CN108299648A - A method of control linear polyphosphazene intermediate molecule amount - Google Patents
A method of control linear polyphosphazene intermediate molecule amount Download PDFInfo
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- CN108299648A CN108299648A CN201810139149.6A CN201810139149A CN108299648A CN 108299648 A CN108299648 A CN 108299648A CN 201810139149 A CN201810139149 A CN 201810139149A CN 108299648 A CN108299648 A CN 108299648A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
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Abstract
The invention discloses a kind of synthetic methods of control linear polyphosphazene intermediate molecule amount, it realizes the controllable of linear polyphosphazene intermediate molecule amount, the linear polyphosphazene intermediate of specified molecular weight can be prepared according to the application requirement of follow-up substitution reaction requirement or polyphosphazene material.By the present invention in that with the catalyst of special ratios, specific monomer concentration, specific reaction temperature obtains the linear polyphosphazene intermediate of different molecular weight.Make in the present invention reaction control method used overcome generally existing in existing method control variable is single, control condition not comprehensively, the problems such as control effect is unstable.The present invention controls the number-average molecular weight Mn of linear polyphosphazene intermediate 1 × 103‑9×103、1×104‑9×104、1×105‑9×105Three grades can select specific polymerizing condition according to different substitution requirements or application requirement, prepare the linear polyphosphazene intermediate of specified molecular weight, and the application and production to polyphosphazene are significant.
Description
Technical field：
The invention discloses a kind of each condition of initial concentration, catalyst amount, polymerization temperature by comprehensive adjustment monomer,
The controllable method of the average molecular weight of linear polyphosphazene intermediate is realized in the course of the polymerization process.
Background technology：
The skeleton of polyphosphazene elastomer is alternately arranged with P, N inorganic atoms list double bond, and P-N bond distance is long, and bond angle is big, this imparting
The good compliance of polyphosphazene macromolecular makes polyphosphazene elastomer have low glass transition temperature, while the key of P=N keys
It can be big so that polyphosphazene backbone has good thermal stability.The side group of linear polydichlorophosphazenes can be by different types of parent
Core reagent replaces, and to obtain the polyphosphazene of various functions, is used as bio-medical material, heat-resisting material, low temperature elasticity body, close
Closure material, oil transportation material, macromolecule conductor etc..Polyphosphazene material industry product is seldom, mainly due to polyphosphazene material
Synthesis material is expensive, and the reasons such as complex process, one of them important limiting factor is the synthesis item of linear polyphosphazene intermediate
Part is harsh, and molecular weight is not easy to control, and the linear polyphosphazene intermediate product of synthesis is unstable, hinders the industrialization of polyphosphazene.
Therefore, the molecular weight of stability contorting linear polyphosphazene intermediate is particularly significant for pushing the industrialization of polyphosphazene product.
One United States Patent (USP) of nineteen ninety J.H.Magill, R.L.Merker report, utilizes toluenesulfonic acid, sulphophenyl first
Acid, sulfamic acid ammonia, sulfamic acid etc. are used as catalyst, CaSO4·2H2O、CuSO4·2H2O、NiSO4·2H2O、CoSO4·
2H2O、MgSO4·2H2O、Al(OH)3As co-catalyst, it is catalyzed hexachlorocyclotriph,sphazene solution ring-opening polymerisation, molecular weight can reach
Between to 20 to 30000.There is scholar to carry out stability study to this catalyst system and catalyzing successively later, primarily with regard to impurity to poly-
Phosphonitrile synthesizes and the influence of substitution, previous research lay particular emphasis on (NPCl2)4、(NPCl2)5The influence of equal polymers, 2008 old
It is triumphant etc. greatly to report influence of the hydrolysis impurity to polymerization.But it is all based on activity and production of the change of single condition to polymerisation
Product are crosslinked the influence of problem, but the controllable polymerization in relation to the control of the molecular weight stabilizers of linear polyphosphazene intermediate is not resolved
And report.
Invention content：
In order to overcome the shortcomings of above-mentioned existing research, the present invention provides a kind of control linear polyphosphazene intermediate molecule amounts
Synthetic method.It, can be according to follow-up substitution its object is to realize the controllable of linear polyphosphazene intermediate average molecular weight
The requirement of reaction or the application requirement of polyphosphazene material prepare the linear polyphosphazene intermediate of specified molecular weight.
The technical solution adopted by the present invention is：By using the catalyst of special ratios, specific monomer concentration, specific reaction
Temperature obtains the linear polyphosphazene intermediate of different molecular weight.
Control variable that the control method used in the present invention overcomes generally existing in existing method is single, control strip
The problems such as part is not comprehensive, control effect is unstable.The number-average molecular weight of linear polyphosphazene intermediate can be controlled in the present invention
1 × 103-9×103、1×104-9×104、1×105-9×105Three grades, can according to different substitutions require or
Application requirement selects specific polymerizing condition, the linear polyphosphazene intermediate of specified molecular weight is prepared, to the application side of polyphosphazene
To and the industrial production of polyphosphazene have important meaning.This method can solve current linear polyphosphazene intermediate and prepare simultaneously
The problem of other uncontrollable factors of process, yield, molecular weight, purity of polymerization product etc. is set to tend towards stability, this is not only for reality
The follow-up substitution process for testing room is significant, and means a great to the entire process of industrialization of polyphosphazene material.
