CN101817846A - Thio-phenyl phosphonic piperazine polymer and preparation method thereof - Google Patents
Thio-phenyl phosphonic piperazine polymer and preparation method thereof Download PDFInfo
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- CN101817846A CN101817846A CN201010171127A CN201010171127A CN101817846A CN 101817846 A CN101817846 A CN 101817846A CN 201010171127 A CN201010171127 A CN 201010171127A CN 201010171127 A CN201010171127 A CN 201010171127A CN 101817846 A CN101817846 A CN 101817846A
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Abstract
The invention relates to a thio-phenyl phosphonic piperazine polymer and a preparation method thereof. The structure of the antiflaming polymer is shown as the following formula, wherein n is more than or equal to 1. The method comprises the steps of: under the protection of nitrogen, dripping thio-phenyl-phosphonic dichloride into a mixture of anhydrous piperazine and an acid-binding agent or a mixture of anhydrous piperazine, an acid-binding agent and an organic solvent, and removing hydrogen chloride generated by reaction by utilizing the acid-binding agent under the heating condition to perform the reaction; and purifying and drying to prepare the thio-phenyl phosphonic piperazine polymer. The thio-phenyl phosphonic piperazine polymer has the advantages of stable physical and chemical performance, high flame retardancy, simple production process, safety and environmental protection, and can be widely used for polyester, polyamides, epoxide resin, fiber reinforce plastic resin and the like.
Description
Technical field
The present invention relates to a kind of phosphorus nitrogen synergistic fire retardant and preparation technology, particularly a kind of thio-phenyl phosphonic piperazine polymer and preparation method thereof.
Background technology
Along with the whole world is more and more higher to the environmental requirement of fire retardant, halogenated flame retardant faces huge pressure, and environmental protection, the less expansion type phosphor nitrogen flame retardant of pollution are subjected to people's favor, and especially phosphorus nitrogen cooperative flame retardant compound more is subjected to investigator's attention.Its reason is: this type of flame-retardant compound combines acid source, carbon source, the fire-retardant three elements of source of the gas together, easily brings into play good flame-retarded efficiency; And because of it contains the C-P key, the chemical stability height; The characteristic that also has low cigarette, low toxicity.So become a key areas of current fire retardant development research.The phosphor nitrogen combustion inhibitor that contains ignition-proof element sulphur is more novel research topic, and it has the wholesomeness of sulphur, phosphorus, nitrogen element cooperative flame retardant, and flame-retarded efficiency is higher.And structure of the present invention has possessed sulphur, phosphorus, nitrogen ternary synergistic and has constituted the aggretion type molecular structure again, and it and material have intermiscibility preferably, do not influence the mechanical property of material, and good application and development prospect is arranged.Aspect the organophosphorous fire retardant exploitation, China starts late, and does not release the outstanding organic phosphine fire retardant kind of performance so far, has directly limited the development of relevant fire retardant material.Therefore, to phosphorus nitrogen synergetic, particularly thiophos nitrogen element synergetic organic phosphine Study of Flame Retardant exploitation has more urgent realistic meaning and long-range strategic importance.
Summary of the invention
The objective of the invention is to propose that a kind of physical and chemical performance is stable, flame-retarded efficiency is high, and the thio-phenyl phosphonic piperazine polymer of safety and environmental protection, to overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of thio-phenyl phosphonic piperazine polymer, this flame-retardant compound structure is shown below:
Wherein, n 〉=1.
Another object of the present invention is to propose a kind of preparation method of thio-phenyl phosphonic piperazine polymer as mentioned above, its technology is simple, easy handling, with low cost, is suitable for the demand of various technical scale productions, and this method is:
Under the nitrogen protection condition; with mol ratio is 1: the thio-phenyl phosphonic dichloro of (1～2) and Piperazine anhydrous are raw material; hand thio-phenyl phosphonic dichloro drops in piperazine and the acid binding agent mixture in 70～200 ℃ temperature range; utilize acid binding agent to slough hcl reaction 6～30h that reaction generates; thereafter to reactant purify, drying treatment, make thio-phenyl phosphonic piperazine polymer.
