CN1259359C - Method for synthesizing polymer of benzoxazole class - Google Patents
Method for synthesizing polymer of benzoxazole class Download PDFInfo
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- CN1259359C CN1259359C CN 200410017348 CN200410017348A CN1259359C CN 1259359 C CN1259359 C CN 1259359C CN 200410017348 CN200410017348 CN 200410017348 CN 200410017348 A CN200410017348 A CN 200410017348A CN 1259359 C CN1259359 C CN 1259359C
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- aromatic amine
- ammonia
- amine compounds
- fragrant phenol
- phosphoric acid
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Abstract
The present invention relates to an improved method for preparing polymers of the benzoxazole class. The present invention comprises: carboxylic acid containing aromaticring and ammonia-substituted aromatic phenol or the phosphate of compounds of the aromatic amine class and are used as raw materials, and the present invention is prepared by the polycondensation the raw materials in non-oxide dehydration acid solution. The present invention has the greatest characteristic that in the polycondensation process, the degasification process is not need, and therefore, a plurality of defects existing in the polycondensation reaction in the prior art, which are caused by the degasification process, are overcome.
Description
Technical field
The present invention relates to a kind of preparation method of benzoxazolyl polymer.
Background technology
Benzoxazolyl polymer is high strength of new generation, high-modulus, high temperature-resistant polymer material, its fiber that spinning obtains under the mesomorphic phase solution state, and not only its good mechanical performance, and its thermostability is also more near organic polymer crystalline theoretical boundary.Therefore, the research of benzoxazolyl polymer is received day by day the concern of scientists.
Benzoxazolyl polymer can be AB type unit (its structure as shown in Equation 1), or is AA/BB type unit (its structure as shown in Equation 2).
For synthesizing of the unitary benzoxazolyl polymer of AA/BB type, be that employing contains the carboxylic acid (AA-monomer) of aromatic ring and ammonia replaces fragrant phenol or aromatic amine compounds (BB-monomer) polycondensation in non-oxide dehydracetic acid solution forms.Because used BB-monomer is to contain amino (NH
2) fragrant phenolic compound, it is very easily oxidized, thereby influences polyreaction.Existing solution is: the BB-monomer is made hydrochloride form use.So when adopting monomeric hydrochloride of BB-and AA-monomer to carry out polycondensation, need remove the hydrogen chloride gas in the BB-monomer hydrochloride, its drawback is many: the first, because every mole of BB-monomer hydrochloride will produce two moles of hydrogen chloride gas, these gases can produce a large amount of foams in the heavy-gravity reaction solution, thereby reduced the stirring efficiency of reaction system, and good mixing effect is that the formation high molecular weight polymers is necessary.It two is, hydrogen chloride gas is a severe corrosive gas, and this makes that reaction is very high for the requirement of equipment material, and degasification process is extremely time-consuming, thereby has just reduced the economical efficiency of polyreaction.It three is, in polycondensation, when monomeric charging equivalence ratio is 1: 1, usually can obtain high molecular weight polymers, in case the monomer feed ratio departed from 1: 1, polymer viscosity can sharply reduce, even the poly-phenomenon of resistance takes place, have a strong impact on the final molecular weight of polymkeric substance.That is to say, in order to obtain enough gratifying polymerization degree, must the monomeric charge ratio of strict control.Yet, in the synthetic method of existing benzoxazolyl polymer, the monomeric hydrochloride of the BB-incomplete phenomenon that outgases often appears, like this, control monomeric charge ratio and be unusual difficulty.It four is, in the prior art, what Vanadium Pentoxide in FLAKES adopted usually is the mode that substep adds, promptly in deaeration stage, relatively low as the phosphorus pentoxide content in the polyphosphoric acid of reaction medium, to be de-gassedly add Vanadium Pentoxide in FLAKES to the phosphorus pentoxide content in the reaction system again after fully and reach 83～85wt%.For being easy to the degassing, the temperature of reaction system is raise, yet, under hot conditions, can cause side reaction to increase, on the other hand, under the situation that phosphorus pentoxide content is lower in system, polycondensation but is difficult for carrying out.
Summary of the invention
The objective of the invention is to, a kind of synthetic method of benzoxazolyl polymer is provided,, overcome the defective that exists in the existing polymerization process even BB-monomer hydrochloride forms the BB-monomer phosphoric acid salt that can participate in polycondensation directly in phosphoric acid solution.
Technical scheme:
The synthetic method of the said benzoxazolyl polymer of the present invention, it is a raw material with the salt that the carboxylic acid (AA-monomer) that contains aromatic ring and ammonia replace fragrant phenol or aromatic amine compounds (BB-monomer), polycondensation forms in non-oxide dehydracetic acid solution, it is characterized in that the salt that said ammonia replaces fragrant phenol or aromatic amine compounds is the phosphoric acid salt that ammonia replaces fragrant phenol or aromatic amine compounds.
