CN101928455A - Polyphenylene oxide composition and method for improving heat stability of polyphenylene oxide thereof - Google Patents
Polyphenylene oxide composition and method for improving heat stability of polyphenylene oxide thereof Download PDFInfo
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Abstract
The invention provides a polyphenylene oxide composition which contains the following components in mass percentage: 60.0-92.0 percent of polyphenylene oxide resin raw powder, 7.7-40.0 percent of low-molecular polyphenylene oxide resin raw powder and 0-0.3 percent of hindered phenolic antioxidant. The invention also provides a method for improving the heat stability of polyphenylene oxide. The component distribution of the polyphenylene oxide composition is more reasonable, and the low-molecular component has good antioxidant effect; when the hindered phenolic antioxidants of similar structures are added, the addition quantity of the low-molecular polyphenylene oxide can be reduced, and the heat stability of the polyphenylene oxide composition can be effectively guaranteed. The method for improving the heat stability of the polyphenylene oxide is simple and practicable, has limited cost increase and has strong maneuverability.
Description
Technical field
The present invention relates to a kind of polyphenylene ether composition, with and be used to improve the method for heat stability of polyphenylene oxide.Belong to macromolecular material and forming process field thereof.
Background technology
Since nineteen fifty-nine polyphenylene oxide (PPE) is by the Allan S.Hay of U.S. GE company invention and suitability for industrialized production,, its excellent mechanical property, resistance toheat, chemical resistant properties and electrical property paid close attention to because of enjoying industry.Especially by with polystyrene (PS) blending and modifying, significantly improved its processing fluidity, promoted the development of the synthetic and processing industry of polyphenylene oxide, it is leapt to is the row of five large-engineering plastics.
But, because polyphenylene oxide can generate a certain amount of quinones product in building-up process, even also have the part amines catalyst to be connected on the methyl of its macromolecular main chain phenyl ring, make the yellowness index of the former powder of polyphenylene oxide up to 10 units.The melt-processed process further formation and the amine alkyl substituent of aggravation quinones transforms to dark product, makes its yellowness index up to more than 30.This phenomenon has determined polyphenylene oxide to be difficult to the preparation light-coloured prods on the one hand, has also caused concern and the query of industry to its thermostability on the other hand.
Consider from the molecular structure aspect, contain a large amount of phenolic group aromatic nucleus in the main chain of polyphenylene oxide, and because two methyl have sealed two adjacent active sites, Sauerstoffatom and phenyl ring are in p-π and grip state altogether in addition, so polyphenylene oxide should have higher thermostability.But the end group of polyphenylene oxide macromolecular chain is a phenolic hydroxyl group, easily from the end group oxidation, influences the thermostability of polyphenylene oxide when being heated.Therefore, it is end-capping reagent that patent CN13466377A adopts Whitfield's ointment or anthranilic acid etc., has significantly reduced the capture ability of PPE to free radical.U.S. Pat 4,760,118 have proposed the method for solvent-free scorification blocking polyphenyl ether resin.Patent CN1085694C then adopts the two keys that contain hydroxyl or intramolecularly specific position or the oxy-compound such as the decolourings such as bitter almond oil camphor, acetoin and benzpinacone of aromatics key, effectively reduces the yellowness index of polyphenylene oxide processed products.U.S. Pat 4,588,764 (1986), US4,483,953 (1984) and US4,405,739 (1983) all propose to improve color after polyphenylene oxide and the initial hot-work of blend composition thereof with phosphite.Patent CN101423658 melt extrudes a certain amount of silicon rubber of adding in the course of processing at polyphenyl ether/styrene, can effectively suppress polyphenyl ether resin composition variable color in the course of processing, improves the high-temperature stability of polyphenyl ether resin composition.
