CN118307743A - Method for preparing solid epoxy resin by continuous dynamic reaction process - Google Patents
Method for preparing solid epoxy resin by continuous dynamic reaction processInfo
- Publication number
- CN118307743A CN118307743A CN202310026799.0A CN202310026799A CN118307743A CN 118307743 A CN118307743 A CN 118307743A CN 202310026799 A CN202310026799 A CN 202310026799A CN 118307743 A CN118307743 A CN 118307743A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- solid epoxy
- reaction process
- bisphenol
- continuous dynamic
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 60
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 239000007787 solid Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 86
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 3
- 229920002635 polyurethane Polymers 0.000 claims abstract description 3
- 230000003068 static effect Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- YGRARUNSCNUDNB-UHFFFAOYSA-N (2-ethylphenyl)-diphenylphosphane Chemical class CCC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YGRARUNSCNUDNB-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 35
- 238000003756 stirring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- WGMBWDBRVAKMOO-UHFFFAOYSA-L disodium;4-[2-(4-oxidophenyl)propan-2-yl]phenolate Chemical compound [Na+].[Na+].C=1C=C([O-])C=CC=1C(C)(C)C1=CC=C([O-])C=C1 WGMBWDBRVAKMOO-UHFFFAOYSA-L 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 description 1
- DVFGEIYOLIFSRX-UHFFFAOYSA-N 3-(2-ethylhexoxy)propan-1-amine Chemical compound CCCCC(CC)COCCCN DVFGEIYOLIFSRX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Abstract
The invention discloses a method for preparing solid epoxy resin by a continuous dynamic reaction process. Mixing main materials containing liquid epoxy resin and bisphenol A or mixing main materials containing liquid epoxy resin, bisphenol A and solid epoxy resin with softening point temperature not exceeding 100 ℃; mixing an adjunct comprising a catalyst and a solvent; and mixing the main materials and the auxiliary materials, and then placing the mixture in a screw reactor for ring-opening polymerization reaction to obtain the modified polyurethane. The solid epoxy resin product prepared by the method has the advantages of strong quality stability, high quality, wide softening point range, strong adaptability, simple preparation method, flexible grasp of single batch yield, high efficiency, low cost, environmental protection and suitability for industrialized popularization.
Description
Technical Field
The invention relates to a preparation method of solid epoxy resin, in particular to a method for preparing solid epoxy resin by a continuous dynamic reaction process, and belongs to the technical field of resin materials.
Technical Field
The bisphenol A solid epoxy resin is a polymer containing two epoxy groups, and can be subjected to ring-opening reaction with various active hydrogen-containing compounds due to the chemical activity of the epoxy groups to form a net-shaped condensate, and has the characteristics of corrosion resistance, strong adhesive force, high strength and the like. The solid epoxy resin is widely applied to the fields of paint, heavy-duty anticorrosion, electrophoretic paint and the like.
The bisphenol A type solid epoxy resin has two main synthesis processes: a one-step process and a two-step process. The one-step process is to form bisphenol A sodium salt with NaOH solution, react bisphenol A sodium salt with epichlorohydrin to produce epoxy resin and side product NaCl, and obtain solid epoxy resin through solvent extraction, washing, water diversion, solvent elimination and other steps. The two-step process is to make the liquid epoxy resin with low molecular weight and bisphenol A react with the catalyst to obtain the solid epoxy resin. The one-step method has high product quality balance and good product leveling property, but has long flow, more working procedures, larger wastewater quantity and poorer shock resistance of the cured product prepared by the product, and can not meet the requirements of powder coating. The two-step method has short process flow, less wastewater in the whole period and good shock resistance of the cured product. But has the following problems: firstly, the single batch yield is basically fixed according to the volume of the reaction kettle, and accurate production according to orders is difficult; secondly, after the reaction is finished, the product is fed into a cooling steel belt from the kettle for sheeting packaging, the product discharge duration is longer, and the reaction still occurs in the kettle, so that the front-back difference of the quality indexes of single products is larger. Third, it is difficult to produce a high softening point epoxy resin having a high degree of polymerization in a tank reactor.
