CN103965452B - A kind of phase-transfer catalysis interface polycondensation preparation of polyarylester and separating and purifying method - Google Patents
A kind of phase-transfer catalysis interface polycondensation preparation of polyarylester and separating and purifying method Download PDFInfo
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Abstract
The invention discloses preparation and the method for purification of the aromatic copolyester (PAR) be shown below.Its technical characteristic is that the PAR resin dichloromethane solution prepared by phase-transfer catalysis interface polycondensation adopts single stage method to realize the segregation of resin, pulverizing, purifying and solvent recuperation.Recycling design can be reused by direct circulation without rectifying.The thermo-oxidative stability of obtained PAR resin improves, and can meet the requirement of melt-processed
Description
Technical field:
The present invention relates to the preparation of aromatic copolyester (copolyarylate, PAR) resin.
Technical background:
Phase-transfer catalysis interface polycondensation be with water and with the immiscible organic solvent of water for medium, two or more polymerization single polymerization monomer is soluble in the aqueous phase and organic phase respectively, under rapid stirring shear action, polycondensation is carried out fast at two-phase interface, after polycondensation completes, resin is generally dissolved in organic phase, through deionized water wash desalination, refining resin adhesive liquid is obtained after the techniques such as filtering and impurity removing matter, different according to the technique of resin of emanating from smart glue, be divided into precipitation method, vapour analyses method and film evaporation method is several.Interface polycondensation is a non-reversible process carried out under heterogeneous, the molecular weight distribution of resin is uneven, particularly a small amount of oligopolymer and unreacted monomer are dissolved in resin adhesive liquid, employing vapour analyses method and thin film evaporation precipitation method is difficult to micromolecular compound to remove, the existence of these small molecular weight impurities, although their content is very micro-, have a strong impact on the thermo-oxidative stability of resin.Resin easily occurs oxidation cross-linked under heating status, makes goods xanthochromia, and mechanical property reduces.And the small molecular weight impurity being dissolved in resin liquid can not only eliminate by solvent precipitation method, and the resin particle of separating out is even, tap density large, thermostability improves, and the melt pelletization being conducive to resin makes high transparency material.
The shortcoming of solvent precipitation method is that the consumption of solvent is large, the mixed solvent obtained need adopt the method for rectifying precipitating agent to be separated with organic solvent (methylene dichloride or ethylene dichloride), general precipitating solvent load is 3 ~ 5 times (v/v) of organic phase solvent, the yield of solvent is large, energy consumption is high, and facility investment is large.
Phase-transfer catalysis interface polycondensation is used for phosgenation large-scale production of polycarbonates (PC), synthesis technique becomes better and approaching perfection day by day, aftertreatment technology still needs constantly perfect, one-step technology resin precipitating and solvent recuperation two step operation combined developed at present, this technique has become the hot subject of development research.Existing part achievement has been successfully applied in industrial production, as General Electric Corporation's technology, and Bayer technology and Mitsubishi's forming technology etc.The PC aftertreatment technology that GE succeeded in developing in 1979 adopts acetone as the precipitating agent of resin liquid.The problems such as its common feature is a simplified PC aftertreatment technology, but still there is mixed solvent and need rectifying, and solvent recirculation Energy in use is high.
Prepare bisphenol A-type polyarylester (PAR) and adopt phase-transfer catalysis interface polycondensation equally.Within 1973, first Japanese You Nijika (U-nitika) company succeeds in developing polyphenyl dioctyl phthalate bisphenol A-type polyarylester, thereafter Bayer A.G succeeds in developing the polyarylester that commodity are called APE, and also there are the production and selling of identical or similar polyarylester in Austrian ISOVOLTA company, GE, Hooke company (Hooker) and smooth King Company (Teijin).Wherein the industrial scale of You Nijika company is maximum, and within 1997, industrial scale just reaches 5000 tons/year, and defines U-series, P-series, X-9 series and the PAR commixed type polyblend kind such as AX-is serial.
