CN114349953B - Environment-friendly ether-containing elastomer and preparation method thereof - Google Patents
Environment-friendly ether-containing elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ether-containing polymer and a preparation method thereof, belonging to the field of high gradeThe field of molecular synthesis. The invention provides an environment-friendly ether-containing elastomer, and the structural formula of the environment-friendly ether-containing elastomer is shown as formula I. The invention prepares the environment-friendly ether-containing elastomer with a new structure; the microchannel reactor is introduced, so that the reaction efficiency is higher, the time is saved, and the heat release and the mass transfer of materials in the reaction process can be better controlled; and can produce a polymer having a narrow molecular weight distribution; meanwhile, the proportion of the reaction and the molecular weight and molecular weight distribution of the ether-containing elastomer can be controlled by controlling the feeding amount and feeding speed of the ether-containing reaction solution and the dihalogenated monomer solution and the number of reaction modules of the microchannel reactor.
Description
Technical Field
The invention relates to an ether-containing polymer and a preparation method thereof, belonging to the field of high polymer synthesis.
Background
The elastomer is widely applied to aerospace oil-resistant sealing parts, electronic packages, surface coatings, sports equipment such as sports shoes, sports equipment, infrastructure such as plastic tracks and the like due to the excellent elasticity, deformation and mechanical properties; the traditional elastomer mainly comprises Polyurethane (PU) and polyester copolymer (TPE, TPA, etc.), which have better mechanical property, elastic deformation quantity, etc., but the molecular chain of the elastomer contains ester bonds, so that the elastomer has poor tolerance in a strong corrosive environment, and the elastomer has low heat resistance, generally has a long-term use temperature of less than 130 ℃, is prepared by polycondensation of diisocyanate and polyol or electrophilic copolymerization of a polyester/polyamide chain segment and a flexible long carbon chain, and has limited adjustable space of the molecular structure.
Disclosure of Invention
The invention aims at providing an environment-friendly ether-containing elastomer aiming at the defects of the prior art, and is characterized in that sulfur-containing or oxygen-containing monomers, dihalogenated long-chain ether-containing monomers, alkali, catalysts, end group control agents, solvent leaching agents, catalyst leaching agents and the like are adopted as raw materials, and solution polycondensation reaction is carried out through a microchannel reactor under the action of the catalysts, so that the high-performance environment-friendly ether-containing elastomer with a novel structure is prepared.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide an environment-friendly ether-containing elastomer, wherein the structural formula of the environment-friendly ether-containing elastomer is shown as formula I:
wherein r=o or S;
Further, the Vicat softening point of the environment-friendly ether-containing elastomer is 180-250 ℃.
Further, the molecular weight distribution of the environment-friendly ether-containing elastomer is 1.5-1.6.
The second technical problem to be solved by the invention is to provide a preparation method of the environment-friendly ether-containing elastomer, which comprises the following steps:
1) Dehydrating 32-344 parts of sulfur-containing or oxygen-containing monomers, 0.5-50 parts of catalysts, 0.5-200 parts of alkali and 200-2000 parts of solvents under the protection of inert gases at 130-230 ℃ to obtain dehydrated ether-containing reaction solution; dissolving 50-500 parts of dihalogenated monomer, 10-1200 parts of dihalogenated long-chain ether-containing monomer and 190-1950 parts of solvent to obtain monomer solution completely; then blending the ether-containing reaction solution and the monomer solution in a serial micro-channel reactor (first group) at 165-260 ℃ to obtain an ether-containing polymer solution containing active groups;
2) Feeding the ether polymer solution containing active groups obtained in the step 1) into another group of parallel micro-channel reactors (second group), and reacting with the end group control agent solution at 240-280 ℃ to obtain an ether polymer mixed solution containing active groups;
3) Filtering or hermetically flashing the mixed solution of the ether-containing polymer containing active groups obtained in the step 2) at a temperature of between 150 and 200 ℃ to recover part of the solvent in the mixed solution, and conveying the recovered solvent to a solvent recovery tank; then 100-500 parts of solvent leaching agent and 200-40000 parts of catalyst leaching agent are respectively added to leach the residual solvent and the catalyst; the product obtained after the purification treatment is the environment-friendly ether-containing elastomer.