But the Thermal Decomposition Mechanism of polyphenylene oxide is very complicated.As far back as 1969, EHLERS etc. (JOURNAL OF POLYMER SCIENCE:PART A-1VOL.7,2931-2953,1969) have just furtherd investigate the Thermal Decomposition Mechanism of polyphenylene oxide, mainly generate low-molecular-weight chain segment when thinking the polyphenylene oxide degraded, the part segment contains terminal hydroxy group.The part ehter bond carries out along with ring-opening reaction and degrades, and generates CO, water and CO
2
FACTOR (JOURNAL OF POLYMER SCIENCE:PART A-1VOL.7,363-377,1969) has studied the thermal degradation process of polyphenylene oxide up to 1000 ℃ time the in the rare gas element.The whole degradation process of finding polyphenylene oxide was divided into for two steps: 1) a quick exothermic process is arranged between 430～500 ℃, generated phenol, water, carbon black and highly cross-linked residue; 2) be higher than 500 ℃ and be green coke process slowly, it is characterized in that having generated simultaneously methane, CO and H
2X-ray analysis confirms that the coke that the 2nd step generated is unbodied.The infrared analysis result of sample who is heated to 510 ℃ is almost identical with former powder, shows that the oxidizing reaction in the degraded of the 1st step is unimportant.The data of low temperature degradation process are consistent with the thermal destruction mechanism of the DeR of the 2-methane that generates based on the Free radicals rearrangement reaction of polyphenylene oxide and/or by adjacent methyl-phenyl ether thermal rearrangement.The green coke process can generate H with the Sxwarc mechanism explain of toluene pyrolytic decomposition
2And methane, ring-opening reaction takes place simultaneously, generate CO.
Therefore, only adopt the method for end-blocking, decolouring, can only suitably improve the thermostability or the outward appearance of polyphenylene oxide from different separately angles.Especially to adopting the polyphenylene oxide resin of copper-amine catalyst system interrupter method production; because the problem of its polymerization technique control; even if taked end-blocking measure and aftertreatment washing process; the thermostability of products therefrom is difficult to still guarantee that its heat decomposition temperature (thermogravimetry-TGA method test) usually has 5～10 ℃ fluctuation.If adopt the method for the described adding silicon rubber of patent CN101423658, just utilize the resistance to elevated temperatures of silicon rubber self, improve the thermostability of whole co-mixing system, also fundamentally do not improve the thermostability of PPE resin.
Researchist of the present invention utilizes TGA to further investigate N
2Thermal Decomposition Mechanism with the polyphenylene oxide of different molecular weight under the air atmosphere, think and only adopt the thermal decomposition performance that temperature (being commonly defined as heat decomposition temperature) under the maximum heat weight loss rate can not complete sign polyphenylene oxide, need to adopt the index ability comprehensive representation that is associated with the polyphenylene oxide thermal degradation activation energy to go out the thermostability of polyphenylene oxide.(petrochemical complex, 2009 the 38th the 5th phases of volume think that 563-567) adopting differential scanning calorimetry (DSC) method to measure the oxidation induction time (OIT) of macromolecular material can be related with the thermal degradation activation energy of macromolecular material well to Zheng Qiu Kai etc.If adopt the experimental technique of its recommendation or the DSC oxidation induction period method of GB GB/T17391 test plastic pipe thermostability, also be difficult to judge the starting point of polyphenylene oxide resin DeR.And, if adopt the test of TGA method, in air atmosphere, be lower than 390 ℃, the weightlessness that is difficult to observe the chain rupture of polyphenylene oxide macromole in the short period of time and discharges the small molecules product.Surpass 390 ℃, polyphenylene oxide promptly begins slow weightlessness, is difficult to judge the starting point of DeR again.Therefore, researchist of the present invention considers to adopt pairing zero-g time conduct of transformation efficiency unified under the constant temperature (as 390 ℃, 10% rate of weight loss) and oxidation induction period (OIT) evaluation index of equal value to investigate the thermal decomposition performance or the thermostability of polyphenylene oxide resin.Experiment showed, this evaluation index and classical non-isothermal experimental technique (Flyn-Ozawa-Wall method) (Ozawa T., Bulletin of the Chemical Society of Japan, 1968,38 (11): 1881～1886; Ozawa T., Journal of Thermal Analysis and Calorimetry, 1970,2 (3): 301～324; Flynn J.H., Wall L.A., Journal of Polymer Science Part B:Polymer Letters, 1966,4 (3): 323～328) good correspondence is arranged, can more effectively characterize and estimate the thermostability of polyphenylene oxide.
Simultaneously, we find that the low molecular weight polycaprolactone phenylate of limiting viscosity between 0.10～0.15dL/g has good thermostability, and especially at the elevated temperature heat catabolic phase that is higher than 390 ℃, its thermostability is more remarkable.Trace it to its cause, we think that the polyphenylene oxide molecule of this molecular weight ranges has a certain proportion of hindered phenol structure equally, with oxidation inhibitor Anox 330TDS (1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene)
Has similar molecular structure.The substituting group that different is on its phenolic group aromatic nucleus is not the tertiary butyl, but methyl.Therefore, the polyphenylene oxide of this molecular weight ranges just can add in the high-molecular weight polyphenylene oxide resin as effective antioxidant composition, fundamentally improves the thermostability of polyphenylene oxide resin.Simultaneously, a small amount of low molecular weight polyphenylene ether resins adds in the high molecular weight polybenzimidazole ether resin, can play the effect of softening agent, suitably improves the processing characteristics of polyphenylene oxide resin.If low-molecular polyphenylene ether is being added in the process of high-molecular-weight poly phenylate, a certain proportion of oxidation inhibitor Anox 330 TDS (1 of suitable composite adding, 3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene), can take into account the thermostability of low thermophase polyphenylene ether composition.