PAR is a kind of high transparency amorphous thermoplastic special engineering plastics, its second-order transition temperature (Tg) about 194 DEG C, heat-drawn wire under large load 174 DEG C ~ 175 DEG C, can at 184 DEG C life-time service, the good stability of the dimension of goods, nontoxic, low rate of moisture absorption, high surface hardness, resistance to ultraviolet shielded property are excellent, there is high tensile strength and toughness, be widely used in the fields such as aviation, automobile, electronic apparatus, LED illumination, medicine equipment and energy traffic.
Phase-transfer catalysis interface polycondensation synthesis aromatic copolyester is adopted to have a lot of bibliographical information.By the biphenol monomer of aromatic diacid chloride and different structure, the aromatic copolyester new variety of various different properties are synthesized, but to the separation and purification of the refining resin solution that phase-transfer catalysis interface polycondensation obtains, the recycling of solvent etc. affect the problems such as resin thermo-oxidative stability and manufacturing cost seldom detailed report.
Summary of the invention:
The invention provides a kind of novel method of aromatic copolyester refining and edulcoration, be particularly suitable for phase-transfer catalysis interface polycondensation synthesis aromatic copolyester, through the NaCl that deionized water wash generates except dereaction, the resin isolation of smart resin liquid obtained after crossing the mechanical impurity filtered in resin liquid is purified, is pulverized and solvent recuperation reutilization technology.
The invention provides a kind of phase-transfer catalysis interface polycondensation synthesis the organic solvent dichloromethane of aromatic copolyester (PAR) resin or the recovery of ethylene dichloride re-use, the segregation of resin, pulverizing and purification, the single stage method aftertreatment technology of the recycling use of segregation agent, the tap density of resin and thermo-oxidative stability improve, and adopt scorification processing to can be made into water white transparency PAR pellet and goods.
Technical scheme of the present invention is as follows:
The preparation of polyarylester and a separating and purifying method, it comprises the steps:
Dihydroxyphenyl propane or other biphenol monomer are dissolved in the aqueous solution of NaOH by step 1., volumetric molar concentration is 0.30 ~ 0.70mol/L, the mol ratio of NaOH and biphenol monomer is 2.00 ~ 2.50:1.00, the excessive object of NaOH guarantees that biphenol monomer generates water-soluble sodium salt, in order to stop biphenol monomer in dissolution process oxidation stain, add a small amount of sodium bisulfite as reductive agent, then add tensio-active agent, conventional tensio-active agent is the cationic quaternary ammonium salt such as chlorinating benzyl triethylamine, bromination benzyl triethylamine;
P-phthaloyl chloride (TPC), m-phthaloyl chloride (IPC) are dissolved in halogenated hydrocarbon solvent by step 2., the most frequently used has methylene dichloride (bp:39.8 DEG C), 1,2-ethylene dichloride (bp:83.7 DEG C) or chloroform (bp:61.3 DEG C), be made into the organic phase solution that monomer molar concentration is 0.20 ~ 0.50mol/L, the mol ratio of TPC:IPC is 0.20 ~ 0.80:0.80 ~ 0.20, and aromatic diacid chloride controls in 0.95 ~ 1.03:1.05 ~ 0.95 than the mol ratio of bisphenol A monomer.
The halohydrocarbon solution of TPC, IPC slowly joins in the aqueous phase that step 1 prepares by step 3. under fast stirring, temperature of reaction controls at 0 DEG C ~ 30 DEG C, the aqueous solution of the NaOH of single phenolic molecules amount conditioning agent and equimolar amount is added after adding, stop stirring after reaction 3 ~ 6h, add first acid for adjusting pH to 3-5, static layering, separates organic phase, use deionized water wash desalination, filtering and impurity removing obtains the refining glue of PAR;
The refining glue that step 3 is obtained under agitation slowly joins in the segregation agent of heating by step 4., while add refining glue limit to distill out halogenated hydrocarbon solvent, described segregation agent can be tetrahydrofuran (THF) (THF), the ether solvent such as n-butyl ether or glycol dimethyl ether, or N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc) or N-Methyl pyrrolidone (NMP), segregation agent add-on is 0.50 ~ 2.00 times of halogenated hydrocarbon solvent volume, preferably 0.8 ~ 1.20 times, in segregation agent, substep adds water, water is 1.00 ~ 3.00:1.00 with the volume ratio of segregation agent, preferably 1.00:1.00, the effect adding water is by precipitate particle shape resin dispersion after complete for steaming segregation agent,
After step 5. adds refining glue, continue halogenated hydrocarbon solvent to steam, then controlled by mixing speed, at 60 turns ~ 1200 turns/min, to steam segregation agent, obtained polyarylester then becomes particulate state to separate out.