The invention patent CN102666632A describes the preparation of solid epoxy resins by reacting polyphenolic compounds with epichlorohydrin, dichloropropanol, epoxy novolac and their homologs in a single homogeneous system formed by water, organic solvent, catalyst and dispersant. The method reduces reaction interface resistance, promotes reaction, inhibits side reaction, and simultaneously precipitates reaction products from the homogeneous system to obtain the solid epoxy resin. However, the concentration of the reactant in the homogeneous dispersion is low, and the amount of wastewater is large; the solid epoxy resin is directly separated out and dried from a system with higher NaCl concentration, and the content of Cl - ions is high; the addition of the dispersing agent has great influence on the purity of the product and the wastewater treatment.
The invention patent CN104788648B describes a method for preparing high-glass transition temperature and high-toughness modified epoxy resin by adopting liquid epoxy resin, siloxane and isobutyl cyanide, but the softening point is still low, and the softening point of the product obtained in the examples is 115 ℃ at most.
The invention patent CN1133305A describes a preparation method of solid epoxy resin, bisphenol A and epichlorohydrin are reacted in the presence of NaOH, methyl ethyl ketone, toluene, water and isopropanol, after the reaction is completed, the organic phase is separated from the water phase by adding the bisphenol A and the epichlorohydrin into a reactor, then the organic phase is washed successively, and the solvent is removed to obtain the solid epoxy resin. The method has lower Cl-ion content and higher yield, but the solid epoxy resin with higher molecular weight and higher softening point cannot be prepared because the viscosity of the system is rapidly increased after the solid epoxy resin is generated, and the mass and heat transfer of the reaction system are seriously affected.
The invention patent CN104130379A introduces a preparation method of bisphenol A epoxy resin with higher softening point, which comprises the steps of pre-reacting bisphenol A, epichlorohydrin and caustic soda at 58-62 ℃, dropwise adding liquid alkali under vacuum condition, performing ring-opening ring-closing reaction, dissolving, refining, neutralizing and desolventizing to obtain the epoxy resin with the softening point of about 18.5 ℃.
In summary, the existing solid epoxy resin production method has the problems of complicated process, high cost, unstable product, high energy consumption, easy environmental pollution, low production efficiency, difficult production of high softening point products and the like, so that the development of a flexible, stable and high production efficiency solid epoxy resin preparation method is urgently needed.
Disclosure of Invention
Aiming at the defects of complex process, high cost, large pollution, unstable product, low production efficiency and the like in the prior art, the invention aims to provide a preparation method of solid epoxy resin by a continuous dynamic reaction process. The method is simple, low in cost, high in product quality stability, energy-saving, environment-friendly and high in production efficiency, and effectively solves the problems existing in the prior art.
In order to achieve the above technical object, the present invention provides a method for preparing a solid epoxy resin by a continuous dynamic reaction process, which comprises mixing a main material comprising a liquid epoxy resin and bisphenol a, or mixing a main material comprising a liquid epoxy resin, bisphenol a and a solid epoxy resin having a softening point temperature of not more than 100 ℃; mixing an adjunct comprising a catalyst and a solvent; and mixing the main materials and the auxiliary materials, and then placing the mixture in a screw reactor for ring-opening polymerization reaction to obtain the modified polyurethane.
In the preparation process, the reaction materials are added into the screw reactor port, the materials react in a flowing mode in the screw reactor by controlling the conveying speed of the materials, and when the materials flow out of the outlet of the screw reactor, the reaction is stopped, so that the reaction time of the same batch of materials is accurately controlled. The invention controls the material proportion, the mixing mode and the screw reactor, so that the system has the advantages of high mass transfer efficiency, accurate temperature control, strong driving force and the like, and the single batch yield can be flexibly mastered, and the quality of the same batch of products is more stable. In addition, the method can prepare solid epoxy resin with different softening points of low, medium and high, has stronger adaptability and can meet market demands.
As a preferable scheme, the epoxy equivalent weight of the liquid epoxy resin is 184-194 g/eq, the viscosity is 11000-14000 mPa.s, and the hydrolysis chlorine is less than 300ppm.