Further, in step 1), the sulfur-containing or oxygen-containing monomer is:
at least one of them.
Further, in step 1), the dihalogenated long-chain ether-containing monomer is: X-Ar 1 X, x=f, cl or Br,
the dihalogenated monomer is X-Ar 2 X, wherein x=f, cl or Br,
Further, in step 2), the end group control agent is:
In step 1), the ether-containing reaction solution and the monomer solution are subjected to a serial microchannel reaction at 165-260 ℃ for 5-1800 s to obtain an ether-containing polymer solution.
In step 1), the ether-containing reaction solution and the monomer solution are fed into a series-type microchannel reactor through a high-pressure metering pump, and the feeding speed is 15-1500 g/min.
Further, in the step 1), the number of reaction modules of the serial microchannel reactor is 1 to 100 groups (preferably 10 to 60 groups), and the diameter of the microchannel is 1 to 10000 micrometers (preferably 5 to 500 micrometers).
In step 1), the dehydration reaction time is 0.5 to 4 hours.
In step 2), the number of reaction modules of the parallel microchannel reactor is 1-20 groups, and the diameter of the microchannel is 1-20000 micrometers (preferably 100-600 micrometers).
Further, in the step 2), the end-group controlling agent solution refers to a solution prepared from 0.01 to 10 parts of the end-group controlling agent and 5 to 50ml of a solvent.
Further, in the step 3), the solvent leaching agent is added to carry out the residual solvent leaching by the following steps: adding leaching agent, leaching the residual solvent for 2-5 times under the sealed condition at the temperature of 10-150 ℃ and the pressure of 0.5-40 MPa; the leached mixed gas is sent to a gas-liquid separator through a filter screen to separate leaching agent from solvent.
Further, the purity of the solvent after the solvent leaching agent is added to leach the residual solvent is more than or equal to 97.5 percent, and the solvent is directly sent into a solvent recovery tank to be mixed with the solvent recovered by high-temperature filtration or closed flash evaporation, so that the solvent can be directly applied to the preparation of subsequent products without purification or refining; the obtained leaching agent enters a closed circulation system and is recovered by a pump to be sent to a leaching agent recovery storage tank for recycling.
Further, in step 3), the method of catalyst leaching is: the solid crude product obtained after leaching the residual solvent adopts a catalyst leaching agent to recycle and separate the catalyst; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recovered and used as a catalyst leaching agent of the next batch, and the solid is the recovered catalyst and can be directly used without post-treatment.
Further, in step 1) to step 3), the solvent is selected from the group consisting of: formamide, acetamide, N, N ', N' -tetramethyl urea, N, N-dimethylformamide, N, N-dimethylacetamide, isoquinoline, sulfolane, 1-methyl-3-propylimidazole bromide, 1-methyl-3-isopropylimidazole bromide, 1, 3-dipropyiimidazole bromide, dimethyl sulfone, 2, 4-dimethyl sulfolane, diphenyl sulfone, hexamethylphosphoric triamide, dimethylformamide, epsilon-caprolactam, N-methylcaprolactam, N, N-dimethylpropylurea, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-cyclohexylpyrrolidone, or 2-pyrrolidone, or any one of them.
Further, in the step 1), the catalyst is LiCl or CeCl 2 Lithium phosphate, sodium phosphate, potassium phosphate, CH 3 COOLi、CH 3 COONa、(CH 3 COO) 2 Ce、HCOOLi、HCOONa、(HCOO) 2 Ce、LiOOCCOOLi、NaOOCCOONa、LiOOCCH 2 CH 2 COOLi、NaOOCCH 2 CH 2 COONa、LiOOCCH 2 CH 2 CH 2 CH 2 COOLi、NaOOCCH 2 CH 2 CH 2 CH 2 COONa, 15-crown-5, 18-crown-6, zinc formate, zinc acetate, lithium benzoate, sodium benzoate, potassium benzoate, zinc benzoate, lithium ethylenediamine tetraacetate, sodium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, zinc ethylenediamine tetraacetate, lithium alginate, lithium gluconate, lithium heptonate, lithium glycocholate, lithium dioctyl succinate, lithium ethylenediamine tetramethylene phosphate, lithium diethylenetriamine pentamethylene phosphonate, lithium amine trimethophosphate, sodium alginate, sodium gluconate, sodium heptonate, sodium glycocholate, sodium dioctylsuccinate, sodium ethylenediamine tetramethylene phosphate, sodium diethylenetriamine pentamethylene phosphonate, or sodium amine trimethophosphate.
