CN102942696A - Atmospheric pressure high-glass temperature polyarylene sulfide sulfone and preparation method thereof - Google Patents
Atmospheric pressure high-glass temperature polyarylene sulfide sulfone and preparation method thereof Download PDFInfo
- Publication number
- CN102942696A CN102942696A CN2012104569169A CN201210456916A CN102942696A CN 102942696 A CN102942696 A CN 102942696A CN 2012104569169 A CN2012104569169 A CN 2012104569169A CN 201210456916 A CN201210456916 A CN 201210456916A CN 102942696 A CN102942696 A CN 102942696A
- Authority
- CN
- China
- Prior art keywords
- temperature
- transition temperature
- glass transition
- high glass
- sulfone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses atmospheric pressure high-glass temperature polyarylene sulfide sulfone and a preparation method thereof which are characterized in that 0.1 part to 20 parts of additive, 0.1 part to 50 parts of catalyst, 0.1 part to 100 parts of alkali and 200 parts to 1000 parts of organic solvent are added into a reaction kettle with a nitrogen outlet and inlet pipe, a water distributor, a stirrer and a thermometer, are added with 130 parts to 498 parts of sulfide, have dehydration reaction for 0.5 hours to 6 hours at the temperature of 150DEG C to 200DEG C under the protection of nitrogen, are cooled to 60DEG C to 160DEG C, are added with 0 part to 272.6 parts of 4, 4'- dichloro diphenyl sulfone and 25.2 parts to 503 parts of 4,4'-bis[(4-chlorophenyl)sulfonyl, react for 1 hour to 12 hours at the temperature of 110DEG C to 220DEG C and are maintained for 1 hour to 12 hours at the temperature of 150DEG C to 230DEG C; reaction liquid is poured into tap water, and linear precipitation is separated out; the precipitation is respectively washed by water and ethanol for one to three times, dried for 2 hours to 8 hours at the temperature of 50DEG C to 200DEG C, crushed, respectively extracted and purified with deionized water and acetone, and dried for 1 hour to 20 hours at the temperature of 80DEGC to 200DEG C, and then high-glass temperature polyarylene sulfide sulfone resin is obtained.
Description
Technical field
The present invention relates to a kind of normal pressure high glass transition temperature polyaryl thioether sulfone and preparation method thereof, belong to the Polymer Synthesizing field.
Background technology
Poly arylidene thio-ester owing to its corrosion-resistant, good electrical property, mechanical property, dimensional stability and processing characteristics, can be widely used in automobile, space flight and aviation, electronics and Food Engineering Development aspect such as polyphenylene sulfide, polyphenylene sulfide ketone, PPSS; The poly arylidene thio-ester resinoid is with respect to aromatic polyamide at present, its thermal characteristics of polyimide is slightly poor, second-order transition temperature such as polyphenylene sulfide (PPS) is 85-90 ℃, the second-order transition temperature of polyphenylene sulfide ketone (PPSK) is 150-160 ℃, the second-order transition temperature of polyaryl thioether sulfone (PASS) is 210-220 ℃, difficulty satisfies the requirement of high-end insulating material (such as the H level, the C class F insulating material F requires 180 ℃ of long-term heatproofs, more than 200 ℃), and aromatic polyamide, the second-order transition temperature of polyimide is 260-345 ℃, can satisfy the requirement of some special harshnesses, but aromatic polyamide, polyimide since the extremely strong rigidity of its molecular chain so that its very difficult forming process, cause its production cost higher, the relative poly arylidene thio-ester of its erosion resistance is relatively poor simultaneously, thereby has limited its large-scale promotion and application in suitability for industrialized production.
Summary of the invention
The objective of the invention is to provide for the deficiencies in the prior art a kind of preparation method of normal pressure high glass transition temperature polyaryl thioether sulfone, be characterized in adopting connection 4,4 '-dichloro diphenyl sulfone and connection (4-chloro-diphenyl sulfone) are raw material with sulfide, in polar solvent, adopt the complex phase catalyst system, by two elementary reactions, preparation high molecular high glass transition temperature poly arylidene thio-ester sulphone resin.
Purpose of the present invention realizes by following technical measures, and wherein said raw material umber is parts by weight except specified otherwise.
