CN101153075A - Hyperbranched polyphenylene sulfide and method for preparing the same - Google Patents
Hyperbranched polyphenylene sulfide and method for preparing the same Download PDFInfo
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- CN101153075A CN101153075A CNA200710046844XA CN200710046844A CN101153075A CN 101153075 A CN101153075 A CN 101153075A CN A200710046844X A CNA200710046844X A CN A200710046844XA CN 200710046844 A CN200710046844 A CN 200710046844A CN 101153075 A CN101153075 A CN 101153075A
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- thiophenol
- polyphenylene sulfide
- dichlorobenzene
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Abstract
The present invention discloses a super branching polyphenylene sulfide and a preparation method thereof. The preparation method comprises the following steps: with the protection of the nitrogen, the thiophenol benzene monomer containing two chlorine terminal groups and the alkali metal salt catalyst react for 2 hours to 40 hours in the non-proton solvent and at a temperature between 100 DEG C and 200 DEG C; the target polymer can be collected from the reaction products. The super branching polyphenylene sulfide of the present invention has the significant advantages of the cheap raw materials, fewer reaction steps, simple operation, high production rate and short reaction time. The general formula of the structure is as shown in the figure.
Description
Technical field
The present invention relates to hyperbranched polyphenylene sulfide and preparation method thereof, particularly hold chloro hyperbranched polyphenylene sulfide and preparation method thereof.
Background technology
The nineties in 20th century, experiment researchist Kim of department of E.I.Du Pont Company and Webster etc. are in carrying out the research process of dendrimer as rheology modifier and spherical polyfunctionality initiator, the building-up process of considering tree shaped polymer is too difficult and loaded down with trivial details, and they have developed by AB
2The method of hyperbranched polymers such as type monomer one-step synthesis polyphenyl.
These polymkeric substance have excellent solubility property, and can be used as rheology modifier.From then on hyperbranched polymer becomes one of focus of polymer science research in recent decades.In following patent: US5587441, US5587446, US5663260, SE92005644, report is arranged.Hyperbranched polymer is obtained through single step reaction by Abx type (x 〉=2) monomer usually, do not need the operations such as synthetic, separation, purifying of multistep, be simple and easy to, and has similar structure and the character of getting to branch-shape polymer, can get surrogate as branch-shape polymer in many Application Areass, therefore large-scale industrial production more likely has more application potential.Since hyperbranched polymer unique three-dimensional molecular structure and a large amount of functional end-group, make it to have low viscosity, high reaction activity and good premium propertiess such as solubility property.Thereby obtained application in many fields such as coating, tamanori, auxiliary rheological agents, medicament slow release, self-assemblies.
At present, the synthetic method of said hyperbranched polyphenylene sulfide has had many documents to report, as:
Macromolecules, in 1996,29, Masa-aki Kakimoto is with 1,3, and the 5-tribromo-benzene is a raw material, " multistep processes " synthesis of super branched polyphenylene sulfide;
There is a raw material costliness in the technology of above-mentioned bibliographical information, and reactions steps is various, long reaction time, and the defective of productive rate low (productive rate is less than 10%), so this invention does not have practical value.
Chemical Mater, in 2005,17, James E.Hanson is with 3, and the 4-thiophenol dichlorobenzene is a raw material, and salt of wormwood is catalyzer, at N-N-methyl-2-2-pyrrolidone N-or N, " single stage method " synthesis of super branched polyphenylene sulfide in the dinethylformamide solvent;
The technology of above-mentioned bibliographical information exists one to use raw material 3, the defective that the 4-thiophenol dichlorobenzene is very expensive, so production cost is too high, is unfavorable for large-scale promotion.
Journal ofPolymer Science:Part B, in 2006,44, Liu and Wen are with 2, and the 4-thiophenol is a raw material, and potassium hydroxide is catalyzer, " accurate single stage method " synthesis of super branched polyphenylene sulfide in HMPA.
The technology of above-mentioned bibliographical information exists a significant defective to be, synthesis step is various, the reaction solvent costliness, and productive rate low (productive rate is less than 45%), so it is more to produce refuse (waste liquid) in the reaction process, the production cost height.