Further, in step 1), the base is any one of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate.
Further, in the step 3), the solvent leaching agent is any one of dichloromethane, chloroform, dichloroethane, acetone, butanone, pentanone, cyclohexanone, dioxane, tetrahydrofuran, diethyl ether, carbon dioxide, sulfur hexafluoride, difluoromethane, trifluoromethane, tetrafluoromethane, tetrafluorodichloromethane, hexafluoroethane, tetrafluoroethane, hexafluoropropane or perfluorocyclobutane.
Further, in the step 3), the catalyst leaching agent is any one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isobutanol, tertiary butanol, n-pentanol, isopentanol, n-hexanol, n-heptanol, n-octanol or isooctanol.
In the invention, the raw materials are all weight parts except special descriptions.
The invention has the beneficial effects that:
1. the invention prepares the environment-friendly ether-containing elastomer with a new structure; the microchannel reactor is introduced, so that the reaction efficiency is higher, the time is saved, and the heat release and the mass transfer of materials in the reaction process can be better controlled; and can produce a polymer having a narrow molecular weight distribution; meanwhile, the proportion of the reaction and the molecular weight and molecular weight distribution of the ether-containing elastomer can be controlled by controlling the feeding amount and feeding speed of the ether-containing reaction solution and the dihalogenated monomer solution and the number of reaction modules of the microchannel reactor.
2. The reaction is carried out in two sections, compared with the traditional technical method, the end group of the product can be controlled more effectively, and the end capping efficiency is higher by using the method of a micro-channel reactor, and the melt processing stability and the ageing resistance of the product are more excellent.
3. In the solvent recovery process, a combined mode of flash evaporation (or hot filtration) and leaching is adopted, so that the solvent recovery rate is greatly improved and can reach 98-99%, the purity is more than or equal to 97.5%, the rectification and purification are not needed, the energy consumption is greatly reduced, the cost is reduced, and the three-waste discharge amount is also greatly reduced.
4. The catalyst is recovered in a step-by-step and sectional mode, and finally is recovered and separated along with the catalyst leaching agent in a multi-effect evaporation mode, so that the catalyst is low in energy consumption and high in purity.
5. Compared with the traditional elastomer, the ether-containing elastomer has higher service temperature, corrosion resistance, mechanical property and flame retardant property, and can adapt to more severe service environment.
Description of the drawings:
FIG. 1 is a graph showing the results of infrared tests on the ether-containing elastomer obtained in example 1 of the present invention.
FIG. 2 is a graph showing the results of infrared tests on the ether-containing elastomer obtained in example 2 of the present invention.
FIG. 3 is a graph showing the results of infrared tests on the ether-containing elastomer obtained in example 3 of the present invention.
Detailed Description
The invention adopts a brand-new nucleophilic substitution route, adopts diphenol or sulfur-containing compound monomer and dihalogenated monomer containing long carbon chain to carry out copolycondensation, prepares the polyamide type thermoplastic elastomer with novel structure and different chain segment primitives, has wide adjustable range of molecular chain structure (can utilize diphenol or sulfur-containing monomer and dihalogenated monomer with various structures to carry out copolymerization), and can greatly improve the use temperature; because the whole molecular chain segment has no ester group structure, the corrosion resistance of the polymer is greatly improved, and meanwhile, the mechanical property of the polymer is greatly improved due to the high-density amide structure.
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations thereof will be to those skilled in the art in light of the foregoing disclosure.