The chemical reaction structural formula of normal pressure high glass transition temperature polyaryl thioether sulfone is:
Wherein, 0≤p≤200,0＜q≤200; Sulfide X is:
The raw material of normal pressure high glass transition temperature polyaryl thioether sulfone is composed of the following components to be:
Wherein auxiliary agent is at least a in lithium formate, Lithium Acetate, lithium benzoate, Trilithium phosphate, lithium chloride, sodium formiate, sodium-acetate, Sodium Benzoate, sodium phosphate, sodium-chlor, calcium formiate, calcium acetate, calcium benzoate, calcium phosphate and the calcium chloride.
The preparation method of normal pressure high glass transition temperature polyaryl thioether sulfone may further comprise the steps:
With auxiliary agent 0.1-20 part; catalyzer 0.1-50 part; alkali 0.1-100 part and organic solvent 200-1000 part; adding is come in and gone out with nitrogen and is managed; water trap is in the reactor of agitator and thermometer, after stirring; add sulfide 130-498 part; under nitrogen protection, in temperature 150-200 ℃ of dehydration reaction 0.5-6h, the solution after obtaining dewatering; when treating that the mentioned solution temperature is down to 60-160 ℃; add again 4,4 '-dichloro diphenyl sulfone 0-272.6 part, connection (4-chloro-diphenyl sulfone) 25.2-503 part; in temperature 110-220 ℃ of reaction 1-12h; keep 1-12h at temperature 150-230 ℃ again, reaction solution is poured in 2000 parts of tap water, separate out the linear precipitation; through water; ethanol washs 1-3 time respectively; in temperature 50-200 ℃ of dry 2-8h, pulverize, use respectively deionized water; acetone extract is purified; at temperature 80-200 ℃ of dry 1-20h, obtain high glass transition temperature poly arylidene thio-ester sulphone resin.
Described solvent is any in N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), HMPA, N-cyclohexyl pyrrolidone, tetramethylene sulfone, tetramethyl-urea, N,N-DIMETHYLACETAMIDE, dimethyl formamide or the N-methyl caprolactam.
Described catalyzer be in cuprous chloride, cuprous bromide, triphenylphosphine, stannous octoate, hydroxy acid sodium, hexanolactam, epsilon-amino caproic acid, para-aminotoluene or the Sodium sulfanilate any.
In described alkali sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, Quilonum Retard, sodium bicarbonate or the saleratus any.
Described normal pressure high glass transition temperature polyaryl thioether sulfone is used for automobile, space flight and aviation, electronics and food engineering field.
Performance test
1, the structure of the high glass transition temperature poly arylidene thio-ester sulphone resin of the present invention's preparation has obtained confirmation through examination of infrared spectrum, the results detailed in shown in Figure 1.
2, the structure warp of the high glass transition temperature poly arylidene thio-ester sulphone resin of the present invention's preparation
1H-NMR has obtained confirmation, shown in Fig. 2 ~ 4.
3, by regulation and control reactant concn, material proportion and temperature of reaction, the high glass transition temperature poly arylidene thio-ester sulphone resin of preparation different viscosity; And take NMP as solvent, the sample liquid of preparation 0.5g/dl is at 30.0 ± 0.1 ℃ of lower intrinsic viscosity=0.10-0.9dl/g with the determination of ubbelohde viscometer polymkeric substance of temperature.
4, adopt the second-order transition temperature of differential scanning calorimetric analysis method (DSC) test high glass transition temperature poly arylidene thio-ester sulphone resin, the results detailed in shown in Figure 5.
5, polymkeric substance has been carried out respectively the solubility experiment test, shown in 1.
