CN102634023A - Preparation method of poly-p-phenylenebenzobisthiazole (PBO) polymer - Google Patents
Preparation method of poly-p-phenylenebenzobisthiazole (PBO) polymer Download PDFInfo
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- CN102634023A CN102634023A CN2012101224049A CN201210122404A CN102634023A CN 102634023 A CN102634023 A CN 102634023A CN 2012101224049 A CN2012101224049 A CN 2012101224049A CN 201210122404 A CN201210122404 A CN 201210122404A CN 102634023 A CN102634023 A CN 102634023A
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- polyparaphenylene ben
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- DPYROBMRMXHROQ-UHFFFAOYSA-N Nc(c(O)c1)cc(N)c1O Chemical compound Nc(c(O)c1)cc(N)c1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N OC(c(cc1)ccc1C(O)=O)=O Chemical compound OC(c(cc1)ccc1C(O)=O)=O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GSNFUPMZTQZJEV-UHFFFAOYSA-N Cc1nc(cc2nc(-c3ccc(C)cc3)[o]c2c2)c2[o]1 Chemical compound Cc1nc(cc2nc(-c3ccc(C)cc3)[o]c2c2)c2[o]1 GSNFUPMZTQZJEV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method of a polymer, particularly relates to a preparation method of a poly-p-phenylenebenzobisthiazole (PBO) polymer, and is used for solving the problems of long hydrogen chloride gas removing time and low reaction efficiency in the prior art. The method comprises the following steps of: preparing complex salt, putting 4,6-diamino resorcinol hydrochloride and polyphosphoric acid in a polymerization reaction kettle, removing hydrogen chloride gas, adding the hydrogen chloride gas in the polymerization reaction kettle, adding phosphorus pentoxide in the polymerization reaction kettle to obtain a prepolymerization material, and putting the prepolymerization material in a double-screw reactor to obtain the PBO polymer. According to the preparation method disclosed by the invention, the reaction time for removing hydrogen chloride is shortened through reducing the dosage of 4,6-diamino resorcinol hydrochloride, and the extremely easy oxidation of the complex slat is avoided through the complete protection on amino groups of 4,6-diamino resorcinol hydrochloride. The PBO polymer prepared by the method is short in reaction time, high in molecular weight and low in impurity content, thus facilitating the conducting of a following spinning process.
Description
Technical field
The present invention relates to a kind of preparation method of polymkeric substance.
Background technology
(PBO Poly-p-phenylenebenzobisthiazole) belongs to a kind of heteroaromatic rigid rod liquid crystalline polymers to polyparaphenylene Ben Bing Er oxazole, has good chemical property; Flame retardant resistance; High-temperature stability, creep resistance, chemical resistance and anti-physical abrasion property.PBO is the new polymers of developing according to molecular structure and performance principle, and its molecular structural formula is following:
Its link angle (being the angle between the ring external key on the stiff backbone unit) is 180 °, and only has two singly-bounds of phenyl ring both sides in the repeat unit structure, can not internal rotation, and institute thinks can form lytropic liquid crystals by rigid rod-like molecules.There is not weak bond in the PBO molecular structure; Fiber spinning from crystalline state technology makes and has not only kept the good orientation of liquid crystal molecule in the fiber in addition; And given fiber two and three dimensions order to a certain degree; Its excellent performance at first shows as tensile strength and reaches 5.8GPa, and tensile modulus is 280～380GPa, and its density is merely 1.56 * 10
3Kg/m
3, heat decomposition temperature is up to 650 ℃.
The performance that pbo fiber is excellent has determined it in aerospace, war products, and application prospect is very wide in many fields such as sports goods.Pbo fiber as strongthener at the BM housing, the application in thrust chamber and planetary exploration balloon field, to the lightweight of weaponry, miniaturized and high performance play crucial effects.With high temperature filtration bag and filter felt that pbo fiber is made, life-time service still can keep high-strength, high-anti-friction property under the high temperature; Do not burn in flame with heat-resisting working suit such as the high-performance bunker clothing of its manufacturing and welding job clothes, do not shrink, very soft; Utilize pbo fiber high-modulus characteristic, can be used for fibre-optic enhancing.Aspect the rubber enhancing, replace the strongthener of steel wire with it as tire, make the tire lightweight, help energy-conservation.Pbo fiber also can be at gasket seal, rubber items such as sebific duct, various resins, plastics, in Steel Concrete antidetonation cement components and the high performance synchronous transmission belt as strongthener; Simultaneously, pbo fiber is still made various high-performance ropes, cable protection layer material, tSportswear, aviation clothes, sports equipment, the ideal material of bullet resistant material.