Example 1 (hydroquinone-C12-80% -2000-20%)
(1) 36g of CH 3 Adding COONa,138g of sodium carbonate, 2000g of solvent isoquinoline and 110g of hydroquinone into a pre-reaction kettle, dehydrating and reacting for 1.5h at 220 ℃ under the protection of nitrogen to obtain a dehydrated pre-reaction solution, and keeping the temperature constant; 356g of bis (4-fluorobenzoyl) -1, 12-dodecadiamine, 449g of bis (4-fluorobenzoyl) -isopropyl ether diamine with a polymerization degree of 33 and 1000g of solvent isoquinoline are added into a pre-mixer, after dihalogenated monomers are dissolved, a high-pressure metering pump is adopted to respectively send the pre-reaction solution and the monomer solution in the pre-mixer into a serial micro-channel reactor (the number of modules is 30), the feeding mole ratio of the pre-reaction solution to the monomer solution in the pre-mixer is controlled to be 1:1.001 (oxygen-containing monomer: dihalogenated monomer), the feeding speed is 150g/min, the polymerization is carried out for about 1400s, and the temperature is 220 ℃, so that the ether-containing elastomer polymer solution with certain molecular weight and molecular weight distribution is obtained;
(2) Then the obtained polymer solution containing the ether elastomer is sent to another group of parallel micro-channel reactors (the number of modules is 6), 0.5g of end group control agent phenol dissolved in 50ml of solvent isoquinoline is reacted with the obtained polymer solution containing the ether elastomer through a high-pressure metering pump, and the temperature is 225 ℃, so as to prepare a crude product mixed solution after the end capping of the polymer containing the ether elastomer;
(3) Flash evaporating the reaction product mixed solution at 200 ℃ to recover part of the solvent in the reaction product mixed solution, adding the solid material into a high-pressure leaching kettle, adding 2000g of acetone, and leaching the residual solvent for 5 times under the sealed condition at 100 ℃ and 1 MPa; the leached mixed gas fluid is sent to a 2-level gas-liquid separator through a filter screen to separate leaching agent and solvent, the solvent is automatically liquefied to obtain high-purity solvent with purity of 98.3 percent after passing through the 2-level gas-liquid separator, and the high-purity solvent is directly sent to a solvent recovery tank to be mixed with the recovered solvent in the step (1), so that the solvent can be directly applied to preparing subsequent products without purification or refining; acetone enters a closed-loop circulation system after passing through a 2-stage gas-liquid separator, is recovered by a pump and is sent to a leaching agent recovery storage tank for recycling;
(4) The solid crude product obtained after the treatment in the step (3) is subjected to catalyst recovery and separation by adopting 2000g of catalyst leaching agent methanol; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recovered to be used as a catalyst leaching agent of the next batch, and the solid is the recovered catalyst which can be directly used without post-treatment; carrying out countercurrent water washing and solid-liquid separation on the leached solid resin crude product for 5 times by adopting desalted water or washing water of the previous batch of products, and drying the separated water-containing ether-containing elastomer to obtain the environment-friendly ether-containing elastomer; the yield is 99.1 percent, and the intrinsic viscosity [ eta ] is]The weight average molecular weight is 88050, the molecular weight distribution is 1.60 (DMF is taken as solvent, the mobile phase is also DMF, the concentration of the prepared resin is 2mg/ml, the sample injection speed is 0.200 ml/min), the solvent recovery rate is 98.9%, the catalyst recovery rate is 97.4%, the infrared characterization is shown in figure 1, the Vicat softening point is shown in detail (standard impact spline is placed in silicone oil with a set temperature, under the conditions of a certain load and 2 ℃/min heating, the sample is 1mm 2 Temperature at which needle is pressed 1 mm) and machineryThe properties are shown in Table 1: the Vicat softening point is 203.8 ℃, the tensile strength is 26MPa, and the elongation at break is 1120%; corrosion resistance experiments are shown in table 2: the corrosion resistance of the polyurethane is improved greatly compared with the corrosion resistance of traditional thermoplastic elastomers PU, TPE and the like.