Description of drawings
Fig. 1 is the infrared spectrogram of high glass transition temperature poly arylidene thio-ester sulphone resin
Fig. 2 is the nuclear magnetic spectrum of poly arylidene thio-ester biphenyl sulfone
Fig. 3 is the nuclear magnetic spectrum of polyaryl thioether sulfone biphenyl sulfone
Fig. 4 is the nuclear magnetic spectrum of poly arylidene thio-ester biphenyl sulfone-biphenyl sulfone
Fig. 5 is the differential scanning calorimetric thermogram of high glass transition temperature poly arylidene thio-ester sulphone resin
The present invention has following advantage:
1.4,4 '-dichloro diphenyl sulfone and connection (4-chloro-diphenyl sulfone) synthesize in the process of high glass transition temperature poly arylidene thio-ester sulphone resin with sulfide, adopt the normal pressure composite catalyst system, it have advantages of security good, than environmental protection, repeatability is strong, molecular weight is high, yield is high and purity is high, its raw material is easy to get (such as sodium sulphite, 4 simultaneously, 4 '-dichloro diphenyl sulfone, connection (4-chloro-diphenyl sulfone) etc.), low, the easy popularization of production cost.
2. this base polymer has advantages of high, the easy processing of second-order transition temperature, high temperature resistant and erosion resistance.
3. such polymer phase has lower degree of crystallinity for traditional polyphenylene sulfide, and as the preparation high tenacity, high temperature resistant, corrosion-resistant, the high-end film resin base that electrical property is good has wide practical use.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
With the 0.1g Sodium Benzoate, 0.1g para-aminotoluene, 0.1g sodium hydroxide and 200g N,N-DIMETHYLACETAMIDE add with nitrogen discrepancy pipe, water trap is in the reactor of agitator and thermometer, after stirring, adding is in the sodium sulphite 130g of content 60%, under nitrogen protection, in 150 ℃ of dehydration reaction 0.5h of temperature, the solution after obtaining dewatering, when treating that the mentioned solution temperature is down to 60 ℃, add again 503g connection (4-chloro-diphenyl sulfone), at 110 ℃ of reactions of temperature 1h, keep 1h at 150 ℃ again, reaction solution is poured in the tap water, separate out linear precipitation, with it through water, ethanol washs respectively 1 time, in the dry 2h of temperature 50 C, pulverize, use respectively deionized water, acetone extract is purified, and at 80 ℃ of dry 1h of temperature, obtains high glass transition temperature poly arylidene thio-ester sulphone resin; Its productive rate is 86%, intrinsic viscosity=0.12, infrared and nuclear-magnetism characterizes and sees respectively Fig. 1, shown in Figure 2 for details, dsc analysis as shown in Figure 5: its second-order transition temperature is 243.3 ℃, has preferably thermal characteristics; Solvent resistance is as shown in Table 1 below.
With 20g calcium chloride, the 50g hexanolactam, 100g potassium hydroxide and 1000g HMPA add with nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer, after stirring, add 4,4 '-dimercapto sulfobenzide 282g is under nitrogen protection, in 200 ℃ of dehydration reaction 6h of temperature, solution after obtaining dewatering when treating that the mentioned solution temperature is down to 160 ℃, adds 503g connection (4-chloro-diphenyl sulfone) again, at 220 ℃ of reactions of temperature 12h, keep 12h at 230 ℃ again, reaction solution is poured in the tap water, separate out the linear precipitation, with it through water, ethanol washs respectively 2 times, in 200 ℃ of dry 8h of temperature, pulverize, use respectively deionized water, acetone extract is purified, at 200 ℃ of dry 20h of temperature, obtain high glass transition temperature poly arylidene thio-ester sulphone resin; Its productive rate is 84%, intrinsic viscosity=0.1, infrared and nuclear-magnetism characterizes and sees respectively Fig. 1, shown in Figure 3 for details, dsc analysis as shown in Figure 5: its second-order transition temperature is 263.6 ℃, has preferably thermal characteristics; Solvent resistance is as shown in Table 1 below.
With the 10g lithium chloride, the 20g epsilon-amino caproic acid, 10g salt of wormwood and 500g tetramethylene sulfone add with nitrogen discrepancy pipe, water trap is in the reactor of agitator and thermometer, after stirring, add connection (4-sulfydryl sulfobenzide) 498g, under nitrogen protection, in 180 ℃ of dehydration reaction 3h of temperature, the solution after obtaining dewatering, when treating that the mentioned solution temperature is down to 130 ℃, add again 503g connection (4-chloro-diphenyl sulfone), 170 ℃ of reactions of temperature 6 hours, keep 6h at 200 ℃ again, reaction solution is poured in the tap water, separate out linear precipitation, with it through water, ethanol washs respectively 3 times, in 100 ℃ of dry 4h of temperature, pulverize, use respectively deionized water, acetone extract is purified, and at 120 ℃ of dry 10h of temperature, obtains high glass transition temperature poly arylidene thio-ester sulphone resin; Its productive rate is 91%, intrinsic viscosity=0.73, infrared and nuclear-magnetism characterizes and sees respectively Fig. 1, shown in Figure 4 for details, dsc analysis as shown in Figure 5: its second-order transition temperature is 282.2 ℃, has preferably thermal characteristics; Solvent resistance is as shown in Table 1 below.