Prepare that said ammonia replaces fragrant phenol or the phosphatic key step of aromatic amine compounds (BB-monomer) is: with BB-monomer hydrochloride under 10～80 ℃ and non-oxidizing atmosphere condition, be dissolved in the phosphoric acid, the weight ratio of BB-monomer hydrochloride and phosphoric acid is 1: 15～40, treat that it dissolves the back fully and adds precipitation agent, precipitate in 0～20 ℃, promptly get the monomeric phosphoric acid salt of BB-behind filtration, washing and the dry sediment.
Wherein said precipitation agent is C
2～C
6Primary alconol, preferred alcohol or n-propyl alcohol; Preferred solvent temperature is 50～60 ℃; Precipitation temperature is advisable with 0 ℃.In addition, not oxidized for guaranteeing the BB-monomer, also can in above-mentioned system, add reductive agent (as tin protochloride etc.), the add-on of reductive agent is 1%～3% of the ammonia hydrochloride weight that replaces fragrant phenol or aromatic amine compounds.
The carboxylic acid that the present invention replaces fragrant phenol or aromatic amine compounds phosphoric acid salt with ammonia and contains aromatic ring is a raw material, make benzoxazolyl polymer by polycondensation, its maximum characteristics are, in polycondensation process, need not pass through degasification process, thus overcome since degasification process to many defectives that polycondensation caused.
Embodiment
The invention will be further elaborated below by embodiment, its objective is better understanding content of the present invention.Therefore, protection scope of the present invention is not subjected to the restriction of embodiment:
Embodiment 1
The phosphatic preparation of BB-monomer
With 10g (0.0469mol) 4, the 6-diamino resorcin hydrochlorate, 0.3g tin protochloride and 100ml 85% phosphoric acid mix stirring under argon atmospher, be warming up to 60 ℃, treat that solution clarification back is cooled to 0 ℃ with mixture of ice and water, drip the 80ml n-propyl alcohol, filtering and washing gets 14.6g (efficiency of pcr product is 92.5%) white powder solid, according to efficient liquid phase chromatographic analysis, product purity is 99.75%.
Ultimate analysis: the mass percent of Elements C, H, N is followed successively by 21.74%, 4.26%, 8.24% in the product,
Theoretical value: C:21.43%, H:4.17%, 0:8.33%.
Embodiment 2
The phosphatic preparation of BB-monomer
With 12g (0.0563mol) 4, the 6-diamino resorcin hydrochlorate, 0.3g tin protochloride and 140ml 85% phosphoric acid mix stirring under argon atmospher, be warming up to 50 ℃, treat that solution clarification back is cooled to 0 ℃ with mixture of ice and water, drip the 100ml n-propyl alcohol, filtering and washing gets 16.6g (efficiency of pcr product is 87.8%) white powder solid.
Embodiment 3
The phosphatic preparation of BB-monomer
According to feeding intake of embodiment 2, different is that solvent temperature is 60 ℃, finally obtains the solid product 17.9g (efficiency of pcr product is 94.7%) of white powder.
Embodiment 4
The phosphatic preparation of BB-monomer
With 12g (0.0563mol) 4, the 6-diamino resorcin hydrochlorate, 0.3g tin protochloride and 280ml 85% phosphoric acid mix stirring under argon atmospher, be warming up to 50 ℃, treat that solution clarification back is cooled to 0 ℃ with mixture of ice and water, drip the 100ml n-propyl alcohol, filtering and washing gets 9.7g (efficiency of pcr product is 51.3%) white powder solid.
Embodiment 5
The phosphatic preparation of BB-monomer
With 12g (0.0563mol) 4, the 6-diamino resorcin hydrochlorate, 0.3g tin protochloride and 140ml 85% phosphoric acid mix stirring under argon atmospher, be warming up to 60 ℃, treat that solution clarification back filtered while hot is to being cooled in 0 ℃ the 100ml n-propyl alcohol with mixture of ice and water in advance, a large amount of white precipitates appear immediately, suction filtration, wash 17.1g (efficiency of pcr product is 90.5%) white powder solid.
Embodiment 6
The phosphatic preparation of BB-monomer
With 25g (0.1173mol) 4, the 6-diamino resorcin hydrochlorate, 0.5g tin protochloride and 450ml 85% phosphoric acid mix stirring under argon atmospher, be warming up to 60 ℃, treat that solution clarification back filtered while hot is to being cooled in 0 ℃ the 200ml n-propyl alcohol with mixture of ice and water in advance, a large amount of white precipitates appear immediately, suction filtration, wash 35.2g (efficiency of pcr product is 89.3%) white powder solid.
Embodiment 7
The polyreaction of BB-monomer phosphoric acid salt and terephthalic acid
Under argon atmospher, with 10g monomer phosphoric acid salt (by embodiment 1 prepared compound), 4.945g the polyphosphoric acid that terephthalic acid and 23.20g contain the 80wt% Vanadium Pentoxide in FLAKES is violent stirring 1h at room temperature, be warming up to 80 ℃ and add the 19.90g Vanadium Pentoxide in FLAKES, insulation 1h under 100 ℃, 120 ℃ are incubated 1h down, and 130 ℃ are incubated 10h down and opalescence occurs stirring, 150 ℃ are incubated 10h down, and 180 ℃ are incubated 3h down and obtain yellow polymer.This polymkeric substance that takes a morsel is dissolved in methylsulphonic acid and prepares to such an extent that concentration is the solution of 0.044g/dl and to survey its intrinsic viscosity under 30 ℃ be 10.37dl/g.