Example 2 (hydroquinone-C6-75% -2000-25%)
(1) 30g of zinc benzoate, 140g of potassium carbonate, 1500g of solvent N-methylpyrrolidone and 110g of hydroquinone are added into a pre-reaction kettle, dehydration reaction is carried out for 1.5h at the temperature of 200 ℃ under the protection of nitrogen, and a dehydrated pre-reaction solution is obtained and is kept at a constant temperature; 270g of bis (4-fluorobenzoyl) -1, 6-hexamethylenediamine, 562g of isopropyl ether diamine with the polymerization degree of 33 of bis (4-fluorobenzoyl) and 1000g of solvent N-methylpyrrolidone are added into a pre-mixer, after dihalogenated monomers are dissolved, a high-pressure metering pump is respectively adopted to send the pre-reaction solution and the monomer solution in the pre-mixer into a serial micro-channel reactor (the number of modules is 60), the feeding mole ratio of the pre-reaction solution to the monomer solution in the pre-mixer is controlled to be 1:1.001 (oxygen-containing monomer: dihalogenated monomer), the feeding speed is 150g/min, the polymerization is carried out for about 1600s, and the temperature is 200 ℃, so that the ether-containing elastomer polymer solution with certain molecular weight and molecular weight distribution is obtained;
(2) Then the obtained polymer solution containing the ether elastomer is sent to another group of parallel micro-channel reactors (the number of modules is 7), and 2g of end group control agent diphenol dissolved in 30ml of solvent N-methyl pyrrolidone is reacted with the obtained polymer solution containing the ether elastomer by a high-pressure metering pump, the temperature is 200 ℃, and the crude product mixed solution containing the ether elastomer polymer after end capping is prepared;
(3) Flash evaporating the reaction product mixed solution at 200 ℃ to recover part of the solvent in the reaction product mixed solution, adding the solid material into a high-pressure leaching kettle, adding 2000g of tetrahydrofuran, and leaching the residual solvent for 5 times under the sealed condition at 140 ℃ and 1.2 MPa; the leached mixed gas fluid is sent to a 2-level gas-liquid separator through a filter screen to separate leaching agent and solvent, the solvent is automatically liquefied to obtain high-purity solvent with purity of 98.6 percent after passing through the 2-level gas-liquid separator, and the high-purity solvent is directly sent to a solvent recovery tank to be mixed with the recovered solvent in the step (1), so that the solvent can be directly applied to preparing subsequent products without purification or refining; tetrahydrofuran enters a closed circulation system after passing through a 2-stage gas-liquid separator, and is recovered and sent to a leaching agent recovery storage tank through a pump for recycling;
(4) The solid crude product obtained after the treatment in the step (3) is subjected to catalyst recovery and separation by adopting 1500g of isooctanol serving as a catalyst leaching agent; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recovered to be used as a catalyst leaching agent of the next batch, and the solid is the recovered catalyst which can be directly used without post-treatment; carrying out countercurrent water washing and solid-liquid separation on the leached solid resin crude product for 4 times by adopting desalted water or washing water of the previous batch of products, and drying the separated water-containing ether-containing elastomer to obtain the environment-friendly ether-containing elastomer; the yield is 99.2%, the intrinsic viscosity [ eta ] =0.75, the weight average molecular weight is 89460, the molecular weight distribution is 1.52, the solvent recovery rate is 99.0%, the catalyst recovery rate is 97.8%, the infrared characterization is shown in figure 2, and the vicat softening point and the mechanical properties are shown in table 1: the Vicat softening point is 184.3 ℃, the tensile strength is 28MPa, and the elongation at break is 910%; corrosion resistance experiments are shown in table 2: the corrosion resistance of the polyurethane is improved greatly compared with the corrosion resistance of traditional thermoplastic elastomers PU, TPE and the like.