With 15g lithium formate and 3g sodium phosphate, the 5g cuprous chloride, 10g saleratus and 600gN-methyl-2-pyrrolidone add with nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer, after stirring, adding is in the sodium sulphite 130g of content 60%, under nitrogen protection, in 160 ℃ of dehydration reactions of temperature 1 hour, solution after obtaining dewatering, when treating that the mentioned solution temperature is down to 130 ℃, add again 272.6g 4,4 '-dichloro diphenyl sulfone and 25.2g connection (4-chloro-diphenyl sulfone), at 160 ℃ of reactions of temperature 10h, keep 12h at 190 ℃ again, reaction solution is poured in the tap water, separate out the linear precipitation, with it through water, ethanol washs respectively 2 times, in 120 ℃ of dry 6h of temperature, pulverize, use respectively deionized water, acetone extract is purified, at 180 ℃ of dry 4h of temperature, obtain high glass transition temperature poly arylidene thio-ester sulphone resin; Its productive rate is 93%, intrinsic viscosity=0.66.
With 12g calcium phosphate and 6g sodium-acetate, 50g triphenylphosphine, 100g yellow soda ash and 800g dimethyl sulfoxide (DMSO) add with nitrogen discrepancy pipe, water trap, in the reactor of agitator and thermometer, after stirring, add 4,4 '-dimercapto sulfobenzide 282g, under nitrogen protection, in 180 ℃ of dehydration reactions of temperature 5 hours, the solution after obtaining dewatering was when treating that the mentioned solution temperature is down to 80 ℃, add again 28.7g 4,4 '-dichloro diphenyl sulfone and 452.7g connection (4-chloro-diphenyl sulfone) at 110 ℃ of reactions of temperature 12h, keep 12h at 150 ℃ again, reaction solution is poured in the tap water, separate out linear precipitation, with it through water, ethanol washs respectively 1 time, in 110 ℃ of dry 3h of temperature, pulverize, use respectively deionized water, acetone extract is purified, and at 120 ℃ of dry 6h of temperature, obtains high glass transition temperature poly arylidene thio-ester sulphone resin; Its productive rate is 89%, intrinsic viscosity=0.60.
With the 20g lithium benzoate, the 40g Sodium sulfanilate, 90g sodium bicarbonate and 400gN-cyclohexyl pyrrolidone add with nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer, after stirring, add connection (4-sulfydryl sulfobenzide) 498g, under nitrogen protection, in 200 ℃ of dehydration reaction 6h of temperature, solution after obtaining dewatering, when treating that the mentioned solution temperature is down to 60 ℃, add again 143.5g 4,4 '-dichloro diphenyl sulfone and 251.2g connection (4-chloro-diphenyl sulfone), at 210 ℃ of reactions of temperature 12h, keep 6h at 220 ℃ again, reaction solution is poured in the tap water, separate out the linear precipitation, with it through water, ethanol washs respectively 3 times, in 100 ℃ of dry 4h of temperature, pulverize, use respectively deionized water, acetone extract is purified, at 120 ℃ of dry 10h of temperature, obtain high glass transition temperature poly arylidene thio-ester sulphone resin; Its productive rate is 93%, intrinsic viscosity=0.90.
Table 1 is the solubility experiment form of super-high glass temperature poly arylidene thio-ester sulphone resin
﹡
In the table 1+be that room temperature is solvable; +-be room temperature slightly soluble;-be that room temperature is insoluble.