Perhaps
Under the nitrogen protection condition; with mol ratio is 1: the thio-phenyl phosphonic dichloro of (1～2) and Piperazine anhydrous are raw material; in 70～200 ℃ temperature range, the thio-phenyl phosphonic dichloro is dropped in the mixture of piperazine, acid binding agent and organic solvent; utilize acid binding agent to remove hcl reaction 6～30h that dereaction generates; thereafter to reactant purify, drying treatment, make thio-phenyl phosphonic piperazine polymer.
Particularly, this method is specially:
Under the nitrogen protection condition; the thio-phenyl phosphonic dichloro is dropped in Piperazine anhydrous, acid binding agent and the dimethylbenzene three mixture; and make it slowly to be warming up to 140 ℃ of backflows; and sustained reaction 18～20h; utilize acid binding agent to remove the hydrogenchloride that dereaction generates; itself after purify, drying treatment, make thio-phenyl phosphonic piperazine polymer.
This method also can be:
The thio-phenyl phosphonic dichloro is dropped in Piperazine anhydrous, acid binding agent and the chlorobenzene three mixture, and make it slowly to be warming up to 135 ℃ of backflows, and sustained reaction 18～20h, utilize acid binding agent to remove the hydrogenchloride that dereaction generates, itself after purify, drying treatment, make thio-phenyl phosphonic piperazine polymer.
This method also can be:
Under the nitrogen protection condition; the thio-phenyl phosphonic dichloro is dropped in Piperazine anhydrous, acid binding agent and the ethylene dichloride three mixture; and make it slowly to be warming up to 150 ℃ of backflows; and sustained reaction 18～20h; utilize acid binding agent to remove the hydrogenchloride that dereaction generates; itself after purify, drying treatment, make thio-phenyl phosphonic piperazine polymer.
This method also can be:
Under the nitrogen protection condition; the thio-phenyl phosphonic dichloro is dropped in Piperazine anhydrous, acid binding agent and the dichlorobenzene three mixture; and make it slowly to be warming up to 160 ℃; and sustained reaction 18～20h; utilize acid binding agent to remove the hydrogenchloride that dereaction generates; itself after purify, drying treatment, make thio-phenyl phosphonic piperazine polymer.
Further, described acid binding agent can be pyridine, triethylamine, N, accelerine or N, N-Diethyl Aniline.
Describedly purify, the detailed process of drying treatment is: product is washed through washing, ethanol, suction filtration, drying is dissolved in the organic solvent, add adequate amount of ethanol again and make it separate out crystallization, suction filtration, ethanol is washed, is washed then, drying.This goes on foot described organic solvent and can be phenylcarbinol, dimethyl formamide, methyl-sulphoxide or pyridine.
Among the present invention, be raw material, synthesize thio-phenyl phosphonic piperazine polymer through the simple process process with thio-phenyl phosphonic dichloro and Piperazine anhydrous, its physical and chemical performance is stable, flame-retarded efficiency is high, and safety and environmental protection, can be used for polyester and polymeric amide, Resins, epoxy is among the fiber glass resin etc.The synthesis technique principle of this thio-phenyl phosphonic piperazine polymer is shown below:
Wherein: n 〉=1.
Compared with prior art, beneficial effect of the present invention is:
1. thio-phenyl phosphonic piperazine polymer thermostability of the present invention and chemical stability are better, the high temperature process of energy adaptation material;
2. not halogen-containing, nontoxic, the safety of compound structure of the present invention's proposition helps environmental protection;
3. preparation method of the present invention is simple, need not catalyzer, need not reaction under high pressure, need not complex apparatus, and is with low cost, is easy to control, is easy to change into batch process.
Embodiment
Below in conjunction with specific embodiment technology contents of the present invention is described further.