Patent, paper that the collaborative Hinered phenols antioxidant of relevant employing low molecular weight polycaprolactone phenylate component improves the thermostability of polyphenylene oxide resin yet there are no report.
Summary of the invention
The purpose of this invention is to provide a kind of polyphenylene ether composition, the thermostability that it can improve the former powder of polyphenylene oxide resin that copper-amine catalyst system interrupter method produces overcomes the defective of its component irrational distribution, poor heat stability.
Another object of the present invention provides a kind of preparation method of polyphenylene ether composition.
An also purpose of the present invention provides a kind of method that improves heat stability of polyphenylene oxide.
A further object of the present invention provides a kind of method of estimating heat stability of polyphenylene oxide.
In order to realize the object of the invention, the invention provides a kind of polyphenylene ether composition, its component by following content is formed:
The former powder of polyphenylene oxide resin (PPE) 60.0～92.0 quality %,
Low molecular weight polycaprolactone phenylate resinogen powder (LPPE) 7.7～40.0 quality %,
Hinered phenols antioxidant 0～0.3 quality %.
Wherein, described polyphenylene oxide resin (PPE) poly-(2, the 6-dimethyl benzene) ether for adopting copper-amine catalyst system interrupter method to produce; Its limiting viscosity of measuring in 25 ℃ of chloroforms is 0.40～0.45dL/g.
Poly-(2, the 6-dimethyl benzene) ether of lower molecular weight that described low molecular weight polycaprolactone phenylate resin (LPPE) is produced for adopting copper-amine catalyst system interrupter method; Its limiting viscosity of measuring in 25 ℃ of chloroforms is 0.10～0.15dL/g.
Described Hinered phenols antioxidant is oxidation inhibitor Anox 330TDS (1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene).
The preparation method of polyphenylene ether composition of the present invention, it comprises the steps:
Earlier the former powder of polyphenylene oxide resin at room temperature is dissolved in the toluene solvant, forms the solution of concentration 10～15 quality %, add low molecular weight polycaprolactone phenylate resinogen powder and Hinered phenols antioxidant by the quality proportioning simultaneously, placed 18～36 hours, form complete homogeneous phase solution; 30～60 ℃ of dryings form under 0.05～0.08MPa vacuum tightness then.
Polyphenylene ether composition of the present invention can improve the thermostability of the former powder of polyphenylene oxide resin, promptly is used to improve the heat-staple method of polyphenylene oxide, and this method may further comprise the steps:
Earlier the former powder of polyphenylene oxide resin at room temperature is dissolved in the toluene solvant, adds low molecular weight polycaprolactone phenylate resinogen powder and Hinered phenols antioxidant by weight ratio simultaneously, placed 18～36 hours, form complete homogeneous phase solution; 30～60 ℃ of dryings form under 0.05～0.08MPa vacuum tightness then.
The present invention also provides and adopts thermal gravimetric analyzer (TGA), estimates the method for the thermostability of polyphenylene oxide resin under 390 ℃ of constant temperatures and composition thereof.Its evaluation index is 10% rate of weight loss time (t
390 ℃).
Concrete evaluation method is:
Adopt Perkin﹠amp; Elmer TGA6 hot weightless instrument is tested weightless 10% (mass percent) required time (t of polyphenylene oxide (PPE) in 390 ℃ of following air atmospheres
390 ℃).At first adding 20～25mgPPE sample in ceramic crucible, is the nitrogen (N of 40ml/min at flow
2) speed with 100 ℃/min in the atmosphere rises to 390 ℃ with temperature rapidly from 30 ℃.Then, switch to the air atmosphere of flow 40ml/min rapidly, pick up counting, sample weightlessness 10% (mass percent) is the test terminal point, and required time is 10% rate of weight loss time t
390 ℃
Polyphenylene ether composition of the present invention is compared with the former powder of polyphenylene oxide resin of copper-amine catalyst system interrupter method production, and it is more reasonable that the component of this polyphenylene ether composition distributes, and its low-molecular-weight component plays good antioxygenation; The Hinered phenols antioxidant Anox 330TDS of interpolation similar (1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene) after, both can reduce the addition of low-molecular polyphenylene ether, and can effectively guarantee the thermostability of polyphenylene ether composition again.