Example 3 (paradithiol-C10-80% -400-20%)
(1) Adding 20g of sodium succinate, 2g of potassium hydroxide, 800g of sulfolane serving as a solvent and 142g of p-phenylene dithiol into a pre-reaction kettle, carrying out dehydration reaction for 2.5h at 220 ℃ under the protection of nitrogen, and obtaining a dehydrated pre-reaction solution, and keeping the temperature constant; 332.8g of bis (4-fluorobenzoyl) -1, 10-decanediamine, 129g of bis (4-fluorobenzoyl) -isopropyl ether diamine with polymerization degree of 6 and 1000g of solvent N-sulfolane are added into a pre-mixer, after dihalogenated monomers are dissolved, a high-pressure metering pump is respectively adopted to feed the pre-reaction solution and the monomer solution in the pre-mixer into a serial micro-channel reactor (the number of modules is 50), the feeding mole ratio of the pre-reaction solution to the monomer solution in the pre-mixer is controlled to be 1:1.001 (sulfur-containing monomers: dihalogenated monomers), the feeding speed is 80g/min, the polymerization is carried out for about 1500s, and the temperature is 230 ℃, so that the ether-containing elastomer polymer solution with certain molecular weight and molecular weight distribution is obtained;
(2) Then the obtained polymer solution containing the ether elastomer is sent to another group of parallel micro-channel reactors (the number of modules is 7), and 1g of thiophenol which is a terminal control agent and is dissolved in 30ml of solvent sulfolane is reacted with the obtained polymer solution containing the ether elastomer by a high-pressure metering pump, the temperature is 240 ℃, and the crude product mixed solution containing the ether elastomer after end capping is prepared;
(3) Filtering the mixed solution of the reaction products at the temperature of 200 ℃ to recover part of the solvent in the mixed solution of the reaction products, adding solid materials into a high-pressure leaching kettle, adding 2000g of butanone, and leaching the residual solvent for 5 times under the sealed condition at the temperature of 140 ℃ and the pressure of 1.2 MPa; the leached mixed gas fluid is sent to a 2-level gas-liquid separator through a filter screen to separate leaching agent and solvent, the solvent is automatically liquefied to obtain high-purity solvent with purity of 98.6 percent after passing through the 2-level gas-liquid separator, and the high-purity solvent is directly sent to a solvent recovery tank to be mixed with the recovered solvent in the step (1), so that the solvent can be directly applied to preparing subsequent products without purification or refining; butanone enters a closed-loop circulation system after passing through a 2-stage gas-liquid separator, is recovered by a pump and is sent to a leaching agent recovery storage tank for recycling;
(4) The solid crude product obtained after the treatment in the step (3) is subjected to catalyst recovery and separation by adopting 1800g of ethanol serving as a catalyst leaching agent; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recovered to be used as a catalyst leaching agent of the next batch, and the solid is the recovered catalyst which can be directly used without post-treatment; carrying out countercurrent water washing and solid-liquid separation on the leached solid resin crude product for 5 times by adopting desalted water or washing water of the previous batch of products, and drying the separated water-containing ether-containing elastomer to obtain the environment-friendly ether-containing elastomer; the yield is 99.0%, the intrinsic viscosity [ eta ] =0.82, the weight average molecular weight is 82011, the molecular weight distribution is 1.50, the solvent recovery rate is 98.7%, the catalyst recovery rate is 97.9%, the infrared characterization is shown in figure 3, and the Vicat softening point and the mechanical properties are shown in table 1: the Vicat softening point is 242.3 ℃, the tensile strength is 56MPa, and the elongation at break is 710%; corrosion resistance experiments are shown in table 2: the corrosion resistance of the polyurethane is improved greatly compared with the corrosion resistance of traditional thermoplastic elastomers PU, TPE and the like.
TABLE 1 Vicat softening Point and mechanical Properties of the Environment-friendly Ether-containing elastomer obtained in examples 1-3
| Sample of | Vicat softening point (DEG C) | Tensile Strength (MPa) | Elongation at break (%) |
| Example 1 | 203.8 | 26 | 1120 |
| Example 2 | 184.3 | 28 | 910 |
| Example 3 | 242.3 | 56 | 710 |
TABLE 2 Corrosion resistance experiments on Environment-friendly Ether-containing Elastomers obtained in examples 1-3
+ -: the swelling is carried out, ++, of: room temperature dissolution, -: insoluble in water
Comparative example 1
The same procedure as in the first four steps of example 1 was used, except that: the materials adopted in comparative example 1 are various raw materials for preparing polyarylate, other process parameters are similar to those of example 1, and the weight average molecular weight of the obtained product is 35000-41000, and the molecular weight distribution is 8.9-11.6; when the traditional kettle type reactor is adopted, the weight average molecular weight of the obtained polyarylate product is 39000-51000, and the molecular weight distribution is 2-3.5; it follows that not all polymers produced by the microchannel reactor have a narrow molecular weight distribution.