At present, the preparation method of PBO polymkeric substance has intermediate phase polymerization, TMS method, monomer salt forming method and polyphosphoric acid method, and wherein back two kinds of methods are widely used.But also there are relative merits separately in monomer salt forming method and polyphosphoric acid method: the monomer salt forming method can avoid removing process, the shortening reaction times of hydrogenchloride, guarantees that two monomer DAR and TPA equivalent compare polymerization; But this salt is prone to oxidation; Difficult operation and storage are not suitable for industriallization, and reaction scheme is following:
The PBO polymkeric substance of
polyphosphoric acid method preparation has HMW; But initial reaction stage needs 4 days～7 days time to remove hydrogen chloride gas, and the polymerization early-stage preparations time is long; Simultaneously, in the polymerization process, receive the influence of phthalic acid granularity and solubleness, reduced speed of reaction.
Remove hydrogen chloride and prepare the PBO polymkeric substance, it is long to remove the hydrogenchloride time, and the hydrogen chloride gas of generation has corrodibility, to having relatively high expectations of equipment.The effect that removes hydrogenchloride has significant effects for the polyreaction for preparing the PBO polymkeric substance, removes hydrogenchloride and thoroughly will not cause terephthalic acid and 4, and the mol ratio of 6-diamino resorcin departed from 1: 1, and the polymericular weight that reaction obtains is low; The complexing salt legal system is equipped with the step that the PBO polymkeric substance can avoid removing hydrogenchloride; But very easily oxidation of complexing salt performed polymer through this method preparation; The reactive behavior point loss of activity that has caused complexing salt not only can not be participated in reaction in polymerization process, becomes impurity on the contrary; Hinder further polyreaction, the polymericular weight that reaction obtains is lower.The molecular weight of PBO polymkeric substance and the purity of spinning solution all will influence the mechanical property of the pbo fiber of preparation.
Summary of the invention
The present invention removes the problem that the hydrogen chloride gas time is long, reaction efficiency is low in order to solve existing method, and a kind of method of the polyparaphenylene of preparation Ben Bing Er oxazole polymkeric substance is provided.
The method that the present invention prepares polyparaphenylene Ben Bing Er oxazole polymkeric substance is following:
One, tindichloride is joined the concentration to tindichloride is 0.01mol/L～0.1mol/L in the aqueous sodium hydroxide solution that concentration is 0.01～0.1mol/L; And then with 2mol terephthalic acid and 1mol 4; The 6-diamino resorcin joins in the aqueous sodium hydroxide solution that concentration is 0.01～0.1mol/L, reaction 1h～1.5h, lyophilize; Promptly get complexing salt, reaction equation is following:
Two, with 1mol 4,6-diamino resorcin hydrochlorate and 560g polyphosphoric acid are put into polymerization reaction kettle, and the mass concentration of polyphosphoric acid is 85%; Vacuum removal hydrogen chloride gas under 80 ℃ condition adds polymerization reaction kettle with the 1mol complexing salt then, at 120 ℃ of reaction 12h～18h; Again 350～420g Vanadium Pentoxide in FLAKES is added polymerization reaction kettle,, get the pre-polymerization material at 140 ℃～160 ℃ reaction 16～24h; The pre-polymerization material is put into double-screw reactor, at 180 ℃ of reaction 2～4h, again at 200 ℃ of reaction 1～2h; Promptly get polyparaphenylene Ben Bing Er oxazole polymkeric substance (PBO polymkeric substance), reaction equation is following:
The method that the present invention relates to is through reducing 4, and the consumption of 6-diamino resorcin hydrochlorate has shortened the reaction times that removes hydrogenchloride; Through to 4, the very easily oxidation of complexing salt has been avoided in the protection fully of the amino group of 6-diamino resorcin, has reduced the specification requirement to polymerization unit; Use the PBO polymkeric substance of present method preparation, the reaction times is short, and molecular weight is high; Foreign matter content is low, helps the carrying out of follow-up spinning technique.