As a preferred embodiment, the solid epoxy resin having a softening point temperature of not more than 100 ℃ has a software point temperature of 50 to 90 ℃. When the high-softening-point solid epoxy resin is prepared, the solid epoxy resin with a relatively lower softening point is added into the raw materials, so that the preparation efficiency of the high-softening-point solid epoxy resin is improved.
As a preferred embodiment, the catalyst includes at least one of triphenylphosphine, imidazole, and ethyl triphenylphosphine salt. The catalyst can rapidly initiate epoxy groups in raw materials to carry out ring-opening reaction, has few side reactions, does not introduce halogen substances, and prevents environmental pollution.
As a preferred embodiment, the solvent includes at least one of methanol, ethanol, water, toluene, xylene, MIBK, acetone, and solvent oil. The solvent can be used for well dissolving the catalyst, and has good intersolubility with a main material containing liquid epoxy resin, thereby being beneficial to carrying out homogeneous phase reaction.
As a preferable scheme, the mass ratio of the liquid epoxy resin to the bisphenol A is 6.5-7.5:2.5-3.5. Controlling the mass ratio of the liquid epoxy resin to bisphenol A in a proper range is beneficial to obtaining a resin product with excellent performance. When the dosage of the liquid epoxy resin is too large, the epoxy equivalent of the obtained solid epoxy resin is relatively small, and the softening point is relatively low; when the bisphenol A is used in an excessive amount, the epoxy equivalent of the obtained solid epoxy resin is relatively large and the softening point is relatively high.
As a preferable scheme, the mass ratio of the liquid epoxy resin to the bisphenol A to the solid epoxy resin with the softening point temperature not exceeding 100 ℃ is 1-3.7:3.8-7:2-2.5. The three raw materials are controlled in proper ranges, so that the stability of the product is improved, and the fluctuation of the product index is easily caused by the excessive consumption of the liquid epoxy resin.
As a preferable scheme, the main material mixing process is as follows: stirring for 1-3 h at 60-120 ℃ with the stirring speed of 50-300rmp. During the mixing process of the main materials, bisphenol A can be completely dissolved in liquid epoxy resin, so that the whole main materials are in a uniform and stable liquid phase.
As a preferable embodiment, the mass ratio of the catalyst to the solvent is 10 to 65:90 to 35, more preferably 15 to 50:85 to 50. Controlling the ratio of catalyst to solvent in a suitable range is advantageous for improving the reaction efficiency. Too low catalyst consumption can affect the reaction rate and prolong the reaction time; too high a catalyst amount will reduce the solubility to some extent.
As a preferable scheme, the auxiliary material mixing process is as follows: stirring for 1-3 h at 30-70 ℃ with stirring speed of 50-300 rmp. In the process, the catalyst can be dissolved in a solvent to form a catalyst solution, and can be fully mixed with the main material to form a uniform liquid phase so as to improve the ring-opening polymerization reaction efficiency.
As a preferable scheme, in the mixing process of the main material and the auxiliary material, the mass of the catalyst in the auxiliary material is 0.5-5 per mill of the mass of bisphenol A in the main material. The catalyst dosage in the mixed system is controlled in a proper range, which is beneficial to obtaining products with excellent performance. Too low a catalyst amount will cause a relatively decrease in reaction efficiency, and too high a catalyst amount will cause the catalyst to remain in the product.
As a preferred embodiment, the main ingredient and the auxiliary ingredient are mixed in a static mixer. When the mixture enters a static mixer, the temperature of the main materials is controlled to be 60-120 ℃, the temperature of the auxiliary materials is controlled to be 30-70 ℃, and the mixing and stirring speed is controlled to be 50-300 rmp. The adoption of the static mixer can lead the main materials and the auxiliary materials to form a liquid state uniformly mixed material system before the reaction, so that the materials in the reaction process are carried out in a homogeneous system.
As a preferred embodiment, the main material is fed to the static mixer by at least one of a gear pump, a screw pump, and a twin screw pump.
As a preferred scheme, the auxiliary material is conveyed to the static mixer by adopting at least one of a peristaltic pump and a plunger pump.
