WO2024074069A1 - Stirring equipment and method for preparing epoxy resin-based flame-retardant composite material by using equipment - Google Patents
Stirring equipment and method for preparing epoxy resin-based flame-retardant composite material by using equipment Download PDFInfo
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- WO2024074069A1 WO2024074069A1 PCT/CN2023/106218 CN2023106218W WO2024074069A1 WO 2024074069 A1 WO2024074069 A1 WO 2024074069A1 CN 2023106218 W CN2023106218 W CN 2023106218W WO 2024074069 A1 WO2024074069 A1 WO 2024074069A1
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- Prior art keywords
- stirring
- parts
- epoxy resin
- composite material
- curing
- Prior art date
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- 238000003756 stirring Methods 0.000 title claims abstract description 147
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000003063 flame retardant Substances 0.000 title claims abstract description 42
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 26
- 238000001723 curing Methods 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 238000001556 precipitation Methods 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 16
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 16
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 16
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 16
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 16
- 238000001514 detection method Methods 0.000 claims description 16
- 235000002906 tartaric acid Nutrition 0.000 claims description 16
- 239000011975 tartaric acid Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 alicyclic amine Chemical class 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000012796 inorganic flame retardant Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 claims description 7
- 239000012783 reinforcing fiber Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 238000013035 low temperature curing Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 7
- 239000009261 D 400 Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract 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
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/32—Cellulose ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the invention relates to the technical field of epoxy resin-based flame-retardant composite materials, and in particular to a stirring device and a method for preparing the epoxy resin-based flame-retardant composite material by using the device.
- Epoxy resin is the earliest developed and most widely used composite resin matrix with excellent processability and adhesion, and has high strength and modulus after curing.
- epoxy resin has flammability and cannot meet the flame retardant performance requirements.
- the existing commonly used technical approach to prepare epoxy resins with flame retardant properties is mainly to modify them by adding flame retardants to the epoxy resin system.
- bisphenol A epoxy resin E44 and dipropylene glycol diglycidyl ether active diluent need to be stirred by a stirring device.
- the existing stirring device is difficult to fully stir and feed the raw materials when preparing epoxy resin-based flame retardant composite materials, so it is necessary to solve the above problems.
- the object of the present invention is to provide a stirring device and a method for preparing an epoxy resin-based flame-retardant composite material using the device, so as to overcome the above-mentioned defects in the prior art.
- the stirring device comprises a stirring drum and a stirring assembly.
- the stirring drum is arranged on a supporting frame.
- a feeding pipe is arranged at the upper end of the stirring drum.
- a discharge pipe with a valve is arranged at the lower end of the stirring drum.
- the stirring assembly is arranged in the stirring drum and is used for stirring the raw materials.
- the stirring assembly includes a motor and a stirring rod
- the motor is installed on the top of the stirring drum
- the stirring rod is arranged in the stirring drum and the upper end of the stirring rod is connected to the output shaft of the motor
- a plurality of mounting blocks are provided on the stirring rod
- inclined side panels are provided around the mounting blocks, each side panel is connected to a stirring plate by screws
- a plurality of arc scrapers are evenly distributed along the circumference of the lower end of the stirring rod, and the arc scrapers cooperate with the inner bottom wall of the stirring drum.
- a plurality of connecting support plates are evenly distributed along the outer side of the circumference of the mixing drum, and the connecting support plates are connected to the support frame by bolts.
- a method for preparing an epoxy resin-based flame-retardant composite material, using the above-mentioned stirring device for preparation, the preparation method comprises the following steps:
- Step 1 resin component: 15-40 parts of bisphenol A epoxy resin, 5-15 parts of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20-40 parts of inorganic flame retardant filler, 20-30 parts of triphenyl phosphate, and 0.5-3 parts of anti-precipitation dispersant are added;
- Step 2 curing agent component: 40-55 parts of polyetheramine, 50-60 parts of alicyclic amine;
- Step 3 composite material: mix the resin and curing agent in a ratio of 100:18-20, take 30-45 parts, and vacuum introduce 50-70 parts of reinforcing fiber;
- Step 4 introduction process: preheat the resin at 45°C, stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with the fiber fabric with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;
- Step 5 curing process: curing at 40-50°C for 4h, curing at 5-10°C for 2h, curing at 70-80°C for 4h. After curing is complete, remove the vacuum bag material to obtain a flame retardant composite material.