Description of drawings
Fig. 1 is the PBO polymkeric substance that adopts experiment one, experiment two and test three method preparation; The limiting viscosity curve of the PBO polymkeric substance of the method preparation of
expression experiment one; The limiting viscosity curve of the PBO polymkeric substance of the method preparation of
expression experiment two, the limiting viscosity curve of the PBO polymkeric substance of the method preparation of
expression experiment three.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method that this embodiment prepares polyparaphenylene Ben Bing Er oxazole polymkeric substance is following:
One, tindichloride is joined the concentration to tindichloride is 0.01mol/L～0.1mol/L in the aqueous sodium hydroxide solution that concentration is 0.01～0.1mol/L; And then with 2mol terephthalic acid and 1mol 4; The 6-diamino resorcin joins in the aqueous sodium hydroxide solution that concentration is 0.01～0.1mol/L, reaction 1h～1.5h, lyophilize; Promptly get complexing salt, reaction equation is following:
Two, with 1mol 4,6-diamino resorcin hydrochlorate and 560g polyphosphoric acid are put into polymerization reaction kettle, and the mass concentration of polyphosphoric acid is 85%; Vacuum removal hydrogen chloride gas under 80 ℃ condition adds polymerization reaction kettle with the 1mol complexing salt then, at 120 ℃ of reaction 12h～18h; Again 350～420g Vanadium Pentoxide in FLAKES is added polymerization reaction kettle,, get the pre-polymerization material at 140 ℃～160 ℃ reaction 16～24h; The pre-polymerization material is put into double-screw reactor, at 180 ℃ of reaction 2～4h, again at 200 ℃ of reaction 1～2h; Promptly get polyparaphenylene Ben Bing Er oxazole polymkeric substance (PBO polymkeric substance), reaction equation is following:
Embodiment two: this embodiment and embodiment one are different is that the concentration of tindichloride in the step 1 is 0.02mol/L～0.09mol/L.Other is identical with embodiment one.
Embodiment three: this embodiment and embodiment one are different is that the concentration of tindichloride in the step 1 is 0.05mol/L.Other is identical with embodiment one.
Embodiment four: this embodiment and embodiment one are different be in the step 1 with 2mol terephthalic acid and 1mol 4, the 6-diamino resorcin joins in the aqueous sodium hydroxide solution that concentration is 0.1mol/L, reaction 1.2h.Other is identical with embodiment one.
Embodiment five: what this embodiment and embodiment one were different is at 120 ℃ of reaction 13h in the step 2.Other is identical with embodiment one.
Embodiment six: what this embodiment and embodiment one were different is at 120 ℃ of reaction 14h in the step 2.Other is identical with embodiment one.
Embodiment seven: what this embodiment and embodiment one were different is at 120 ℃ of reaction 15h in the step 2.Other is identical with embodiment one.
Embodiment eight: what this embodiment and embodiment one were different is at 120 ℃ of reaction 16h in the step 2.Other is identical with embodiment one.
Embodiment nine: what this embodiment and embodiment one were different is at 120 ℃ of reaction 17h in the step 2.Other is identical with embodiment one.
Embodiment ten: what this embodiment and embodiment one were different is at 150 ℃ of reaction 24h in the step 2.Other is identical with embodiment one.
Adopt following experimental verification effect of the present invention:
Experiment one:
The monomer salt forming method prepares the PBO polymkeric substance:
2mol complexing salt and 560g polyphosphoric acid are joined in the polymerization reaction kettle,, then the 420g Vanadium Pentoxide in FLAKES is added in the polymerization reaction kettle at 120 ℃ of reaction 12h; At 140～160 ℃; Behind the reaction 24h, the pre-polymerization material is put into double-screw reactor, at 180 ℃ of reaction 2h; At 200 ℃ of reaction 1h, promptly get polyparaphenylene Ben Bing Er oxazole polymkeric substance (PBO polymkeric substance) again.
Experiment two:
The polyphosphoric acid legal system is equipped with the PBO polymkeric substance:
One, with 2mol 4,6-diamino resorcin hydrochlorate, 2mol terephthalic acid and 560g polyphosphoric acid join in the polymerization reaction kettle, vacuum removal hydrogen chloride gas under 80 ℃ condition, and after gas removal is clean,
Two, the 1mol complexing salt is added polymerization reaction kettle,, then the 420g Vanadium Pentoxide in FLAKES is added polymerization reaction kettle at 120 ℃ of reaction 12h; Between 140～160 ℃, reaction 24h gets the pre-polymerization material; The pre-polymerization material is put into double-screw reactor; At 180 ℃ of reaction 2h, at 200 ℃ of reaction 1h, promptly get polyparaphenylene Ben Bing Er oxazole polymkeric substance (PBO polymkeric substance) again.