Embodiment 1
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add 0.1mol piperazine and 0.2mol pyridine; stir, slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro; wait to be added dropwise to complete be warming up to 120 ℃ the reaction 18～20h; water, washing with alcohol while hot, suction filtration, drying; it is dissolved in the phenylcarbinol; add an amount of ethanol and make product separate out crystallization, suction filtration washs respectively with ethanol, water; dry; get thio-phenyl phosphonic piperazine polymer, its productive rate is 79%, and decomposition starting temperature is 280.6 ℃.
Embodiment 2
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add 0.1mol piperazine and 0.2mol pyridine; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 120 ℃ the reaction 18～20h; water, washing with alcohol while hot; suction filtration, drying is dissolved in it in methyl-sulphoxide; adding an amount of ethanol makes it separate out crystallization; suction filtration washs respectively with ethanol, water, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 77%, and decomposition temperature is about 280.6 ℃.
Embodiment 3
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add 0.12mol piperazine and 0.2mol triethylamine; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete and be warming up to 100 ℃ of back flow reaction 18～20h; water, washing with alcohol while hot; suction filtration, drying is dissolved in it in phenylcarbinol; adding an amount of ethanol makes it separate out crystallization; suction filtration washs respectively with ethanol, water, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 73%, and decomposition temperature is about 280.6 ℃.
Embodiment 4
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.1mol piperazine; 0.2mol pyridine and 40mL dimethylbenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete and be warming up to 140 ℃ of back flow reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in phenylcarbinol; adding an amount of ethanol makes it separate out crystallization; suction filtration is used ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 74%, and decomposition temperature is about 280.6 ℃.
Embodiment 5
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.14mol piperazine; 0.2mol pyridine and 40mL dimethylbenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete and be warming up to 140 ℃ of back flow reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in methyl-sulphoxide; adding an amount of ethanol makes it separate out crystallization; suction filtration is used ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 82%, and decomposition temperature is about 280.6 ℃.
Embodiment 6
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.1mol piperazine; 0.2mol triethylamine and 40mL dimethylbenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 90 ℃ the reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in dimethyl formamide; adding an amount of ethanol makes it separate out crystallization; suction filtration is used ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 67%, and decomposition temperature is about 280.6 ℃.
Embodiment 7
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.1mol piperazine; 0.2molN; accelerine and 40mL dimethylbenzene stir, and slowly are warmed up to 80 ℃; begin to drip 0.1mol thio-phenyl phosphonic dichloro; wait to be added dropwise to complete and be warming up to 140 ℃ of back flow reaction 18～20h, waters while hot; washing with alcohol, suction filtration; dry; it is dissolved in the phenylcarbinol, adds an amount of ethanol and make it separate out crystallization, suction filtration; use ethanol; water washs respectively; be thio-phenyl phosphonic piperazine polymer after the drying treatment, its productive rate is 52%, and decomposition temperature is about 280.6 ℃.
Embodiment 8
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.16mol piperazine; 0.2molN; N-Diethyl Aniline and 40mL chlorobenzene stir, and slowly are warmed up to 80 ℃; begin to drip 0.1mol thio-phenyl phosphonic dichloro; wait to be added dropwise to complete be warming up to 135 ℃ the reaction 18～20h, waters while hot; washing with alcohol, suction filtration; dry; it is dissolved in the phenylcarbinol, adds an amount of ethanol and make it separate out crystallization, suction filtration; use ethanol; water washs respectively; be thio-phenyl phosphonic piperazine polymer after the drying treatment, its productive rate is 86%, and decomposition temperature is about 280.6 ℃.
Embodiment 9
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add 0.1mol piperazine, 0.2mol triethylamine and 40mL chlorobenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 100 ℃ the reaction 18～20h; water, washing with alcohol while hot; suction filtration, drying is dissolved in it in phenylcarbinol; adding an amount of ethanol makes it separate out crystallization; suction filtration washs respectively with ethanol, water, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 71%, and decomposition temperature is about 280.6 ℃.