- the anti-precipitation dispersant is carboxymethyl cellulose/tartaric acid
- its preparation method is as follows: add 30 parts of carboxymethyl cellulose to an appropriate amount of deionized water, and stir at room temperature until it is completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1 part of ferrocene and 20 parts of tartaric acid, heat to 70-80°C and stir for 2-3h, and an oily substance appears in the reaction system; cool to 30-40°C, add 3 parts of sodium chloride and 3 parts of sodium glycocholate and stir for 0.5-1h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
- the reinforcing fibers are selected from carbon fibers or glass fibers.
- the stirring rod of the stirring assembly driven by the stirring device motor rotates, and the bisphenol A epoxy resin E44 and the dipropylene glycol diglycidyl ether active diluent mixture in the stirring drum are fully stirred by the stirring plate arranged obliquely on the stirring rod.
- the stirring plate arranged obliquely on the stirring rod.
- the bisphenol A epoxy resin is modified in the preparation method, so that the thermal stability and tensile properties of the bisphenol A epoxy resin are enhanced, and the flame retardant property of the bisphenol A epoxy resin is enhanced while the viscosity is reduced; the synthesized anti-precipitation dispersant can prevent polymerization and precipitation between resin components, and reduce the viscosity of the resin system; on the basis of the conventional curing process, low-temperature curing is added to enhance the curing efficiency and tensile properties of the resin.
- FIG1 is a schematic diagram of the overall three-dimensional structure of the present invention.
- FIG. 2 is a front view of the mixing drum of the present invention.
- 3 and 4 are schematic structural diagrams of the stirring assembly of the present invention at different angles.
- the present invention provides a stirring device, including a stirring drum 1 and a stirring assembly 3, wherein the stirring drum 1 is arranged on a support frame 2, and a plurality of connecting support plates 14 are evenly distributed along the outer side of the circumference of the stirring drum 1, and the connecting support plates 14 are connected to the support frame 2 by bolts 15, and a feed pipe 11 is arranged at the upper end of the stirring drum 1, and a discharge pipe 12 with a valve 13 is arranged at the lower end of the stirring drum 1, and the stirring assembly 3 is arranged in the stirring drum 1 and used for stirring the raw materials;
- the stirring assembly 3 includes a motor 31 and a stirring rod 32, wherein the motor 31 is installed on the top of the stirring drum 1, the stirring rod 32 is arranged in the stirring drum 1 and its upper end is connected to the output shaft of the motor 31, a plurality of mounting blocks 33 are arranged on the stirring rod 32, and inclined side plates 34 are arranged around the mounting blocks 33, each side plate 34 is connected to a stirring plate 35 by screws, and a plurality of arc scrapers 36 are evenly distributed along the circumference of the lower end of the stirring rod 32, and the arc scrapers 36 are matched with the inner bottom wall of the stirring drum 1;
- Resin component 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added.
- the motor 31 of the stirring device drives the stirring rod 32 to rotate through its output shaft.
- the stirring plate 35 on the stirring rod 32 stirs the mixture of bisphenol A epoxy resin E44 and dipropylene glycol diglycidyl ether active diluent in the mixing drum 1 to make them fully mixed.
- the valve on the discharge pipe 12 is opened, and the arc scraper 36 on the stirring rod 32 scrapes the raw materials on the inner bottom wall of the mixing drum 1 out of the mixing drum 1;
- Curing agent component polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
- Composite material Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
- Preparation of anti-precipitation dispersant Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium chloride and 3g of sodium glycocholate and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
- Example 1 The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
- Resin component 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
- Curing agent component polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
- Composite material Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
- Modification of bisphenol A epoxy resin dissolve 11g of sodium hydroxymethyl sulfonate in an appropriate amount of 60% ethanol aqueous solution, add 20g of bisphenol A epoxy resin and heat to reflux state, keep warm and stir for 1-2h, filter while hot, cool the precipitate to room temperature, wash with deionized water 3 times, then wash with anhydrous ethanol 2 times, send it to a dryer for drying, dissolve the obtained precipitate and 16g of p-hydroxyanisole in DMSO, add 3g of potassium carbonate, heat to 100°C, keep warm and stir for 2-3h, concentrate under reduced pressure to a residual solvent of 30-35%, add an extractant, extract 2-3 times, collect the organic phase and evaporate and concentrate to obtain a modified bisphenol A epoxy resin.
- the extractant was a mixture of ethyl acetate and deionized water in a volume ratio of 3 :2.
- Preparation of anti-precipitation dispersant Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium chloride and 3g of sodium glycocholate and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
- Example 1 The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
- Resin component 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
- Curing agent component polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
- Composite material Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
- Preparation of anti-precipitation dispersant Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium chloride and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
- Example 1 The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
- Resin component 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
- Curing agent component polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
- Composite material Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
- Preparation of anti-precipitation dispersant Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium glycocholate and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
- Example 1 The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
- Resin component 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
- Curing agent component polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
- Composite material Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
- the anti-precipitation dispersant is ZW-2 anti-precipitation dispersant.