Claims (7)
1. normal pressure high glass transition temperature polyaryl thioether sulfone and preparation method thereof is characterized in that the chemical reaction structural formula of this high glass transition temperature polyaryl thioether sulfone is:
Wherein, 0≤p≤200,0＜q≤200; Sulfide X is:
2. according to the described normal pressure high glass transition temperature of claim 1 polyaryl thioether sulfone, it is characterized in that the raw material of this high glass transition temperature polyaryl thioether sulfone is composed of the following components, be by weight:
Wherein, auxiliary agent is at least a in lithium formate, Lithium Acetate, lithium benzoate, Trilithium phosphate, lithium chloride, sodium formiate, sodium-acetate, Sodium Benzoate, sodium phosphate, sodium-chlor, calcium formiate, calcium acetate, calcium benzoate, calcium phosphate and the calcium chloride.
3. according to the preparation method of claim 1 or 2 described normal pressure high glass transition temperature polyaryl thioether sulfones, it is characterized in that the method may further comprise the steps, be by weight:
With auxiliary agent 0.1-20 part; catalyzer 0.1-50 part; alkali 0.1-100 part and organic solvent 200-1000 part; adding is come in and gone out with nitrogen and is managed; water trap is in the reactor of agitator and thermometer, after stirring; add sulfide 130-498 part; under nitrogen protection, in temperature 150-200 ℃ of dehydration reaction 0.5-6h, the solution after obtaining dewatering; when treating that the mentioned solution temperature is down to 60-160 ℃; add again 4,4 '-dichloro diphenyl sulfone 0-272.6 part, connection (4-chloro-diphenyl sulfone) 25.2-503 part; in temperature 110-220 ℃ of reaction 1-12h; keep 1-12h at temperature 150-230 ℃ again, reaction solution is poured in the tap water, separate out the linear precipitation; through water; ethanol washs 1-3 time respectively; in temperature 50-200 ℃ of dry 2-8h, pulverize, use respectively deionized water; acetone extract is purified; at temperature 80-200 ℃ of dry 1-20h, obtain high glass transition temperature poly arylidene thio-ester sulphone resin.
4. according to the preparation method of the described normal pressure high glass transition temperature of claim 3 polyaryl thioether sulfone, it is characterized in that solvent is any in N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), HMPA, N-cyclohexyl pyrrolidone, tetramethylene sulfone, tetramethyl-urea, N,N-DIMETHYLACETAMIDE, dimethyl formamide or the N-methyl caprolactam.
5. according to the preparation method of the described normal pressure high glass transition temperature of claim 3 polyaryl thioether sulfone, it is characterized in that catalyzer is any in cuprous chloride, cuprous bromide, triphenylphosphine, stannous octoate, hydroxy acid sodium, hexanolactam, epsilon-amino caproic acid, para-aminotoluene or the Sodium sulfanilate.
6. according to the preparation method of the described normal pressure high glass transition temperature of claim 3 polyaryl thioether sulfone, it is characterized in that in alkali sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, Quilonum Retard, sodium bicarbonate or the saleratus any.