Embodiment 10
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.1mol piperazine; 0.2mol N; N-Diethyl Aniline and 40mL chlorobenzene stir, and slowly are warmed up to 80 ℃; begin to drip 0.1mol thio-phenyl phosphonic dichloro; wait to be added dropwise to complete be warming up to 135 ℃ the reaction 18～20h, waters while hot; washing with alcohol, suction filtration; dry; it is dissolved in the methyl-sulphoxide, adds an amount of ethanol and make it separate out crystallization, suction filtration; use ethanol; water washs respectively; be thio-phenyl phosphonic piperazine polymer after the drying treatment, its productive rate is 69%, and decomposition temperature is about 280.6 ℃.
Embodiment 11
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.16mol piperazine; 0.2mol pyridine and 40mL chlorobenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 135 ℃ the reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in dimethyl formamide; adding an amount of ethanol makes it separate out crystallization; filter, use ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 78%, and decomposition temperature is about 280.6 ℃.
Embodiment 12
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.18mol piperazine; 0.2mol triethylamine and 40mL ethylene dichloride; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 90 ℃ the reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in phenylcarbinol; adding an amount of ethanol makes it separate out crystallization; suction filtration is used ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 74%, and decomposition temperature is about 280.6 ℃.
Embodiment 13
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.1mol piperazine; 0.2mol triethylamine and 40mL ethylene dichloride; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 90 ℃ the reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in methyl-sulphoxide; adding an amount of ethanol makes it separate out crystallization; suction filtration is used ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 51%, and decomposition temperature is about 280.6 ℃.
Embodiment 14
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.1mol piperazine; 0.2mol pyridine and 40mL dichlorobenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 160 ℃ the reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in dimethyl formamide; adding an amount of ethanol makes it separate out crystallization; suction filtration is used ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 69%, and decomposition temperature is about 280.6 ℃.
Embodiment 15
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.1mol piperazine; 0.2mol pyridine and 40mL dichlorobenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 160 ℃ the reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in methyl-sulphoxide; adding an amount of ethanol makes it separate out crystallization; suction filtration is used ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 69%, and decomposition temperature is about 280.6 ℃.
Embodiment 16
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.18mol piperazine; 0.2molN; N-Diethyl Aniline and 40mL dichlorobenzene stir, and slowly are warmed up to 80 ℃; begin to drip 0.1mol thio-phenyl phosphonic dichloro; wait to be added dropwise to complete be warming up to 180 ℃ the reaction 18～20h, waters while hot; washing with alcohol, suction filtration; dry; it is dissolved in the phenylcarbinol, adds an amount of ethanol and make it separate out crystallization, suction filtration; use ethanol; water washs respectively; be thio-phenyl phosphonic piperazine polymer after the drying treatment, its productive rate is 81%, and decomposition temperature is about 280.6 ℃.
Embodiment 17
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.1mol piperazine; 0.2mol triethylamine and 40mL dichlorobenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 90 ℃ the reaction 18～20h; water while hot; washing with alcohol; suction filtration, drying is dissolved in it in methyl-sulphoxide; adding an amount of ethanol makes it separate out crystallization; suction filtration is used ethanol; water washs respectively, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 69%, and decomposition temperature is about 280.6 ℃.
Embodiment 18
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add 0.1mol piperazine, 0.2mol triethylamine and 40mL dichlorobenzene; stir; slowly be warmed up to 80 ℃, begin to drip 0.1mol thio-phenyl phosphonic dichloro, wait to be added dropwise to complete be warming up to 100 ℃ the reaction 18～20h; water, washing with alcohol while hot; suction filtration, drying is dissolved in it in pyridine; adding an amount of ethanol makes it separate out crystallization; suction filtration washs respectively with ethanol, water, is thio-phenyl phosphonic piperazine polymer after the drying treatment; its productive rate is 71%, and decomposition temperature is about 280.6 ℃.