The preparation of above-mentioned polyarylester and separating and purifying method, other biphenol monomer described in step 1 can be 9,9-bis-(4 '-hydroxy phenyl) fluorenes (bisphenol fluorene), bisphenol S, Bisphenol F, 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxy benaophenonel, 1,1-bis-(4 '-hydroxy phenyl) hexanaphthene etc., or the mixture of they and dihydroxyphenyl propane.
The preparation of above-mentioned polyarylester and separating and purifying method, the amount adding sodium bisulfite described in step 1 is 0.2 ~ 0.5% of dihydroxyphenyl propane quality.
The preparation of above-mentioned polyarylester and separating and purifying method, the amount adding tensio-active agent described in step 1 is the 0.7-1.4% of dihydroxyphenyl propane quality.
The preparation of above-mentioned polyarylester and separating and purifying method, the p-phthaloyl chloride (TPC) described in step 2, m-phthaloyl chloride (IPC) can select 1,6-naphthalene dimethyl chloride or 4, and 4 '-biphenyl dimethyl chloride substitutes.
Technical characterstic of the present invention is:
1) smart PAR glue by single stage method treatment process complete methylene dichloride and segregation solvents tetrahydrofurane (THF) recovery, resin segregation, pulverize and the operation such as refining and edulcoration.
2) methylene dichloride reclaimed does not need rectification process just can be directly used in the organic solvent of polycondensation next time.Simplify technique, be conducive to energy efficient.
3) the segregation agent of Distillation recovery can be recycled, and recovery utilization rate is high, consumes little, is conducive to reducing production cost.
4) PAR resin is after refined by one-step method purifying, molecular weight (η
inh), thermo-oxidative stability improve, melt-processed can be made into transparent pellet and goods.
The segregation agent of indication of the present invention can be the ether compounds such as THF, n-butyl ether, glycol dimethyl ether; The amide solvents such as DMF (DMF), N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP); The lower boiling such as acetone, butanone ketones solvent and hexane, heptane etc. are to the organic solvent of TPC, IPC inertia.The low-boiling point alcohol compounds such as methyl alcohol, ethanol, Virahol can not be used as segregation agent, because form azeotrope during Distillation recovery methylene dichloride to steam, make the alcohols impurity that methylene dichloride contains easily and aromatic diacid chloride reacts, have a strong impact on recycling of methylene dichloride.Because PAR resin is insoluble to ketone compounds, add a large amount of acetone or butanone, PAR resin meeting Precipitation, by filtering resin isolation, methylene dichloride and acetone could will be separated by rectifying by filtrate, and the complicated energy consumption of recovery process is high.
The present invention selects has certain deliquescent ethers and amide solvent to do segregation agent to PAR under normal temperature or heating, and best segregation agent is THF, is secondly DMF.The boiling point of THF is 66 DEG C, 26 DEG C are differed with the boiling point (bp:39.8 DEG C) of methylene dichloride, the method of distillation is adopted to intercept 37 DEG C ~ 41 DEG C cuts, reclaim methylene dichloride, after having reclaimed methylene dichloride, PAR resin is dissolved in THF, continues to stir intensification and steam THF after adding a certain amount of water, along with steaming of THF, PAR resin is slowly separated out with small-particle and is dispersed in water, until distillate temperature reaches about 75 DEG C, makes THF steam completely as far as possible.DMF is adopted to be that segregation agent can reach effect same, its advantage is that the boiling-point difference of DMF and methylene dichloride is large, the methylene dichloride first steamed does not carry DMF secretly, is particularly suitable for the process of the PAR resin adhesive liquid obtained with the solvent that 1,2-ethylene dichloride (bp:83 DEG C ~ 85 DEG C) does polycondensation.