A method of control linear polyphosphazene intermediate molecule amount, it is characterised in that：
A. the hexachlorocyclotriph,sphazene solution that 0.8g/ml-1.6g/ml initial concentrations are prepared using trichloro-benzenes as solvent, by solution
It is put into fully dry reaction kettle, is incorporated to nitrogen protection；
A. the catalyst system and catalyzing used is using sulphonic acids as catalyst, and water is synergistic catalyst, and the dosage of catalyst is monomer
Between the 0.8%-1.2% of quality, the mass ratio of synergistic catalyst and catalyst is 1：10；Monomer is hexachlorocyclotriph,sphazene；
B. the control of ring-opening polymerization temperature is between 200 DEG C -215 DEG C；
C. the as polymerisation terminal when rod climbing phenomenon occurs in polymeric solution.
By controlling catalyst amount, initial monomer concentration and/or polymeric reaction temperature, the linear of different molecular weight is obtained
Poly- phosphorus
Nitrile intermediate.
Further, it is 1 × 10 to prepare number-average molecular weight3-9×103Initial list needed for the linear polyphosphazene intermediate of grade
For bulk concentration between 1.0g/ml-1.2g/ml, catalyst amount is reaction temperature between the 1.8wt%-1.2wt% of monomer mass
Degree is between 200 DEG C -215 DEG C.
Further, it is 1 × 10 to prepare number-average molecular weight4-9×104Initial list needed for the linear polyphosphazene intermediate of grade
For bulk concentration between 0.9g/ml-1.1g/ml, catalyst amount is reaction temperature between the 0.8wt%-1.1wt% of monomer mass
Degree is between 208 DEG C -211 DEG C.
Further, it is 1 × 10 to prepare number-average molecular weight5-9×105Initial list needed for the linear polyphosphazene intermediate of grade
For bulk concentration between 0.6g/ml-0.9g/ml, catalyst amount is reaction temperature between the 0.8wt%-1.0wt% of monomer mass
Degree is between 200 DEG C -209 DEG C.
Want three kinds of influence factors of Comprehensive Control most important to the control of molecular weight in the present invention, be catalyst first with
The dosage of the dosage of synergistic catalyst, catalyst is more, will increase the quantity in activated centre, on the one hand promotes the progress of reaction, increases
The frequency in big activated centre and reaction monomers collision, shortens the reaction time.On the other hand, increasing for activated centre can improve instead
The yield answered.Initial monomer concentration is followed by controlled, for controlling the reaction time, monomer concentration is also big, is touched with activated centre
The frequency hit is also bigger, and the terminal of polymerisation is determined by the viscosity of polymeric solution, so when initial monomer is dense
Spend smaller, when terminal viscosity is identical, the molecular weight of polymer is also higher, and polymer content is also bigger, therefore controls initial
Monomer concentration is most important.It is finally the influence of polymerization temperature, temperature is higher, and the quantity of polymer chain is more, works as polymerization system
Reach same viscosity, the attainable molecular weight levels of system institute more than polymer chain quantity are also corresponding relatively low.Therefore, temperature is got over
Height, the molecular weight of polydichlorophosphazenes is lower., the molecular weight product of preparation is bigger.Polymerization temperature is lower, the activity in activated centre
Smaller, the molecular weight product of preparation is smaller.Therefore, pass through Comprehensive Control catalyst amount, initial monomer concentration, polymerisation temperature
Degree, can just accurately control the product quality of linear polyphosphazene intermediate, obtain the linear polyphosphazene intermediate of different molecular weight.
Specific implementation mode：
In order to better understand the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to following example, and embodiment is not construed as limiting the scope of the invention.
Case study on implementation 1
50g hexachlorocyclotriph,sphazenes are dissolved into 1,2,4- trichloro-benzenes of 40ml, solution is put into fully dry reaction kettle
It is interior, it is incorporated to nitrogen protection；The catalyst system and catalyzing used is the CaSO using sulfamic acid as catalyst4·2H2O is synergistic catalyst, is urged
The dosage of agent is the 1.2wt% of monomer mass, CaSO4·2H2The mass ratio of O and sulfamic acid is 1:10；Ring-opening polymerization
Temperature is controlled at 215 DEG C；The as polymerisation terminal when rod climbing phenomenon occurs in polymeric solution.Prepare linear polyphosphazene intermediate
Number-average molecular weight Mn be 1 × 103-9×103Grade.