In addition, the method for the polyphenylene ether composition of preparation good heat stability of the present invention is simple, and cost increases limited, workable.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
The limiting viscosity that the former powder of polyphenylene oxide resin in the various embodiments of the present invention adopts Ruicheng branch office of Lanxing Chemical New Material Co., Ltd. to produce is the polyphenylene oxide of 0.40～0.45dL/g, is poly-(2, the 6-dimethyl benzene) ether; It is the low-molecular polyphenylene ether of 0.10～0.15dL/g that low molecular weight polycaprolactone phenylate resinogen powder adopts engineering center of Chinese chemical industry group company synthetic limiting viscosity, is low-molecular-weight poly-(2, the 6-dimethyl benzene) ether; The oxidation inhibitor Anox 330TDS (1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene) that Hinered phenols antioxidant is produced for Chemtura company.
Embodiment 1
The former powder of weighing polyphenylene oxide resin (limiting viscosity the is 0.45dL/g) 60g of elder generation, at room temperature be dissolved in the toluene solvant, forming concentration is the solution of 10 quality %, simultaneously 40g low molecular weight polycaprolactone phenylate resinogen powder (limiting viscosity is 0.10dL/g) is added wherein, place 24hr, suitably vibrate into complete homogeneous phase solution.Subsequently, 50 ℃ are dried to constant weight under 0.05MPa vacuum tightness, get polyphenylene ether composition.
Adopt thermal gravimetric analyzer (TGA), estimate the thermostability of the polyphenylene ether composition of present embodiment under 390 ℃ of constant temperatures.Its evaluation index is 10% rate of weight loss time (t
390 ℃).
Concrete evaluation method is:
Adopt Perkin﹠amp; Elmer TGA6 hot weightless instrument is tested weightless 10% (mass percent) required time (t of polyphenylene oxide (PPE) in 390 ℃ of following air atmospheres
390 ℃).The polyphenylene ether composition that at first adds 20～25mg present embodiment in ceramic crucible is the nitrogen (N of 40ml/min at flow
2) speed with 100 ℃/min in the atmosphere rises to 390 ℃ with temperature rapidly from 30 ℃.Then, switch to the air atmosphere of flow 40ml/min rapidly, pick up counting, sample weightlessness 10% (mass percent) is the test terminal point, and required time is 10% rate of weight loss time t
390 ℃
After measured, t
390 ℃Be 54.1min.
Embodiment 2
The former powder of weighing polyphenylene oxide resin (limiting viscosity the is 0.45dL/g) 70g of elder generation, at room temperature be dissolved in the toluene solvant, forming concentration is the solution of 10 quality %, simultaneously 30g low molecular weight polycaprolactone phenylate resinogen powder (limiting viscosity is 0.10dL/g) is added wherein, place 36hr, suitably vibrate into complete homogeneous phase solution.Subsequently, 60 ℃ are dried to constant weight under 0.06MPa vacuum tightness, get polyphenylene ether composition.
Adopt thermal gravimetric analyzer (TGA), estimate the thermostability of the polyphenylene ether composition of present embodiment under 390 ℃ of constant temperatures.Its evaluation index is 10% rate of weight loss time (t
390 ℃).
After measured, t
390 ℃Be 45.5min.
Embodiment 3
The former powder of weighing polyphenylene oxide resin (limiting viscosity the is 0.45dL/g) 80g of elder generation, at room temperature be dissolved in the toluene solvant, forming concentration is the solution of 15 quality %, simultaneously 20g low molecular weight polycaprolactone phenylate resinogen powder (limiting viscosity is 0.10dL/g) is added wherein, place 18hr, suitably vibrate into complete homogeneous phase solution.Subsequently, 30 ℃ are dried to constant weight under 0.08MPa vacuum tightness, get polyphenylene ether composition.
Adopt thermal gravimetric analyzer (TGA), estimate the thermostability of the polyphenylene ether composition of present embodiment under 390 ℃ of constant temperatures.Its evaluation index is 10% rate of weight loss time (t
390 ℃).
After measured, t
390 ℃Be 39.4min.