Embodiment 19
In the 100mL there-necked flask of agitator and condenser is housed; feed nitrogen protection; add the 0.2mol piperazine; 0.2molN; accelerine and 40mL dichlorobenzene stir, and slowly are warmed up to 80 ℃; begin to drip 0.1mol thio-phenyl phosphonic dichloro; wait to be added dropwise to complete be warming up to 160 ℃ the reaction 18～20h, waters while hot; washing with alcohol, suction filtration; dry; it is dissolved in the phenylcarbinol, adds an amount of ethanol and make it separate out crystallization, suction filtration; use ethanol; water washs respectively; be thio-phenyl phosphonic piperazine polymer after the drying treatment, its productive rate is 69%, and decomposition temperature is about 280.6 ℃.
Claims (7)
1. thio-phenyl phosphonic piperazine polymer, it is characterized in that: the structure of described polymkeric substance is shown below:
Wherein, n 〉=1.
2. the preparation method of a thio-phenyl phosphonic piperazine polymer according to claim 1, it is characterized in that: described method is:
Under the nitrogen protection condition; with mol ratio is 1: the thio-phenyl phosphonic dichloro of (1～2) and Piperazine anhydrous are raw material; in 70～200 ℃ temperature range, the thio-phenyl phosphonic dichloro is dropped in piperazine and the acid binding agent mixture; utilize acid binding agent to slough hcl reaction 6～30h that reaction generates; thereafter to reactant purify, drying treatment, make thio-phenyl phosphonic piperazine polymer.
3. the preparation method of a thio-phenyl phosphonic piperazine polymer according to claim 1, it is characterized in that: described method is:
Under the nitrogen protection condition; with mol ratio is 1: the thio-phenyl phosphonic dichloro of (1～2) and Piperazine anhydrous are raw material; in 70～200 ℃ temperature range, the thio-phenyl phosphonic dichloro is dropped in the mixture of piperazine, acid binding agent and organic solvent; utilize acid binding agent to slough hcl reaction 6～30h that reaction generates; thereafter to reactant purify, drying treatment, make thio-phenyl phosphonic piperazine polymer.
4. the preparation method of thio-phenyl phosphonic piperazine polymer according to claim 3, it is characterized in that: described organic solvent can be dimethylbenzene, chlorobenzene, ethylene dichloride or dichlorobenzene.
5. according to the preparation method of claim 2 or 3 described thio-phenyl phosphonic piperazine polymers, it is characterized in that: described acid binding agent can be pyridine, triethylamine, N, accelerine or N, N-Diethyl Aniline.
6. according to the preparation method of claim 2 or 3 described thio-phenyl phosphonic piperazine polymers, it is characterized in that: describedly purify, the detailed process of drying treatment is: product is washed through washing, ethanol, suction filtration, dry, be dissolved in the organic solvent, add adequate amount of ethanol again and make it separate out crystallization, suction filtration, ethanol is washed, is washed then, drying.
7. according to the preparation method of the described thio-phenyl phosphonic piperazine polymer of claim 6, it is characterized in that described organic solvent can be phenylcarbinol, dimethyl formamide, methyl-sulphoxide or pyridine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311547A (en) * | 2011-06-09 | 2012-01-11 | 苏州科技学院 | Polyphenyl butanediol phosphonothioate compound and preparation method thereof |
| CN115746310A (en) * | 2018-05-18 | 2023-03-07 | 瑞士材料试验研究所 | Phosphorus-containing oligomers and polymers |
-
2010
- 2010-05-13 CN CN201010171127A patent/CN101817846A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| SHIZUNOBU HASHIMOTO, ET AL.: "Syntheses of Polyphosphonoamides", 《高分子化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311547A (en) * | 2011-06-09 | 2012-01-11 | 苏州科技学院 | Polyphenyl butanediol phosphonothioate compound and preparation method thereof |
| CN102311547B (en) * | 2011-06-09 | 2012-11-07 | 苏州科技学院 | Polyphenyl butanediol phosphonothioate compound and preparation method thereof |
| CN115746310A (en) * | 2018-05-18 | 2023-03-07 | 瑞士材料试验研究所 | Phosphorus-containing oligomers and polymers |
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Application publication date: 20100901 |