Case study on implementation 2
50g hexachlorocyclotriph,sphazenes are dissolved into 1,2,4- trichloro-benzenes of 50ml, solution is put into fully dry reaction kettle
It is interior, it is incorporated to nitrogen protection；The catalyst system and catalyzing used is the CaSO using sulfamic acid as catalyst4·2H2O is synergistic catalyst, is urged
The dosage of agent is the 1.0wt% of monomer mass, CaSO4·2H2The mass ratio of O and sulfamic acid is 1:10；Ring-opening polymerization
Temperature is controlled at 210 DEG C；The as polymerisation terminal when rod climbing phenomenon occurs in polymeric solution.Prepare linear polyphosphazene intermediate
Number-average molecular weight Mn be 1 × 104-9×104Grade.
Case study on implementation 3
50g hexachlorocyclotriph,sphazenes are dissolved into 1,2,4- trichloro-benzenes of 70ml, solution is put into fully dry reaction kettle
It is interior, it is incorporated to nitrogen protection；The catalyst system and catalyzing used is the CaSO using sulfamic acid as catalyst4·2H2O is synergistic catalyst, is urged
The dosage of agent is the 0.9wt% of monomer mass, CaSO4·2H2The mass ratio of O and sulfamic acid is 1:10；Ring-opening polymerization
Temperature is controlled at 208 DEG C；The as polymerisation terminal when rod climbing phenomenon occurs in polymeric solution.Prepare linear polyphosphazene intermediate
Number-average molecular weight Mn be 1 × 105-9×105Grade.
Claims (4)
1. a kind of synthetic method of control linear polyphosphazene intermediate molecule amount, it is characterised in that：
A. the hexachlorocyclotriph,sphazene solution that 0.6g/ml-1.2g/ml initial concentrations are prepared using trichloro-benzenes as solvent, solution is put into
Fully in dry reaction kettle, and it is passed through nitrogen protection；
B. the catalyst system and catalyzing used is the CaSO using sulphonic acids as catalyst4·2H2O is synergistic catalyst, and the dosage of catalyst is
Between the 0.8%-1.2% of monomer mass, the mass ratio of synergistic catalyst and catalyst is 1：10；Monomer is three phosphorus of chlordene ring
Nitrile；
C. the control of ring-opening polymerization temperature is between 200 DEG C -215 DEG C；
D. the as polymerisation terminal when rod climbing phenomenon occurs in polymeric solution；
By controlling catalyst amount, initial monomer concentration and/or polymeric reaction temperature, the linear poly- phosphorus of different molecular weight is obtained
Nitrile intermediate.
2. according to the method described in claim 1, it is characterized in that：It is 1 × 10 to prepare number-average molecular weight Mn3-9×103Grade
Between a concentration of 1.0g/ml-1.2g/ml of initial monomer needed for linear polyphosphazene intermediate, catalyst amount is monomer mass
1.8wt%-1.2wt% between, reaction temperature is between 200 DEG C -215 DEG C.
3. according to the method described in claim 1, it is characterized in that：It is 1 × 10 to prepare number-average molecular weight Mn4-9×104Grade
Between a concentration of 0.9g/ml-1.1g/ml of initial monomer needed for linear polyphosphazene intermediate, catalyst amount is monomer mass
0.8wt%-1.1wt% between, reaction temperature is between 208 DEG C -211 DEG C.
4. according to the method described in claim 1, it is characterized in that：It is 1 × 10 to prepare number-average molecular weight Mn5-9×105Grade
Between a concentration of 0.6g/ml-0.9g/ml of initial monomer needed for linear polyphosphazene intermediate, catalyst amount is monomer mass
0.8wt%-1.0wt% between, reaction temperature is between 200 DEG C -209 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306111A (en) * | 2018-09-28 | 2019-02-05 | 吴亚琴 | A kind of oil resistant fire-resistant cable material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4946938A (en) * | 1989-08-01 | 1990-08-07 | The University Of Pittsburgh | A process for the catalytic synthesis of polyphosphazenes |
| CN1850832A (en) * | 2006-05-23 | 2006-10-25 | 郑州大学 | Catalytic synthesizing method of hexa chloro cyclotripolyphosphazene |
| CN1916051A (en) * | 2005-08-15 | 2007-02-21 | 中国科学院化学研究所 | Substituent polyphosphonitrile, prepartion method and application |
-
2018
- 2018-02-11 CN CN201810139149.6A patent/CN108299648A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4946938A (en) * | 1989-08-01 | 1990-08-07 | The University Of Pittsburgh | A process for the catalytic synthesis of polyphosphazenes |
| CN1916051A (en) * | 2005-08-15 | 2007-02-21 | 中国科学院化学研究所 | Substituent polyphosphonitrile, prepartion method and application |
| CN1850832A (en) * | 2006-05-23 | 2006-10-25 | 郑州大学 | Catalytic synthesizing method of hexa chloro cyclotripolyphosphazene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306111A (en) * | 2018-09-28 | 2019-02-05 | 吴亚琴 | A kind of oil resistant fire-resistant cable material and preparation method thereof |
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Application publication date: 20180720 |