Embodiment 8
The polyreaction of BB-monomer phosphoric acid salt and terephthalic acid
Under argon atmospher, with 16g monomer phosphoric acid salt (by embodiment 2 prepared compounds), 7.911g the polyphosphoric acid that terephthalic acid and 65.85g contain the 80wt% Vanadium Pentoxide in FLAKES is violent stirring 0.5h at room temperature, add the 35.46g Vanadium Pentoxide in FLAKES after being warming up to 80 ℃ of insulation 1.5h, 90 ℃ of insulation 1h down, 110 ℃ of insulation 2h down, 130 ℃ are incubated 10h down and opalescence occurs stirring, insulation 5h under 150 ℃, 160 ℃ are incubated 5h down, and 180 ℃ are incubated 8h down and obtain the dark yellow polymkeric substance.This polymkeric substance that takes a morsel is dissolved in methylsulphonic acid and prepares to such an extent that concentration is the solution of 0.044g/dl and to survey its intrinsic viscosity under 30 ℃ be 7.97dl/g.
Embodiment 9
The polyreaction of BB-monomer phosphoric acid salt and terephthalic acid
Under argon atmospher, with 16g monomer phosphoric acid salt (by embodiment 5 prepared compounds), 7.911g the polyphosphoric acid that terephthalic acid and 27.23g contain the 80wt% Vanadium Pentoxide in FLAKES is violent stirring 0.5h at room temperature, add the 38.52g Vanadium Pentoxide in FLAKES after being warming up to 80 ℃ of insulation 1h, 80 ℃ of following insulation 1h, 130 ℃ down insulation 8h opalescence appears stirring, 150 ℃ of insulation 7h down, 160 ℃ are incubated 10h down, and 180 ℃ are incubated 5h down and obtain the yellow-green colour polymkeric substance.This polymkeric substance that takes a morsel is dissolved in methylsulphonic acid and prepares to such an extent that concentration is the solution of 0.044g/dl and to survey its intrinsic viscosity under 30 ℃ be 31.47dl/g.
Claims (5)
1, a kind of synthetic method of benzoxazolyl polymer, it is a raw material with the salt that the carboxylic acid that contains aromatic ring and ammonia replace fragrant phenol or aromatic amine compounds, polycondensation forms in non-oxide dehydracetic acid solution, it is characterized in that the salt that said ammonia replaces fragrant phenol or aromatic amine compounds is the phosphoric acid salt that ammonia replaces fragrant phenol or aromatic amine compounds.
2, as the said synthetic method of claim 1, it is characterized in that, wherein said ammonia replaces fragrant phenol or the phosphatic main preparation process of aromatic amine compounds is: ammonia is replaced fragrant phenol or aromatic amine compounds hydrochloride under 10～80 ℃ and non-oxidizing atmosphere condition, be dissolved in the phosphoric acid, the weight ratio that ammonia replaces fragrant phenol or aromatic amine compounds hydrochloride and phosphoric acid is 1: 15～40, treat that it dissolves the back fully and adds precipitation agent, precipitate in 0～20 ℃, filter, promptly get the phosphoric acid salt that ammonia replaces fragrant phenol or aromatic amine compounds behind washing and the dry sediment
Wherein said precipitation agent is C
2～C
6Primary alconol.
As the said synthetic method of claim 2, it is characterized in that 3, wherein said precipitation agent is ethanol or n-propyl alcohol.
As claim 2 or 3 said synthetic methods, it is characterized in that 4, wherein solvent temperature is 50～60 ℃; Precipitation temperature is 0 ℃.
5, as the said synthetic method of claim 4, it is characterized in that, replace in the phosphatic reaction system of fragrant phenol or aromatic amine compounds at preparation ammonia and also to add the reductive agent tin protochloride, the add-on of reductive agent is 1%～3% of the ammonia hydrochloride weight that replaces fragrant phenol or aromatic amine compounds.
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|---|---|---|---|
| CN 200410017348 CN1259359C (en) | 2004-03-31 | 2004-03-31 | Method for synthesizing polymer of benzoxazole class |
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|---|---|---|---|
| CN 200410017348 CN1259359C (en) | 2004-03-31 | 2004-03-31 | Method for synthesizing polymer of benzoxazole class |
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| CN1259359C true CN1259359C (en) | 2006-06-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430430C (en) * | 2006-09-15 | 2008-11-05 | 华东理工大学 | Benzooxazole kind block copolymer |
| CN101445603B (en) * | 2008-12-23 | 2011-01-05 | 华东理工大学 | Polyfluorene poly (benzazole) and preparation method thereof |
| CN109320704A (en) * | 2018-10-09 | 2019-02-12 | 江苏凯普特新材料科技有限公司 | A kind of block copolymerization dacron master grain and its preparation method and application containing benzimidazole structure |
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