As a preferable scheme, the conveying rate of the main material is 0.285-1V Volume of material /h, and the conveying rate of the auxiliary material is 0.285-1V Volume of material /h.
As a preferred embodiment, the main and auxiliary materials are fed to the screw reactor after filling the static mixer.
As a preferred embodiment, the ring-opening polymerization conditions are: the temperature is 120-200 ℃ and the time is 1-3.5 h. The feed rate in the screw reactor was 0.285-1V Volume of material /h. The specific feeding rate can be reasonably regulated and controlled according to the reaction time and the viscosity of the reaction materials.
As a preferable scheme, the outer wall of the screw reactor is a jacket or a half pipe for heat exchange, cooling water is introduced for heat dissipation, the temperature of the cooling water is 0-100 ℃, the temperature in the reactor is maintained at 120-200 ℃, the screw rotating speed of the reactor is regulated, and the dynamic continuous reaction residence time of materials in the reactor is maintained for 1-3.5 h.
As a preferred embodiment, after the ring-opening polymerization reaction is completed, the product flows from the outlet of the reactor into a steel belt or a pot for cooling. The cooling medium is air or water with the temperature of 5-50 ℃.
As a preferred scheme, the main materials are mixed in a mixing tank, and the auxiliary materials are mixed in a catalyst tank.
Before product switching, the equipment lines (reactor, pump, material lines) after the static mixer are purged with compressed air or nitrogen and solvent purged. When the shutdown time exceeds three days, after purging and cleaning are completed, liquid epoxy resin is added into the mixing tank, and meanwhile, the liquid epoxy resin is adopted to replace the reactor, the machine pump and the material pipeline, the replaced material is returned to the mixing tank, and the temperature of the mixing tank is maintained at 20-70 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The screw reactor is adopted for polymerization reaction, so that the mass transfer efficiency of a system is improved, the temperature is precisely controlled, the driving force is strong, the problems of low reaction efficiency and the like caused by high viscosity of the system are effectively solved, and compared with the existing epoxy resin preparation method, the same batch of products prepared by the method are more stable in quality, single batch yield can be flexibly mastered, and the operability is strong;
(2) The solid epoxy resin product with a wide softening point range can be obtained, the flexible preparation of solid epoxy resin with different softening points of low, medium and high is realized, the system adaptability is strong, and the method is suitable for industrial production;
(3) The main raw materials are not introduced with halogen-containing substances, so that the environmental pollution is greatly reduced, the process is simple, the cost is low, and the continuous production can be realized;
(4) The preparation of the high soft point solid epoxy resin does not need to increase the reaction temperature, and the obtained product has the advantages of energy conservation, environmental protection, light color and good quality.
Drawings
FIG. 1 is a schematic diagram of a process flow for preparing a solid epoxy resin using a continuous dynamic reaction process according to the present invention.
Detailed Description
The following examples are intended to further illustrate the present invention, but not to limit the scope of the claims.
The screw reactor used in the present invention was purchased from Nanjing Chuanbo extrusion equipment Co.
Example 1
A. At normal temperature, 802kg of bisphenol A liquid epoxy resin CYD-128 is added into a mixing tank, the temperature is raised to 75 ℃, 237kg of bisphenol A is added, the temperature is raised to 120 ℃, and the temperature is maintained for 1 hour.
B. at normal temperature, 0.237kg of catalyst was added to the catalyst tank, 0.55kg of solvent was added, stirring was started, and the temperature was raised to 60 ℃.
C. The resin transfer pump was started at a flow rate of 350kg/h, while the catalyst pump was started at a flow rate of 0.26kg/h. The streams are mixed and then enter a static mixer.
D. After materials are mixed by a static mixer, the materials enter the reactor through a straight pipe short circuit, and a thermometer is arranged on the straight pipe short circuit.
E. After 353kg/h of material flow rate enters the reactor, a heat tracing jacket or a half pipe is introduced into circulating water to remove heat, and the temperature of the material is maintained at 175 ℃. And after the material reaction is finished, the material flows into a steel belt cooling flaking.