Claims (19)
1. The preparation method of the environment-friendly ether-containing elastomer is characterized by comprising the following steps of:
1) Dehydrating 32-344 parts of sulfur-containing or oxygen-containing monomers, 0.5-50 parts of catalysts, 0.5-200 parts of alkali and 200-2000 parts of solvents under the protection of inert gases at 130-230 ℃ to obtain dehydrated ether-containing reaction solution; dissolving 50-500 parts of dihalogenated monomer, 10-1200 parts of dihalogenated long-chain ether-containing monomer and 190-1950 parts of solvent to obtain monomer solution completely; then blending the ether-containing reaction solution and the monomer solution in a serial micro-channel reactor at 165-260 ℃ to obtain an ether-containing polymer solution containing active groups;
2) The ether polymer solution containing active groups obtained in the step 1) is sent into another group of parallel micro-channel reactors to react with the end group control agent solution at 240-280 ℃ to prepare an ether polymer mixed solution containing active groups;
3) Filtering or hermetically flashing the mixed solution of the ether-containing polymer containing active groups obtained in the step 2) at a temperature of between 150 and 200 ℃ to recover part of the solvent in the mixed solution, and conveying the recovered solvent to a solvent recovery tank; then 100-500 parts of solvent leaching agent and 200-40000 parts of catalyst leaching agent are respectively added to leach the residual solvent and the catalyst; the product obtained after purification treatment is the environment-friendly ether-containing elastomer;
in step 1), the sulfur-containing or oxygen-containing monomer is:
at least one of (a) and (b);
in step 1), the dihalogenated long-chain ether-containing monomer is: X-Ar 1 X, x=f, cl or Br,
the dihalogenated monomer is X-Ar 2 X, wherein x=f, cl or Br,
at least one of them.
2. The method for preparing an environmentally friendly ether-containing elastomer according to claim 1, wherein in the step 2), the end group controlling agent is:
either, x= F, cl or Br.
3. The method for preparing the environment-friendly ether-containing elastomer according to claim 1, wherein in the step 1), the ether-containing reaction solution and the monomer solution are subjected to a serial microchannel reaction and are subjected to a blending reaction for 5-1800 s at 165-260 ℃ to obtain an ether-containing polymer solution.
4. The method for preparing an environment-friendly ether-containing elastomer according to claim 3, wherein in the step 1), the ether-containing reaction solution and the monomer solution are fed into a series-type microchannel reactor through a high-pressure metering pump, and the feeding speed is 15-1500 g/min.
5. The method for preparing an environment-friendly ether-containing elastomer according to claim 1, wherein in the step 1), the number of reaction modules of the serial microchannel reactor is 1-100 groups, and the diameter of the microchannel is 1-10000 microns.
6. The method for preparing the environment-friendly ether-containing elastomer according to claim 5, wherein the number of reaction modules of the serial microchannel reactor is 10-60 groups, and the diameter of the microchannel is 5-500 micrometers.
7. The method for preparing the environment-friendly ether-containing elastomer according to claim 1, wherein in the step 2), the number of reaction modules of the parallel microchannel reactor is 1-20 groups, and the diameter of the microchannel is 1-20000 microns.
8. The method for preparing an environment-friendly ether-containing elastomer according to claim 7, wherein the diameter of the micro-channel is 100-600 microns.
9. The method for preparing an environmentally friendly ether-containing elastomer according to claim 1, wherein in the step 2), the end group controlling agent solution means a solution prepared from 0.01 to 10 parts of the end group controlling agent and 5 to 50ml of a solvent.
10. The method for preparing the environment-friendly ether-containing elastomer according to claim 1, wherein in the step 3), the solvent leaching agent is added to carry out the residual solvent leaching by the following steps: adding leaching agent, leaching the residual solvent for 2-5 times under the sealed condition at the temperature of 10-150 ℃ and the pressure of 0.5-40 MPa; the leached mixed gas is sent to a gas-liquid separator through a filter screen to separate leaching agent from solvent.
11. The method for preparing the environment-friendly ether-containing elastomer according to claim 10, wherein the purity of the solvent after the solvent leaching agent is added to leach the residual solvent is more than or equal to 97.5 percent, and the solvent is directly sent into a solvent recovery tank to be mixed with the solvent recovered by high-temperature filtration or closed flash evaporation, and can be directly applied to preparing subsequent products without purification or refining; the obtained leaching agent enters a closed circulation system and is recovered by a pump to be sent to a leaching agent recovery storage tank for recycling.