Summary of the invention
The purpose of this invention is to provide a kind of hyperbranched polyphenylene sulfide and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
The said hyperbranched polyphenylene sulfide of the present invention is by the branch chain unit, and straight chain unit and end group unit three parts are formed has pulsating as the formula (1) polymkeric substance, and its structural formula is as follows respectively:
Branch end group unit, chain unit straight chain unit
Molecular weight is 3,000～60,000.
Hyperbranched polyphenylene sulfide of the present invention can adopt infrared spectra and nucleus magnetic resonance to identify that molecular weight is measured with GPC.
The preparation method of said hyperbranched polyphenylene sulfide comprises the steps:
Under nitrogen protection, will contain two chlorine end group thiophenol monomers and alkali metal salt catalyst, under 100-200 ℃ of temperature, reaction is 2-40 hour in aprotic solvent, collects subject polymer then from reaction product;
The said mol ratio that contains two chlorine end group thiophenol monomers and alkali metal salt catalyst is:
Contain two chlorine end group thiophenol monomers: alkali metal salt catalyst=1: 0.01～100;
The said monomer that contains two chlorine end group thiophenols is selected from 2,3-thiophenol dichlorobenzene, alkyl replace 2,3-thiophenol dichlorobenzene, 2,4 dichloro benzene thiophenol, alkyl replace 2,4 dichloro benzene thiophenol, 2,5-thiophenol dichlorobenzene, alkyl replace 2,5-thiophenol dichlorobenzene, 2,6-thiophenol dichlorobenzene, alkyl replace 2,6-thiophenol dichlorobenzene, 3,5-thiophenol dichlorobenzene or alkyl replace 3, the 5-thiophenol dichlorobenzene;
The carbonatoms of said alkyl is C
1-C
10
Said alkali metal salt catalyst is selected from more than one in potassium hydroxide, salt of wormwood, potassiumphosphate, Potassium ethanoate, sodium hydroxide, yellow soda ash, sodium phosphate, sodium-acetate or the lithium chloride;
Said aprotic solvent is selected from N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-, chloroform or tetrahydrofuran (THF);
Hyperbranched polyphenylene sulfide of the present invention is that with the difference of prior art maximum heat decomposition temperature is higher, and than delivering high nearly 50 ℃ of document numerical value, therefore, hyperbranched polyphenylene sulfide of the present invention can be used under the hot environment.
Preparation method of the present invention is to adopt cheap raw material and solvent with the difference of prior art maximum, adopts the single stage method synthetic route, and therefore, production cost is low, and synthesis device is simple, and refuse, waste liquid generation are few, help scale operation.
Hyperbranched polyphenylene sulfide of the present invention, have good heat endurance and acid-alkali-corrosive-resisting, dissolve in organic solvents such as tetrahydrofuran (THF), chloroform, pyridine, suitable efficient coating, tensio-active agent, linking agent, the rheology modifiers done, functional materials precursors etc., application prospect is very extensive.
Description of drawings
Fig. 1 is the infrared spectra of embodiment 1.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Under nitrogen protection, 2,4 dichloro benzene thiophenol 14.4 grams, salt of wormwood 19 grams, potassium hydroxide 8 grams, HMPA 100ml under 150 ℃ of temperature, reacted 8 hours, obtained head product.Head product is poured weight concentration 10% aqueous hydrochloric acid precipitation, filtration, separation, drying into, and the product that obtains is dissolved in tetrahydrofuran (THF), and with the hexanaphthene precipitation, filtration, separation, vacuum-drying obtain buff powder, productive rate 76%, molecular weight W
M=6104.
Infrared spectra is seen Fig. 1; Nuclear magnetic resonance data is as follows:
1HNMR(CD
3Cl)7.47，7.43，7.39，7.37，7.26，7.22ppm；
Utilizing TGA to detect its thermo-cracking temperature is 450 ℃, and the fastest thermo-cracking temperature is 480 ℃.
Embodiment 2
Under nitrogen protection, 2,4 dichloro benzene thiophenol 20 grams, salt of wormwood 27.6 grams, potassium hydroxide 5.6 grams, N-N-methyl-2-2-pyrrolidone N-160ml under 150 ℃ of temperature, reacted 8.5 hours, obtained head product.Head product is poured weight concentration 10% aqueous hydrochloric acid precipitation, filtration, separation, drying into, and the product that obtains is dissolved in tetrahydrofuran (THF), and with the hexanaphthene precipitation, filtration, separation, vacuum-drying obtain buff powder, productive rate 84%, molecular weight W
M=12547.