Example 1 and conventional kettle reaction products were taken as sample 1 starting with stable discharge, sample 2 ending with discharge, and the following ratios were set forth in table 1:
TABLE 1 comparison of conventional kettle reactions with product indicators from example 1
Example 2
A. 600kg of bisphenol A type liquid epoxy resin CYD-128 is added into a mixing tank at normal temperature, the temperature is raised to 75 ℃, 265kg of bisphenol A is added, the temperature is raised to 120 ℃, and the temperature is maintained for 1 hour.
B. at normal temperature, 0.265kg of catalyst was added to the catalyst tank, 0.55kg of solvent was added, stirring was started, and the temperature was raised to 60 ℃.
C. The resin transfer pump was started at a flow rate of 288kg/h, while the catalyst pump was started at a flow rate of 0.272kg/h. The streams are mixed and then enter a static mixer.
D. After materials are mixed by a static mixer, the materials enter the reactor through a straight pipe short circuit, and a thermometer is arranged on the straight pipe short circuit.
E. After the materials enter the reactor at the flow rate of 300kg/h, a heat tracing jacket or a half pipe is introduced into circulating water to remove heat, and the temperature of the materials is maintained at 175 ℃. And after the material reaction is finished, the material flows into a steel belt cooling flaking.
Example 2 and conventional kettle reaction products were taken to begin stable discharge as sample 1, and to end discharge as sample 2, respectively, as compared to table 2:
TABLE 2 comparison of conventional kettle reaction with product index of example 2
Example 3
A. 600kg of bisphenol A type solid epoxy resin CYD-011 is added into a mixing tank at normal temperature, the temperature is raised to 90 ℃, 100kg of bisphenol A is added, the temperature is raised to 130 ℃, and the temperature is maintained for 1 hour.
B. At normal temperature, 0.1kg of catalyst was added to the catalyst tank, 0.2kg of solvent was added, stirring was started, and the temperature was raised to 60 ℃.
C. the resin transfer pump was started at a flow rate of 233kg/h, while the catalyst pump was started at a flow rate of 0.1kg/h. The streams are mixed and then enter a static mixer.
D. After materials are mixed by a static mixer, the materials enter the reactor through a straight pipe short circuit, and a thermometer is arranged on the straight pipe short circuit.
E. after the materials enter the reactor at the flow rate of 240kg/h, a heat tracing jacket or a half pipe is introduced into circulating water to remove heat, and the temperature of the materials is maintained at 180 ℃. And after the material reaction is finished, the material flows into a steel belt cooling flaking.
Example 3 and conventional kettle reaction products were taken as sample 1 starting with stable discharge, sample 3 ending with discharge, and the following ratios were set forth in table 3:
TABLE 3 comparison of conventional kettle reaction with product index of example 3
Example 4
A. 600kg of bisphenol A type solid epoxy resin CYD-011 is added into a mixing tank at normal temperature, the temperature is raised to 90 ℃, 115kg of bisphenol A is added, the temperature is raised to 140 ℃, and the temperature is maintained for 1 hour.
B. At normal temperature, 0.115kg of catalyst was added to the catalyst tank, 0.2kg of solvent was added, stirring was started, and the temperature was raised to 60 ℃.
C. The resin transfer pump was started at a flow rate of 238kg/h, while the catalyst pump was started at a flow rate of 0.105kg/h. The streams are mixed and then enter a static mixer.
D. After materials are mixed by a static mixer, the materials enter the reactor through a straight pipe short circuit, and a thermometer is arranged on the straight pipe short circuit.
E. after the materials enter the reactor at the flow rate of 240kg/h, a heat tracing jacket or a half pipe is introduced into circulating water to remove heat, and the temperature of the materials is maintained at 180 ℃. And after the material reaction is finished, the material flows into a steel belt cooling flaking.
Conventional kettle reactions have been difficult to produce such high softening point epoxy resin products, example 4 products are as in table 4:
TABLE 4 comparison of conventional kettle reaction with product index of example 4
Example 5
A. 580kg of bisphenol A type solid epoxy resin CYD-011 is added into a mixing tank at normal temperature, the temperature is raised to 100 ℃, 115kg of bisphenol A is added, the temperature is raised to 140 ℃, and the temperature is maintained for 1 hour.