Embodiment 4
Basic preparation process is with embodiment 1, different is that each set of dispense ratio of the polyphenylene ether composition of present embodiment is: limiting viscosity is that former powder of the polyphenylene oxide resin of 0.45dL/g and limiting viscosity are that the mass ratio of the low molecular weight polycaprolactone phenylate resinogen powder of 0.10dL/g is 90: 10.
After measured, its 10% rate of weight loss time t
390 ℃Be 23.7min.
Embodiment 5
Basic preparation process is with embodiment 1, different is that each set of dispense ratio of the polyphenylene ether composition of present embodiment is: limiting viscosity is that the former powder of the polyphenylene oxide resin of 0.45dL/g, limiting viscosity are that the low molecular weight polycaprolactone phenylate resinogen powder of 0.10dL/g and the mass ratio of oxidation inhibitor Anox 330TDS are 92: 7.7: 0.3.
After measured, its 10% rate of weight loss time t
390 ℃Be 33.1min.
Embodiment 6
Basic preparation process is with embodiment 1, different is that each set of dispense ratio of the polyphenylene ether composition of present embodiment is: limiting viscosity is that the former powder of the polyphenylene oxide resin of 0.45dL/g, limiting viscosity are that the low molecular weight polycaprolactone phenylate resinogen powder of 0.10dL/g and the mass ratio of oxidation inhibitor Anox 330TDS are 92: 7.9: 0.1.
After measured, its 10% rate of weight loss time t
390 ℃Be 26.3min.
Embodiment 7
Basic preparation process is with embodiment 1, different is that each set of dispense ratio of the polyphenylene ether composition of present embodiment is: limiting viscosity is that the former powder of the polyphenylene oxide resin of 0.45dL/g, limiting viscosity are that the low molecular weight polycaprolactone phenylate resinogen powder of 0.15dL/g and the mass ratio of oxidation inhibitor Anox 330TDS are 92: 7.9: 0.1.
After measured, its 10% rate of weight loss time t
390 ℃Be 25.7min.
Embodiment 8
Basic preparation process is with embodiment 1, different is that each set of dispense ratio of the polyphenylene ether composition of present embodiment is: limiting viscosity is that the former powder of the polyphenylene oxide resin of 0.40dL/g, limiting viscosity are that the low molecular weight polycaprolactone phenylate resinogen powder of 0.10dL/g and the mass ratio of oxidation inhibitor Anox 330TDS are 92: 7.7: 0.3.
After measured, its 10% rate of weight loss time t
390 ℃Be 34.5min.
Comparative Examples 1
The former powder of polyphenylene oxide that with limiting viscosity is 0.40dL/g prepares sample according to the method for embodiment 1, does not just add any antioxidant composition, and through embodiment 1 described " 10% rate of weight loss time t
390 ℃" evaluation method records its 10% rate of weight loss time t
390 ℃Be 7.6min.
Comparative Examples 2
The former powder of polyphenylene oxide that with limiting viscosity is 0.45dL/g prepares sample according to the method for embodiment 1, does not just add any antioxidant composition, and through embodiment 1 described " 10% rate of weight loss time t
390 ℃" evaluation method records its 10% rate of weight loss time t
390 ℃Be 6.5min.
Comparative Examples 3
The former powder of low molecular weight polycaprolactone phenylate that with limiting viscosity is 0.10dL/g prepares sample according to the method for embodiment 1, does not just add any antioxidant composition, and through embodiment 1 described " 10% rate of weight loss time t
390 ℃" evaluation method records its 10% rate of weight loss time t
390 ℃Be 54.8min.
Comparative Examples 4
The former powder of low molecular weight polycaprolactone phenylate that with limiting viscosity is 0.15dL/g prepares sample according to the method for embodiment 1, does not just add any antioxidant composition, and through embodiment 1 described " 10% rate of weight loss time t
390 ℃" evaluation method records its 10% rate of weight loss time t
390 ℃Be 50.3min.
Polyphenylene ether composition of the present invention is compared with the former powder of polyphenylene oxide resin of copper-amine catalyst system interrupter method production, and it is more reasonable that the component of this polyphenylene ether composition distributes, and its low-molecular-weight component plays good antioxygenation; The Hinered phenols antioxidant Anox 330TDS of interpolation similar (1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene) after, both can reduce the addition of low-molecular polyphenylene ether, and can effectively guarantee the thermostability of polyphenylene ether composition again.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a polyphenylene ether composition is characterized in that, its component by following content is formed:
Former powder 60.0～92.0 quality % of polyphenylene oxide resin,
Low molecular weight polycaprolactone phenylate resinogen powder 7.7～40.0 quality %,
Hinered phenols antioxidant 0～0.3 quality %.