The present invention adopts THF to do segregation agent, and its consumption is 0.50 ~ 2.00 times of polycondensation methylene chloride volume used, and optimum value is 0.8 ~ 1.20 times.A certain amount of water is added in THF, the volume ratio of water and THF is 1.00 ~ 3.00:1.00, optimum value is 1.00:1.00, moisture is criticized and is added, when reclaiming methylene dichloride, add the water of about total amount 1/4, form azeotrope (bp:38.1 DEG C) steam to reclaim methylene dichloride and water, another effect adding water is by precipitate particle shape resin dispersion after complete for steaming THF.
The present invention reclaims methylene dichloride under adopting low rate mixing condition, and the effect of stirring is that the PAR resin of precipitation is not adhered on reactor wall, and that can accelerate methylene dichloride steams speed simultaneously.When Distillation recovery THF, should stirring velocity be accelerated, the PAR resin of separating out be played to the function of pulverizing.
The present invention adopts slurry leaf agitator, and paddle can be the shape such as blade type or spination, and paddle is two ~ tetra-, distribution can be one deck or two layers or multilayer, stirring arm speed of rotation adopt stepless speed regulation.The granular size that control PAR resin is separated out, in the recovery THF stage, general rotating speed controls at 60 turns ~ 1200 turns/min.
Embodiment
Following examples further illustrate of the present invention, instead of place restrictions on scope of the present invention.The condition determination of the logarithmic specific concentration viscosity of aromatic copolyester (PAR): accurately take dry PAR resin 0.25g and put into 50ml volumetric flask.Add after about 30ml tetrachloroethane makes resin dissolve completely and add solvent to scale, put into 25 DEG C of Water Tanks with Temp.-controlled after shaking up and balance about 30min, with determination of ubbelohde viscometer, by η
inh=c
-1㏑ (t
1/ t
0) calculate, in formula, c is PAR resin concentration (g/dL), t
0, t
1be respectively the time (unit: second) that solvent and PAR resin solution flow through Ubbelohde viscometer kapillary.Thermo-oxidative stability measures: PAR resin is placed on the stainless steel disk with thermometer, is heated to resin melting, at 300 ± 10 DEG C, keep 5min, observes the variable color situation of resin, measures the η before and after resin melting
inh, use Δ η
inhrepresent resin thermo-oxidative stability.
Embodiment TPC, IPC used, dihydroxyphenyl propane, bisphenol fluorene, methylene dichloride, ethylene dichloride, THF, DMAc etc. are industrial goods, without being further purified process directly application.
Embodiment 1
The typical production of PAR resin purification liquid is as follows:
In the 3000mL there-necked flask of cleaning that electric mixer is housed, add deionized water 500mL, sodium bisulfite 0.3g, sodium hydroxide 26.4g (0.66mol).Dihydroxyphenyl propane 68.4g (0.30mol), stirs and makes dihydroxyphenyl propane dissolve the water-soluble sodium salt of generation completely, add 0.50 ~ 1.0g chlorinating benzyl triethylamine, stir and be cooled to less than 10 DEG C.
18.64g (0.0918mol) TPC, 43.48g (0.2142mol) IPC is dissolved in 1000mL ethylene dichloride and is made into organic phase, under fast stirring organic phase is slowly joined the aqueous phase of above-mentioned preparation, about 30min adds.Then 50mL is added containing 1.18g (0.0126mol) phenol and 0.53g (0.013mol) the NaOH aqueous solution, continue stirring reaction about 4h, with NaOH excessive in formic acid neutralization reaction liquid, and make pH value to 3 ~ 5 of reaction mixture, static layering, resin liquid is transferred in 2000mL separating funnel, by deionized water wash resin liquid 5 ~ 6 times, filters obtained smart resin liquid.Sampling records the η of resin
inh=0.68dL/g.
