid that mass percentage concentration is 36.5%
Wash, at 50 DEG C, 24h is dried, obtain white 4,6-diaminoresorcinol hydrochlorate (DADHB), by 30g4, between 6- diaminourea
Benzodiazepiness hydrochlorate is dissolved in SnCl2Mass concentration is 0.05% SnCl2In aqueous solution, add 0.2g amination silicon dioxide
Hydrochloric acid salt powder, stirring and dissolving, obtain solution A；
E, 24g p-phthalic acid (TPA) is dissolved in 1000ml concentration be 0.1mol/L NaOH aqueous solution in, obtain
Solution B；
F, under nitrogen protection, solution B is added drop-wise in solution A, stirring reaction 0.5h under conditions of temperature is 90 DEG C,
There is solid to separate out, the solid sucking filtration separating out, washing, lyophilization obtain compound inner salt ((DADHB/NH2-SNPs)-is-
TPA)；
3rd, the synthesis of SNPs-PBO complex
G, the configuration of polyphosphoric acids：By 32.6g P2O5It is added to the strong phosphoric acid that 48.6g mass concentration is 85% in three times
In, stirring reaction 1h under conditions of temperature is 80 DEG C, obtain the thick poly phosphoric acid solution of water white transparency；
H, by 14.8g be combined inner salt ((DADHB/NH2- SNPs)-is-TPA) it is added in poly phosphoric acid solution, add
0.2g SnCl2·2H2O, stirring reaction 2h at a temperature of 80 DEG C, then heat to 120 DEG C stir completely molten to compound inner salt
Solution in poly phosphoric acid solution, i.e. system mix homogeneously, then with the programming rate of 5 DEG C/h be warming up to 140 DEG C keep reaction 5h,
It is warming up to 160 DEG C with the programming rate of 5 DEG C/h again and keeps reaction 10h, finally 180 DEG C of guarantors are warming up to the programming rate of 5 DEG C/h
Hold reaction 10h, now rod climbing phenomenon in system, and along with opalescence phenomenon, this illustrate polymerization system already at liquid crystalline phase,
Terminate reaction, obtain the nano-silicon dioxide modified PBO polymer of amination.
Nano silicon in step a of this test, the Fourier of the amidized nano silicon obtaining in step b
Leaf infrared absorpting light spectra as shown in figure 1, wherein nano silicon FT-IR spectrum figure as indicated at a, amino
Change nano silicon FT-IR spectrum figure as shown in B, in figure, 801cm-1And 1104cm-1The absworption peak at place
It is to be caused by the symmetric vibration of Si-O key and antisymmetric vibration in silicon dioxide, 463cm-1The absworption peak at place is by Si-O key
Bending vibration causes.And in 3423cm-1Place, the silicon dioxide of nano silicon has a wide absworption peak, and this is by two
Silicon oxide surface has substantial amounts of O-H, and this is also available with silane coupler and carries out surface amination process to silicon dioxide
Reason.In the spectrogram of amidized nano silicon obtaining after being processed by amination, this peak disappears, explanation
KH550 there occurs reaction with the hydroxyl of silica surface.The amidized nanometer titanium dioxide obtaining after display processing on spectrogram
Silicon is also respectively in 1561cm-1、1347cm-1Place creates new absworption peak, 1561cm-1The absworption peak at place is to be caused by N-H vibration
, this directly illustrates that the KH550 with amino has been connected to silica surface；1347cm-1The absworption peak at place is symmetrically curved by C-H
Qu Zhendong causes, this also side light KH550 there occurs reaction in silica surface, be connected to silica surface.
The structural formula of the nano-silicon dioxide modified PBO polymer of amination that this test obtains is represented by：
Wherein n, s represent the degree of polymerization, n=30～60, s=30～60.
Tensile strength 2.37GPa of the nano-silicon dioxide modified PBO polymer of amination that this test obtains, modulus
77.54GPa, is placed on this material irradiation 100h under the ultraviolet light of 300～400nm wave-length coverage, and its tensile strength is
2.04GPa, modulus is 62.32GPa, and its intensity only reduces by 13.9%, modulus reduces by 19.6%, illustrates to use amination nanometer two
Silicon oxide can improve the anti-uv-ray of material to PBO polymer.