2. polyphenylene ether composition according to claim 1 is characterized in that, the former powder of described polyphenylene oxide resin poly-(2, the 6-dimethyl benzene) ether for adopting copper-amine catalyst system interrupter method to produce.
3. polyphenylene ether composition according to claim 2 is characterized in that, the limiting viscosity that the former powder of described polyphenylene oxide resin is measured in 25 ℃ of chloroforms is 0.40～0.45dL/g.
4. according to any described polyphenylene ether composition of claim 1-3, it is characterized in that poly-(2, the 6-dimethyl benzene) ether of lower molecular weight that described low molecular weight polycaprolactone phenylate resinogen powder is produced for adopting copper-amine catalyst system interrupter method.
5. polyphenylene ether composition according to claim 4 is characterized in that, the limiting viscosity that described low molecular weight polycaprolactone phenylate resinogen powder is measured in 25 ℃ of chloroforms is 0.10～0.15dL/g.
6. according to any described polyphenylene ether composition of claim 1-5, it is characterized in that described Hinered phenols antioxidant is 1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene.
7. prepare the method for any described polyphenylene ether composition of claim 1-6, it is characterized in that, it comprises the steps:
Earlier the former powder of polyphenylene oxide resin at room temperature is dissolved in the toluene solvant, adds low molecular weight polycaprolactone phenylate resinogen powder and Hinered phenols antioxidant by the quality proportioning simultaneously, placed 18～36 hours, form complete homogeneous phase solution; 30～60 ℃ of dryings form under 0.05～0.08MPa vacuum tightness then.
8. a method that improves heat stability of polyphenylene oxide is characterized in that it comprises the steps:
1) at room temperature be dissolved in the former powder of polyphenylene oxide resin in the toluene solvant earlier, add low molecular weight polycaprolactone phenylate resinogen powder and Hinered phenols antioxidant simultaneously, placed 18～36 hours, form complete homogeneous phase solution, wherein the consumption of each component is respectively: former powder 60.0～92.0 quality % of polyphenylene oxide resin, low molecular weight polycaprolactone phenylate resinogen powder 7.7～40.0 quality %, Hinered phenols antioxidant 0～0.3 quality %;
2) then under 0.05～0.08MPa vacuum tightness 30～60 ℃ of dryings form.
9. a method of estimating heat stability of polyphenylene oxide is characterized in that, this method adopts Perkin﹠amp; Elmer TGA6 hot weightless instrument, weightless 10% required time of test polyphenylene oxide in 390 ℃ of following air atmospheres.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113308108A (en) * | 2021-06-28 | 2021-08-27 | 大连中沐化工有限公司 | Composition for photovoltaic junction box |
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|---|---|---|---|---|
| US4284735A (en) * | 1980-06-23 | 1981-08-18 | Arco Polymers, Inc. | Polyphenylene oxide blend with rubber-maleimide-styrene copolymer |
| CN1227854A (en) * | 1997-12-15 | 1999-09-08 | 通用电气公司 | Process for producing blends of tackifying resins with low molecular weight polyphenylene ethers |
| CN1353739A (en) * | 1999-04-02 | 2002-06-12 | 通用电气公司 | Compositions of interpolymer and polyphenylene ether resin |
| US7230046B2 (en) * | 2004-08-19 | 2007-06-12 | General Electric Company | Flame-retardant polyphenylene ether compositions, and related articles |
-
2010
- 2010-06-30 CN CN 201010222462 patent/CN101928455A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284735A (en) * | 1980-06-23 | 1981-08-18 | Arco Polymers, Inc. | Polyphenylene oxide blend with rubber-maleimide-styrene copolymer |
| CN1227854A (en) * | 1997-12-15 | 1999-09-08 | 通用电气公司 | Process for producing blends of tackifying resins with low molecular weight polyphenylene ethers |
| CN1353739A (en) * | 1999-04-02 | 2002-06-12 | 通用电气公司 | Compositions of interpolymer and polyphenylene ether resin |
| US7230046B2 (en) * | 2004-08-19 | 2007-06-12 | General Electric Company | Flame-retardant polyphenylene ether compositions, and related articles |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113308108A (en) * | 2021-06-28 | 2021-08-27 | 大连中沐化工有限公司 | Composition for photovoltaic junction box |
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