Experiment three:
The method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance is following:
One, tindichloride is joined the concentration to tindichloride is 0.1mol/L in the aqueous sodium hydroxide solution that concentration is 0.1mol/L; And then with 2mol terephthalic acid and 1mol 4; The 6-diamino resorcin joins in the aqueous sodium hydroxide solution that concentration is 0.1mol/L; Reaction 1.5h, lyophilize promptly gets complexing salt;
Two, with 1mol 4,6-diamino resorcin hydrochlorate and 560g polyphosphoric acid are put into polymerization reaction kettle, and the mass concentration of polyphosphoric acid is 85%; Vacuum removal hydrogen chloride gas under 80 ℃ condition adds polymerization reaction kettle with the 1mol complexing salt then, at 120 ℃ of reaction 15h; Again the 420g Vanadium Pentoxide in FLAKES is added polymerization reaction kettle,, get the pre-polymerization material at 160 ℃ of reaction 24h; The pre-polymerization material is put into double-screw reactor; At 180 ℃ of reaction 2h, at 200 ℃ of reaction 1h, promptly get polyparaphenylene Ben Bing Er oxazole polymkeric substance (PBO polymkeric substance) again.
To test in the process of one to three preparation penylene Ben Bing Er oxazole polymkeric substance (PBO polymkeric substance); Every at a distance from 4h; In reaction, take a sample; Its limiting viscosity is measured, as shown in Figure 1, find out the penylene benzene of the tripartite method preparation of experiment and the height that two oxazole polymkeric substance (PBO polymkeric substance) limiting viscosity ratio adopts experiment one and experiment two by Fig. 1.
Claims (10)
1. the method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance, the method that it is characterized in that preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance is following:
One, tindichloride is joined the concentration to tindichloride is 0.01mol/L～0.1mol/L in the aqueous sodium hydroxide solution that concentration is 0.01～0.1mol/L; And then with 2mol terephthalic acid and 1mol 4; The 6-diamino resorcin joins in the aqueous sodium hydroxide solution that concentration is 0.01～0.1mol/L; Reaction 1h～1.5h, lyophilize promptly gets complexing salt;
Two, with 1mol 4,6-diamino resorcin hydrochlorate and 560g polyphosphoric acid are put into polymerization reaction kettle, and the mass concentration of polyphosphoric acid is 85%; Vacuum removal hydrogen chloride gas under 80 ℃ condition adds polymerization reaction kettle with the 1mol complexing salt then, at 120 ℃ of reaction 12h～18h; Again 350～420g Vanadium Pentoxide in FLAKES is added polymerization reaction kettle,, get the pre-polymerization material at 140 ℃～160 ℃ reaction 16～24h; The pre-polymerization material is put into double-screw reactor; At 180 ℃ of reaction 2～4h, at 200 ℃ of reaction 1～2h, promptly get polyparaphenylene Ben Bing Er oxazole polymkeric substance again.
2. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1, the concentration that it is characterized in that tindichloride in the step 1 is 0.02mol/L～0.09mol/L.
3. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1, the concentration that it is characterized in that tindichloride in the step 1 is 0.05mol/L.
4. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1; It is characterized in that in the step 1 2mol terephthalic acid and 1mol 4; The 6-diamino resorcin joins in the aqueous sodium hydroxide solution that concentration is 0.1mol/L, reaction 1.2h.
5. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1, it is characterized in that in the step 2 at 120 ℃ of reaction 13h.
6. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1, it is characterized in that in the step 2 at 120 ℃ of reaction 14h.
7. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1, it is characterized in that in the step 2 at 120 ℃ of reaction 15h.
8. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1, it is characterized in that in the step 2 at 120 ℃ of reaction 16h.
9. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1, it is characterized in that in the step 2 at 120 ℃ of reaction 17h.
10. according to the said method for preparing polyparaphenylene Ben Bing Er oxazole polymkeric substance of claim 1, it is characterized in that in the step 2 at 150 ℃ of reaction 24h.
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Cited By (3)
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| CN103013113A (en) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | Preparation method of graphene/PBO polymer |
| CN104072771A (en) * | 2014-07-18 | 2014-10-01 | 四川宝利丰科技有限公司 | Preparation method of PBO |
| CN113322535A (en) * | 2020-02-28 | 2021-08-31 | 吉林师范大学 | Preparation method of poly (terephthalic acid-2- (hexyl-5-alkenyl) -succinic acid-1, 4-benzodioxazole) fiber |
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| CN113322535A (en) * | 2020-02-28 | 2021-08-31 | 吉林师范大学 | Preparation method of poly (terephthalic acid-2- (hexyl-5-alkenyl) -succinic acid-1, 4-benzodioxazole) fiber |
| CN113322535B (en) * | 2020-02-28 | 2022-12-06 | 吉林师范大学 | Method for preparing poly (terephthalic acid-2- (hexyl-5-alkenyl) -succinic acid-1, 4-benzodioxazole) fiber |
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Application publication date: 20120815 |