The purifying of the precipitation of PAR resin, solvent recuperation, pulverizing and resin
THF800mL, 100mL deionized water is added in the 3000mL there-necked flask with spination agitator and water distilling apparatus, about heating in water bath to 50 DEG C, above-mentioned resin liquid drop is added in THF/ water mixed solvent, collect 37 ~ 41 DEG C of cuts, reclaim methylene dichloride (bp:39.8 DEG C, with the azeotrope 38.1 DEG C of water, 101.3KPa, containing methylene dichloride 98.5%).Water-bath continues heat temperature raising, Distillation recovery 41 ~ 75 DEG C of cuts, reclaims THF (bp:66 DEG C).Along with constantly steaming of THF, the viscosity of resin liquid increases, and steaming limit, limit adds remaining 700mL deionized water, accelerates stirring velocity, and resin is slowly separated out in small-particle, when distillation temperature is more than 75 DEG C, stops heating, cooling, suction filtration.Resin deionized water wash 2 ~ 3 times, dry 6 ~ 8h at 80 DEG C, in 120 ~ 140 DEG C of vacuum drying ovens, dry 8 ~ 12h, obtains white fine particulate PAR resin 104.7g (theoretical yield 108.6g), η
inh=0.73dL/g, at 300 ± 10 DEG C, melting is water white transparency shape, Δ η
inh=0.01dL/g.
The method that empirically example 1 is same, change the consumption of THF, experimental result lists in table:
The consumption of table 1.THF is on the impact of PAR thermo-oxidative stability
* η
inh1, η
inh2 for PAR refine before and refining after numerical value; η
inh3 is the numerical value of PAR after 300 DEG C ± 10 DEG C melting heating 5min.
Embodiment 2
By the methylene dichloride (37 DEG C ~ 41 DEG C cuts) reclaimed, prepare PAR resin by the operation steps that embodiment 1 is same, experimental result lists in table 2.
Table 2 reclaims methylene dichloride to PAR resin η
inhimpact
* methylene dichloride, THF are the experimental data that industrial goods use first; 2 ~ 6 for reclaiming the data of methylene dichloride and THF.Embodiment 3
Use 1,2-ethylene dichloride instead as organic phase solvent, DMF as segregation agent, according to the method for embodiment 1, the η of PAR resin
inh1 is obtain white granular resin, η after the agent of 0.67dL/g, DMF segregation steams
inh2=0.71dL/g, at 300 DEG C ± 10 DEG C after heating and melting 5min, resin is water white transparency shape, η
inh3 is 0.68dL/g, △ η
inh=-0.03dL/g, resin yield 94.4%.
Embodiment 4
Dihydroxyphenyl propane: bisphenol fluorene mol ratio is 0.95:0.05, TPC:IPC is 0.30:0.70, (TPC+IPC): dihydroxyphenyl propane: bisphenol fluorene=1.02:0.95:0.05.Quarternary copolymerized aromatic ester is obtained according to the experimentation that embodiment 1 is same.The η of resin
inh1 is obtain white granular resin after the agent of 0.84dL/g, THF segregation steams, η
inh2=0.86dL/g, at 300 DEG C ± 10 DEG C after heating and melting 5min, resin is water white transparency shape, η
inh3=0.84dL/g, △ η
inh=-0.02dL/g, resin yield 97.2%.Embodiment 5
The charging capacity of monomeric bisphenol A, TPC, IPC is expanded, i.e. dihydroxyphenyl propane 6.84Kg (30mol), TPC3.106Kg (15mol), TPC3.106Kg (15mol), dihydroxyphenyl propane: (TPC+IPC)=1.00:1.02 (mol/mol), prepare PAR resin 10.57Kg according to the method for embodiment 1, yield is 97.3%, η
inh0.74dL/g, with two spiral shell forcing machine granulation, make master body after obtained transparent pellet, by its heat-drawn wire of state's mapping and mechanical property, test result lists in table 3.