Embodiment 3
Under nitrogen protection, 2,4 dichloro benzene thiophenol 10 grams, potassium hydroxide 11.2 grams, N-N-methyl-2-2-pyrrolidone N-100ml under 180 ℃ of temperature, reacted 10 hours, obtained head product.Head product is poured weight concentration 10% aqueous hydrochloric acid precipitation, filtration, separation, drying into, and the product that obtains is dissolved in tetrahydrofuran (THF), and with the hexanaphthene precipitation, filtration, separation, vacuum-drying obtain buff powder, productive rate 77%, molecular weight WM=23407.
Claims (6)
1. hyperbranched polyphenylene sulfide is characterized in that, the said hyperbranched polyphenylene sulfide of the present invention is by the branch chain unit, and straight chain unit and end group unit three parts are formed has pulsating as the formula (1) polymkeric substance, and its structural formula is as follows respectively:
Branch end group unit, chain unit straight chain unit
Molecular weight is 3,000～60,000.
2. the method for preparing the described hyperbranched polyphenylene sulfide of claim 1; comprise the steps: under nitrogen protection; to contain two chlorine end group thiophenol monomers and alkali metal salt catalyst; under 100-200 ℃ of temperature; reaction is 2-40 hour in aprotic solvent, collects subject polymer then from reaction product.
3. method according to claim 2 is characterized in that, the said mol ratio that contains two chlorine end group thiophenol monomers and alkali metal salt catalyst is:
Contain two chlorine end group thiophenol monomers: alkali metal salt catalyst=1: 0.01～100.
4. method according to claim 2 is characterized in that, the said monomer that contains two chlorine end group thiophenols is selected from 2,3-thiophenol dichlorobenzene, alkyl replace 2, and 3-thiophenol dichlorobenzene, 2,4 dichloro benzene thiophenol, alkyl replace 2,4-thiophenol dichlorobenzene, 2,5-thiophenol dichlorobenzene, alkyl replace 2,5-thiophenol dichlorobenzene, 2, and 6-thiophenol dichlorobenzene, alkyl replace 2,6-thiophenol dichlorobenzene, 3,5-thiophenol dichlorobenzene or alkyl replace 3, and 5-thiophenol dichlorobenzene, the carbonatoms of said alkyl are C
1-C
10
5. method according to claim 2 is characterized in that said alkali metal salt catalyst is selected from more than one in potassium hydroxide, salt of wormwood, potassiumphosphate, Potassium ethanoate, sodium hydroxide, yellow soda ash, sodium phosphate, sodium-acetate or the lithium chloride.
6. said aprotic solvent is selected from N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-, chloroform or tetrahydrofuran (THF).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923317A (en) * | 2014-05-05 | 2014-07-16 | 重庆海洲化学品有限公司 | Application of sodium acetate as catalyst for preparing polyphenylene sulfide and method for preparing polyphenylene sulfide |
| CN104292831A (en) * | 2014-09-29 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Nano attapulgite/glass fiber-modified polyphenylene sulfide resin and preparation method thereof |
| CN110256686A (en) * | 2019-06-10 | 2019-09-20 | 宜宾天原集团股份有限公司 | A kind of preparation method of hyperbranched polyphenylene sulfide |
| CN114395353A (en) * | 2021-12-31 | 2022-04-26 | 建滔(江阴)复合材料有限公司 | Epoxy resin glue solution with uniformly dispersed filler and copper-clad plate prepared from epoxy resin glue solution |
-
2007
- 2007-10-09 CN CNA200710046844XA patent/CN101153075A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923317A (en) * | 2014-05-05 | 2014-07-16 | 重庆海洲化学品有限公司 | Application of sodium acetate as catalyst for preparing polyphenylene sulfide and method for preparing polyphenylene sulfide |
| CN104292831A (en) * | 2014-09-29 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Nano attapulgite/glass fiber-modified polyphenylene sulfide resin and preparation method thereof |
| CN110256686A (en) * | 2019-06-10 | 2019-09-20 | 宜宾天原集团股份有限公司 | A kind of preparation method of hyperbranched polyphenylene sulfide |
| CN114395353A (en) * | 2021-12-31 | 2022-04-26 | 建滔(江阴)复合材料有限公司 | Epoxy resin glue solution with uniformly dispersed filler and copper-clad plate prepared from epoxy resin glue solution |
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