12. The method for preparing the environment-friendly ether-containing elastomer according to claim 1, wherein in the step 3), the catalyst leaching method comprises the following steps: the solid crude product obtained after leaching the residual solvent adopts a catalyst leaching agent to recycle and separate the catalyst; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recovered and used as a catalyst leaching agent of the next batch, and the solid is the recovered catalyst and can be directly used without post-treatment.
13. The method for preparing an environment-friendly ether-containing elastomer according to claim 1, wherein in the steps 1) to 3), the solvent is selected from the group consisting of: formamide, acetamide, N, N ', N' -tetramethylurea, N, N-dimethylformamide, N, N-dimethylacetamide, isoquinoline, sulfolane, 1-methyl-3-propylimidazole bromide, 1-methyl-3-isopropylimidazole bromide, 1, 3-dipropyiimidazole bromide, dimethylsulfone, 2, 4-dimethylsulfolane, diphenylsulfone, hexamethylphosphoric triamide, epsilon-caprolactam, N-methylcaprolactam, N, N-dimethylpropylurea, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-cyclohexylpyrrolidone, or 2-pyrrolidone, or any one of them.
14. The method for preparing the environment-friendly ether-containing elastomer according to claim 1, wherein in the step 1), the catalyst is LiCl or CeCl 2 Lithium phosphate, sodium phosphate, potassium phosphate, CH 3 COOLi、CH 3 COONa、(CH 3 COO) 2 Ce、HCOOLi、HCOONa、(HCOO) 2 Ce、LiOOCCOOLi、NaOOCCOONa、LiOOCCH 2 CH 2 COOLi、NaOOCCH 2 CH 2 COONa、LiOOCCH 2 CH 2 CH 2 CH 2 COOLi、NaOOCCH 2 CH 2 CH 2 CH 2 COONa, 15-crown-5, 18-crown-6, zinc formate, zinc acetate, lithium benzoate, sodium benzoate, potassium benzoate, zinc benzoate, lithium ethylenediamine tetraacetate, sodium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, zinc ethylenediamine tetraacetate, lithium alginate, lithium gluconate, lithium heptonate, lithium glycocholate, lithium dioctyl succinate, lithium ethylenediamine tetramethylene phosphate, lithium diethylenetriamine pentamethylene phosphonate, lithium amine trimethophosphate, sodium alginate, sodium gluconate, sodium heptonate, sodium glycocholate, sodium dioctylsuccinate, sodium ethylenediamine tetramethylene phosphate, sodium diethylenetriamine pentamethylene phosphonate, or sodium amine trimethophosphate.
15. The method for producing an environmentally friendly ether-containing elastomer according to claim 1, wherein in the step 1), the alkali is any one of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate or potassium hydrogencarbonate.
16. The method for preparing the environment-friendly ether-containing elastomer according to claim 1, wherein in the step 3), the solvent leaching agent is any one of dichloromethane, chloroform, dichloroethane, acetone, butanone, pentanone, cyclohexanone, dioxane, tetrahydrofuran, diethyl ether, carbon dioxide, sulfur hexafluoride, difluoro dichloromethane, trifluoro methane, tetrafluoromethane, tetrafluorodichloromethane, hexafluoroethane, tetrafluoroethane, hexafluoropropane or perfluorocyclobutane.
17. The method for preparing an environment-friendly ether-containing elastomer according to claim 1, wherein in the step 3), the catalyst leaching agent is any one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isobutanol, tertiary butanol, n-pentanol, isoamyl alcohol, n-hexanol, n-heptanol, n-octanol or isooctanol.
18. The method for preparing an environment-friendly ether-containing elastomer according to claim 1, wherein the obtained environment-friendly ether-containing elastomer has a vicat softening point of 180-250 ℃.
19. The method for preparing an environment-friendly ether-containing elastomer according to claim 1, wherein the molecular weight distribution of the obtained environment-friendly ether-containing elastomer is 1.5-1.6.
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