Test 2：The preparation method of the nano-silicon dioxide modified PBO polymer of the amination of this test is entered according to the following steps
OK：
First, the amination of nano silicon is processed：
A, by 5g nano silicon add 100ml dry toluene in, stir, obtain silicon dioxide gel, transfer
To in 250ml there-necked flask；
B, again by this silicon dioxide gel heating in water bath to 85 DEG C, be subsequently adding 25ml Silane coupling agent KH550, be warming up to
Boiling reflux simultaneously maintains the reflux for state 10h, and then cooling, standing, remove the supernatant, the product of lower floor is existed with ethanol successively
Rotating speed cleans 3 times under conditions of rotating speed is 8000 revs/min for eccentric cleaning 3 times, deionized water under conditions of 8000 revs/min,
Lyophilization, obtains amidized nano silicon (NH2-SNPs)；
2nd, the pretreatment of comonomer：
C, by amidized for 5g nano silicon (NH2- SNPs) it is dissolved in 500ml deionized water, Deca percent mass
Concentration is 36.5% concentrated hydrochloric acid, has precipitation to produce, and will precipitate sucking filtration, washing, after lyophilization, obtain amination silicon dioxide
Hydrochloric acid salt powder；
D, by 30g4,6- diamino resorcin (DAR) is dissolved in 600ml deionized water, and then Deca concentrated hydrochloric acid has white
Color crystal separates out, and filters out crystal, is washed with concentrated hydrochloric acid, 24h is dried at 50 DEG C, obtains white 4,6-diaminoresorcinol
Hydrochlorate (DADHB), by 30g4,6- diamino resorcin hydrochlorate is dissolved in SnCl2Mass concentration is 0.03% SnCl2Water
In solution, add 0.15g amination silicon dioxide hydrochloric acid salt powder, stirring and dissolving, obtain solution A；
E, 24g p-phthalic acid (TPA) is dissolved in 1000ml concentration be 0.1mol/L NaOH aqueous solution in, obtain
Solution B；
F, under nitrogen protection, solution B is added drop-wise in solution A, stirring reaction 0.5h under conditions of temperature is 92 DEG C,
There is solid to separate out, the solid sucking filtration separating out, washing, lyophilization obtain compound inner salt ((DADHB/NH2-SNPs)-is-
TPA)；
3rd, the synthesis of SNPs-PBO complex
G, the configuration of polyphosphoric acids：By 35g P2O5It is added in three times in the strong phosphoric acid that 50g mass concentration is 85%,
Temperature is stirring reaction 1h under conditions of 78 DEG C, obtains the thick poly phosphoric acid solution of water white transparency；
H, by 18g be combined inner salt ((DADHB/NH2- SNPs)-is-TPA) it is added in poly phosphoric acid solution, add 0.2g
SnCl2·2H2O, stirring reaction 2h at a temperature of 80 DEG C, then heat to 120 DEG C and stir do not observe to solution in compound
The granule of salt exists, i.e. system mix homogeneously, is then warming up to 140 DEG C with the programming rate of 5 DEG C/h and keeps reaction 5h, then with 5
DEG C/programming rate of h is warming up to 160 DEG C and keeps reaction 10h, finally it is warming up to 180 DEG C with the programming rate of 5 DEG C/h and keep reaction
10h, now system rod climbing phenomenon occurs, and along with opalescence phenomenon, this explanation polymerization system, already at liquid crystalline phase, terminates anti-
Should, obtain the nano-silicon dioxide modified PBO polymer of amination.
Nano silicon in step a of this test, the Fourier of the amidized nano silicon obtaining in step b
Leaf infrared absorpting light spectra as shown in Fig. 2 wherein nano silicon FT-IR spectrum figure as indicated at a, amino
As shown at c, A is understood compared with C the FT-IR spectrum figure of the nano silicon changed, after being processed by amination
In the spectrogram of amidized nano silicon obtaining, 3423cm-1The absworption peak at place disappears, and KH550 and titanium dioxide are described
The hydroxyl of silicon face there occurs reaction.The amidized nano silicon obtaining after display processing on spectrogram also exists respectively
1561cm-1、1347cm-1Place creates new absworption peak, 1561cm-1The absworption peak at place is caused by N-H vibration, and this is direct
Illustrate that the KH550 with amino has been connected to silica surface；1347cm-1The absworption peak at place is to be drawn by the symmetric curvature vibration of C-H
Rise, this also side light KH550 there occurs reaction in silica surface, be connected to silica surface.
The structural formula of the nano-silicon dioxide modified PBO polymer of amination that this test obtains is represented by：
Wherein n, s represent the degree of polymerization, n=40～70, s=40～70.
The tensile strength of the nano-silicon dioxide modified PBO polymer of amination that this test obtains is 2.52GPa, modulus
For 76.24GPa, this material is placed on irradiation 100h under the ultraviolet light of wave-length coverage 300nm～400nm, its tensile strength is
2.14GPa, modulus 63.14GPa, its intensity only reduces by 15%, and modulus reduces by 17%, illustrates to use amination nano silicon pair
PBO polymer can improve the anti-uv-ray of material.
Claims (9)
1. a kind of nano-silicon dioxide modified PBO polymer of amination is it is characterised in that the structural representation of this polymer is：
Wherein n, s represent the degree of polymerization, n=30～100, s=30～100.