B. At normal temperature, 0.115kg of catalyst was added to the catalyst tank, 0.2kg of solvent was added, stirring was started, and the temperature was raised to 60 ℃.
C. The resin transfer pump was started at a flow rate of 232kg/h, while the catalyst pump was started at a flow rate of 0.105kg/h. The streams are mixed and then enter a static mixer.
D. After materials are mixed by a static mixer, the materials enter the reactor through a straight pipe short circuit, and a thermometer is arranged on the straight pipe short circuit.
E. After the material enters the reactor at the flow rate of 235kg/h, a heat tracing jacket or a half pipe is introduced into circulating water to remove heat, and the temperature of the material is maintained at 180 ℃. And after the material reaction is finished, the material flows into a steel belt cooling flaking.
Conventional kettle reactions have been difficult to produce such high softening point epoxy resin products, example 5 products are as in table 5:
TABLE 5 comparison of conventional kettle reaction with product index of example 5
By comparing the above examples with the traditional preparation mode, the invention can greatly improve the stability of the quality of the products in batches and can prepare the epoxy resin with high equivalent weight and high softening point.
Claims (10)
1. A method for preparing solid epoxy resin by a continuous dynamic reaction process is characterized in that: mixing a main material comprising a liquid epoxy resin and bisphenol a, or mixing a main material comprising a liquid epoxy resin, bisphenol a and a solid epoxy resin having a softening point temperature of not more than 100 ℃; mixing an adjunct comprising a catalyst and a solvent; and mixing the main materials and the auxiliary materials, and then placing the mixture in a screw reactor for ring-opening polymerization reaction to obtain the modified polyurethane.
2. The method for preparing solid epoxy resin by continuous dynamic reaction process according to claim 1, wherein the method comprises the following steps: the epoxy equivalent weight of the liquid epoxy resin is 184-194 g/eq, the viscosity is 11000-14000 mPa.s, and the hydrolysis chlorine is less than 300ppm.
3. A method for preparing solid epoxy resin by continuous dynamic reaction process according to claim 1 or 2, characterized in that: the software point temperature of the solid epoxy resin with the softening point temperature not exceeding 100 ℃ is 50-90 ℃.
4. The method for preparing solid epoxy resin by continuous dynamic reaction process according to claim 1, wherein the method comprises the following steps: the catalyst comprises at least one of triphenylphosphine, imidazole and ethyl triphenylphosphine salt.
5. The method for preparing solid epoxy resin by continuous dynamic reaction process according to claim 1, wherein the method comprises the following steps: the solvent comprises at least one of methanol, ethanol, water, toluene, xylene, MIBK, acetone and solvent oil.
6. A method for preparing solid epoxy resin by continuous dynamic reaction process according to claim 1 or 2, characterized in that:
The mass ratio of the liquid epoxy resin to the bisphenol A is 6.5-7.5:2.5-3.5.
The mass ratio of the liquid epoxy resin to the bisphenol A to the solid epoxy resin with the softening point temperature not exceeding 100 ℃ is 1-3.7:3.8-7:2-2.5.
7. A method for preparing solid epoxy resin according to claim 1, 4 or 5, characterized in that: the mass ratio of the catalyst to the solvent is 10-65:90-35.
8. The method for preparing solid epoxy resin by continuous dynamic reaction process according to claim 1, wherein the method comprises the following steps: in the mixing process of the main material and the auxiliary material, the mass of the catalyst in the auxiliary material is 0.5-5 per mill of the mass of bisphenol A in the main material.
9. A method for preparing solid epoxy resin by continuous dynamic reaction process according to claim 1 or 8, characterized in that: the main materials and the auxiliary materials are mixed in a static mixer.
10. The method for preparing solid epoxy resin by a continuous dynamic reaction process according to claim 1, wherein the method comprises the following steps: the ring-opening polymerization reaction conditions are as follows: the temperature is 120-200 ℃ and the time is 1-3.5 h.
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| Publication Number | Publication Date |
|---|---|
| CN118307743A true CN118307743A (en) | 2024-07-09 |
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