7. according to the described normal pressure high glass transition temperature of claim 1 polyaryl thioether sulfone, it is characterized in that this normal pressure high glass transition temperature polyaryl thioether sulfone is used for automobile, space flight and aviation, electronics and food engineering field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104569169A CN102942696A (en) | 2012-11-14 | 2012-11-14 | Atmospheric pressure high-glass temperature polyarylene sulfide sulfone and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104569169A CN102942696A (en) | 2012-11-14 | 2012-11-14 | Atmospheric pressure high-glass temperature polyarylene sulfide sulfone and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102942696A true CN102942696A (en) | 2013-02-27 |
Family
ID=47725702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012104569169A Pending CN102942696A (en) | 2012-11-14 | 2012-11-14 | Atmospheric pressure high-glass temperature polyarylene sulfide sulfone and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102942696A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102098A (en) * | 2017-12-19 | 2018-06-01 | 西藏睿兴新材料科技有限公司 | The medium temperature two-step synthetic method of polyaryl thioether sulfone |
| CN118620206B (en) * | 2024-08-12 | 2024-11-15 | 苏州港睿通纳米材料科技有限公司 | High-purity polyphenylene sulfide and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5093467A (en) * | 1988-06-23 | 1992-03-03 | Tosoh Corporation | Production of poly(arylene sulfide sulfone) with excess water to alkali metal sulfide |
| US5180796A (en) * | 1990-02-26 | 1993-01-19 | Phillips Petroleum Company | Derivatization of arylene sulfide polymers |
| CN1461763A (en) * | 2002-05-31 | 2003-12-17 | 四川大学 | Polyaryl thioether sulfone and its preparation method |
-
2012
- 2012-11-14 CN CN2012104569169A patent/CN102942696A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5093467A (en) * | 1988-06-23 | 1992-03-03 | Tosoh Corporation | Production of poly(arylene sulfide sulfone) with excess water to alkali metal sulfide |
| US5180796A (en) * | 1990-02-26 | 1993-01-19 | Phillips Petroleum Company | Derivatization of arylene sulfide polymers |
| CN1461763A (en) * | 2002-05-31 | 2003-12-17 | 四川大学 | Polyaryl thioether sulfone and its preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102098A (en) * | 2017-12-19 | 2018-06-01 | 西藏睿兴新材料科技有限公司 | The medium temperature two-step synthetic method of polyaryl thioether sulfone |
| CN108102098B (en) * | 2017-12-19 | 2020-07-10 | 西藏睿兴新材料科技有限公司 | Medium-temperature two-step synthesis method of polyarylene sulfide sulfone |
| CN118620206B (en) * | 2024-08-12 | 2024-11-15 | 苏州港睿通纳米材料科技有限公司 | High-purity polyphenylene sulfide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172864B (en) | Preparation method of organic acid salt catalytic polyarylene sulfide | |
| CN102127226B (en) | Preparation method of polyarylene sulfide film | |
| CN103709405B (en) | A kind of High-purity autocatalytic polyarylene sulfide and preparation method thereof | |
| CN108285535A (en) | A kind of ternary, the synthetic method of multi-component copolymer polysulfone resin | |
| CN102702506A (en) | Soluble polyaryletherketone and preparation method thereof | |
| CN106589348A (en) | Polyarylether with main chain containing bisbenzofiurene and triaryl-s-triazine structure and preparation method of polyarylether | |
| CN102952269B (en) | Polyarylenesulfidesulfone/polyethersulfone copolymer and preparation method thereof | |
| CN107573501A (en) | A kind of cross-linking fluorine-containing sulfonated polyether compound and preparation method thereof | |
| CN110922598B (en) | Synthetic method of benzenediol derivative type polysulfate | |
| CN103467741A (en) | Polyphenylene sulfide and preparation method thereof | |
| CN102659526A (en) | Tetraphenolic hydroxyfluorene compound and preparation method thereof | |
| CN101864077B (en) | Polyarylene sulfide ketone and preparation method thereof | |
| CN102942696A (en) | Atmospheric pressure high-glass temperature polyarylene sulfide sulfone and preparation method thereof | |
| CN104109236A (en) | Fatty cyclosemi aromatic polyarylether amide and preparation method thereof | |
| CN102558558A (en) | Polyether sulphone-nitrile resin and industrialization synthetic method thereof | |
| CN111205452B (en) | Phenolphthalein type high-dielectric polyarylether resin with side chain containing methylsulfonyl and preparation method thereof | |
| CN106750302B (en) | A kind of preparation method of heat-resisting, corrosion resistant high molecular weight poly arylidene thio-ester sulfone | |
| CN101381307B (en) | 4-ethyl benzoate phenyl p-dihydroxy benzene and preparation method and application thereof | |
| CN104311828A (en) | Polyarylether containing adamantine structure and preparation method | |
| CN112409596B (en) | Polysulfone and preparation method thereof | |
| CN101580591B (en) | Method for preparing aromatic nucleophilic substitution polymer under anhydrous condition | |
| CN111875791A (en) | Preparation method of polyaryletherketone resin | |
| CN101735446B (en) | Preparation method of chlorosulfonylated polyarylether resins | |
| CN108129654A (en) | A kind of readily soluble flame retardant type fluorinated poly arylene ether nitrile resin of high temperature resistant and preparation method thereof | |
| CN112979940A (en) | All-biphenyl polyaryletherketone precursor as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130227 |