2. the method preparing the nano-silicon dioxide modified PBO polymer of a kind of amination as claimed in claim 1, its feature
It is that the method is carried out according to the following steps：
First, the amination of nano silicon is processed：
A, by nano silicon add dry toluene in, stir, obtain silicon dioxide gel,
B, again by this silicon dioxide gel heating in water bath to 80～85 DEG C, be subsequently adding silane coupler, be warming up to boiling reflux
And maintain the reflux for state 8～12h, then cooling, standing, remove the supernatant, the product of lower floor are used successively ethanol, deionization
Water eccentric cleaning, lyophilization, obtain amidized nano silicon；
2nd, the pretreatment of comonomer：
C, amidized nano silicon is dissolved in deionized water, Deca concentrated hydrochloric acid, has precipitation to produce, will precipitate sucking filtration,
After washing, lyophilization, obtain amination silicon dioxide hydrochloric acid salt powder；
D, 4,6- diamino resorcin hydrochlorate is dissolved in SnCl2In aqueous solution, add amination silicon dioxide hydrochloric acid salt fines
End, stirring and dissolving, obtain solution A；
E, p-phthalic acid is dissolved in NaOH aqueous solution, obtains solution B；
F, under nitrogen protection, solution B is added drop-wise in solution A, under conditions of temperature is 90～95 DEG C stirring reaction 0.5～
1h, has solid to separate out, and the solid sucking filtration separating out, washing, lyophilization obtain compound inner salt；
3rd, the synthesis of the nano-silicon dioxide modified PBO polymer of amination：
G, the configuration of polyphosphoric acids：By P2O5Add mass concentration to be in 82%～85% strong phosphoric acid, be 78～85 DEG C in temperature
Under conditions of stirring reaction 1～1.5h, obtain poly phosphoric acid solution；
H, compound inner salt is added in poly phosphoric acid solution, adds the SnCl of catalytic amount2·2H2O, in 76～85 DEG C of temperature
The lower stirring reaction 2～3h of degree, then heating to 120 DEG C stirs to system mix homogeneously, then with the programming rate of 4～5 DEG C/h
It is warming up to 138～145 DEG C of holding reaction 5～5.5h, then is warming up to 158～165 DEG C with the programming rate of 4～5 DEG C/h and keep anti-
Answer 10～10.5h, finally 178～185 DEG C of holding reaction 10～10.5h are warming up to the programming rate of 4～5 DEG C/h, obtain ammonia
The nano-silicon dioxide modified PBO polymer of baseization.
3. the preparation method of the nano-silicon dioxide modified PBO polymer of a kind of amination according to claim 2, it is special
Levy and be that in step a, the quality of nano silicon and the ratio of the volume of silane coupler in step b are 1g：(4～5) mL.
4. the preparation method of the nano-silicon dioxide modified PBO polymer of a kind of amination according to Claims 2 or 3,
It is characterized in that the quality of amidized nano silicon and the ratio of the volume of deionized water are 1g in step c：(150～
200)mL.
5. the preparation method of the nano-silicon dioxide modified PBO polymer of a kind of amination according to Claims 2 or 3,
It is characterized in that SnCl in step d2The mass percentage concentration of aqueous solution is 0.01%～0.05%, 4,6-diaminoresorcinol
The quality of hydrochlorate and SnCl2SnCl in aqueous solution2Quality ratio be (250～300)：1.
6. the preparation method of the nano-silicon dioxide modified PBO polymer of a kind of amination according to Claims 2 or 3,
It is characterized in that 4,6- diamino resorcin hydrochlorate and the mass ratio of amination silicon dioxide hydrochlorate are (100 in step d
～200)：1.
7. the preparation method of the nano-silicon dioxide modified PBO polymer of a kind of amination according to Claims 2 or 3,
It is characterized in that the preparation method of 4,6- diamino resorcin hydrochlorate is as follows in step d：By 4,6- diamino resorcin
It is dissolved in deionized water, then Deca concentrated hydrochloric acid, have crystal to separate out, crystal is filtered out, is washed with concentrated hydrochloric acid, re-dry,
Obtain 4,6- diamino resorcin hydrochlorate.
8. the preparation method of the nano-silicon dioxide modified PBO polymer of a kind of amination according to Claims 2 or 3,
It is characterized in that the concentration of NaOH aqueous solution is 0.1～0.12mol/L in step e.
9. the preparation method of the nano-silicon dioxide modified PBO polymer of a kind of amination according to Claims 2 or 3,
It is characterized in that 4,6- diamino resorcin hydrochlorate and the mass ratio of p-phthalic acid in solution B are in solution A in step f
1：(0.8～1.5).
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| CN102634976B (en) * | 2012-04-20 | 2013-12-11 | 哈尔滨工业大学 | Method for enhancing ultraviolet resistance stability of PBO (poly-p-phenylenebenzobisthiazole) fibers by depositing (POSS (polyhedral oligomeric silsesquioxane)/TiO2)n films on surfaces |
| CN103789754A (en) * | 2014-03-04 | 2014-05-14 | 哈尔滨工业大学 | Method for preparing Ni/P/nano-SiO2 ternary composite coating on PBO fiber surface |
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