The thermal characteristics of table 3PAR resin and mechanical property
| Test event | Touchstone | Detect data |
| Tensile strength, MPa | GB/T1040,2-2006 | 75.4 |
| Tensile modulus, MPa | GB/T1042,2-2006 | 2.49×10 3 |
| Elongation at break, % | GB/T1042,2-2006 | 24 |
| Flexural strength, MPa | GB/T9341-2008 | 105 |
| Modulus in flexure, MPa | GB/T9341-2008 | 2.32×10 3 |
| Izod notched impact strength, KJ/m 2 | GB/T1843-2008 | 32 |
| Socle girder unnotched impact strength, KJ/m 2 | GB/T1843-2008 | Do not break |
| Heat-drawn wire (Tff0.45), DEG C | GB/T1634-2004 | 180 |
Claims (7)
1. the preparation of polyarylester and a separating and purifying method, is characterized in that it comprises the steps:
Dihydroxyphenyl propane or other biphenol monomer are dissolved in the aqueous solution of NaOH by step 1., and volumetric molar concentration is 0.30 ~
The mol ratio of 0.70mol/L, NaOH and biphenol monomer is 2.00 ~ 2.50:1.00, adds sodium bisulfite as reductive agent, then adds tensio-active agent, and tensio-active agent is chlorinating benzyl triethylamine, bromination benzyl triethylamine cationic quaternary ammonium salt;
P-phthaloyl chloride (TPC), m-phthaloyl chloride (IPC) are dissolved in halogenated hydrocarbon solvent by step 2., halogenated hydrocarbon solvent is methylene dichloride, 1,2-ethylene dichloride or chloroform, be made into the organic phase solution that monomer molar concentration is 0.20 ~ 0.50mol/L, the mol ratio of TPC:IPC is 0.20 ~ 0.80:0.80 ~ 0.20, and aromatic diacid chloride controls in 0.95 ~ 1.03:1.05 ~ 0.95 than the mol ratio of bisphenol A monomer;
The halohydrocarbon solution of TPC and IPC slowly joins in the aqueous phase that step 1 prepares by step 3. under fast stirring, temperature of reaction controls at 0 DEG C ~ 30 DEG C, the aqueous solution of single phenolic molecules amount conditioning agent and the NaOH with single phenolic molecules amount conditioning agent equimolar amount is added after adding, stop stirring after reaction 3 ~ 6h, add first acid for adjusting pH to 3-5, static layering, separates organic phase, use deionized water wash desalination, filtering and impurity removing obtains the refining glue of PAR;
The refining glue that step 3 is obtained under agitation slowly joins in the segregation agent of heating by step 4., while add refining glue limit to distill out halogenated hydrocarbon solvent, described segregation agent is tetrahydrofuran (THF), n-butyl ether or glycol dimethyl ether ether solvent, or N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone, segregation agent add-on is 0.50 ~ 2.00 times of halogenated hydrocarbon solvent volume, in segregation agent, substep adds water, and water is 1.00 ~ 3.00:1.00 with the volume ratio of segregation agent;
After step 5. adds refining glue, continue halogenated hydrocarbon solvent to steam, then controlled by mixing speed, at 60 turns ~ 1200 turns/min, to steam segregation agent, obtained polyarylester then becomes particulate state to separate out.
2. the preparation of polyarylester according to claim 1 and separating and purifying method, is characterized in that: the amount that the segregation agent described in step 4 adds is halogenated hydrocarbon solvent volume 0.8 ~ 1.20 times.
3. the preparation of polyarylester according to claim 1 and separating and purifying method, is characterized in that: the water described in step 4 is 1.00:1.00 with the volume ratio of segregation agent.
4. the preparation of polyarylester according to claim 1 and separating and purifying method, it is characterized in that: other biphenol monomer described in step 1 is 9,9-bis-(4 '-hydroxy phenyl) fluorenes, bisphenol S, Bisphenol F, 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxy benaophenonel or 1,1-bis-(4 '-hydroxy phenyl) hexanaphthene, or the mixture of they and dihydroxyphenyl propane.
5. the preparation of polyarylester according to claim 1 and separating and purifying method, is characterized in that: the amount adding sodium bisulfite described in step 1 is 0.2 ~ 0.5% of dihydroxyphenyl propane quality.
6. the preparation of polyarylester according to claim 1 and separating and purifying method, is characterized in that: the amount adding tensio-active agent described in step 1 is the 0.7-1.4% of dihydroxyphenyl propane quality.
7. the preparation of polyarylester according to claim 1 and separating and purifying method, is characterized in that: described p-phthaloyl chloride (TPC), m-phthaloyl chloride (IPC) 1,6-naphthalene dimethyl chloride or 4, and 4 '-biphenyl dimethyl chloride substitutes.
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| C06 | Publication | ||
| PB01 | Publication | ||
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