- Example 1 The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
- Resin component 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
- Curing agent component polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
- Composite material Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
- Preparation of anti-precipitation dispersant Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium chloride and 3g of sodium glycocholate and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
- a vacuum-introduced epoxy resin-based flame-retardant composite material was prepared using Examples 1-2, and a control example 1 without adding sodium glycocholate, a control example 2 without adding sodium chloride, a control example 3 using a ZW-2 anti-precipitation dispersant, and a control example 4 without adding a low-temperature curing process were set up, and the performance of Examples 1-2 and Control Examples 1-4 was measured, and the results are shown in Table 1.
- the test conditions for the viscosity of the resin component are: pressure 101.32 kPa, temperature 20°C, and the determination method refers to GB/T 12007.4-1989;
- the oxygen index refers to the minimum oxygen concentration when the material just maintains flame combustion in a mixture of O2 and N2 at room temperature under specified experimental conditions, expressed as a percentage of volume. The higher the oxygen index, the better the flame retardant performance.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention relates to the technical field of epoxy resin-based flame-retardant composite materials, and disclosed in the present invention is a stirring equipment and a method for preparing an epoxy resin-based flame-retardant composite material by using the equipment. The stirring equipment comprises a stirring cylinder and a stirring assembly. In the present invention, raw materials in the stirring cylinder are fully stirred by means of a stirring plate, which is obliquely arranged on a stirring rod, and when discharged, the raw materials on the bottom of the stirring cylinder are fully scraped into a discharging pipe by means of an arc-shaped scraping plate at the bottom of the stirring rod; in addition, a bisphenol A epoxy resin is modified in the preparation method, such that the thermal stability and tensile property of the bisphenol A epoxy resin are enhanced, and the flame retardance thereof is enhanced while the viscosity is reduced; a synthesized anti-precipitation dispersant can prevent polymerization and precipitation among resin components, thereby reducing the viscosity of a resin system; and on the basis of a conventional curing process, low-temperature curing is added, thereby enhancing the curing efficiency and tensile property of the resin.
Description
本发明涉及环氧树脂基阻燃复合材料的技术领域,具体涉及搅拌设备及用该设备制备环氧树脂基阻燃复合材料的方法。The invention relates to the technical field of epoxy resin-based flame-retardant composite materials, and in particular to a stirring device and a method for preparing the epoxy resin-based flame-retardant composite material by using the device.
环氧树脂作为开发最早、应用最为广泛的复合材料树脂基体,具有优良的加工性、粘结性,固化后具有较高的强度和模量。但是环氧树脂具有燃烧性能,不能满足阻燃的性能要求。现有常用的制备具有阻燃性能的环氧树脂的技术途径主要为通过在环氧树脂体系中添加阻燃剂的方式进行改性,其中在阻燃复合材料的制备中需要将双酚A环氧树脂E44及二丙二醇二缩水甘油醚活性稀释剂通过搅拌装置进行搅拌,但是现有搅拌装置在制备环氧树脂基阻燃复合材料时难以对原料进行充分的搅拌及下料,因此需要对上述问题进行解决。Epoxy resin is the earliest developed and most widely used composite resin matrix with excellent processability and adhesion, and has high strength and modulus after curing. However, epoxy resin has flammability and cannot meet the flame retardant performance requirements. The existing commonly used technical approach to prepare epoxy resins with flame retardant properties is mainly to modify them by adding flame retardants to the epoxy resin system. In the preparation of flame retardant composite materials, bisphenol A epoxy resin E44 and dipropylene glycol diglycidyl ether active diluent need to be stirred by a stirring device. However, the existing stirring device is difficult to fully stir and feed the raw materials when preparing epoxy resin-based flame retardant composite materials, so it is necessary to solve the above problems.
本发明的目的在于提供搅拌设备及用该设备制备环氧树脂基阻燃复合材料的方法,以克服现有技术中的上述缺陷。The object of the present invention is to provide a stirring device and a method for preparing an epoxy resin-based flame-retardant composite material using the device, so as to overcome the above-mentioned defects in the prior art.
搅拌设备,包括搅拌筒及搅拌组件,所述搅拌筒设于支撑架上,搅拌筒上端设有进料管,搅拌筒的下端设有安装有阀门的出料管,搅拌组件设于搅拌筒中并用于对原料进行搅拌操作。The stirring device comprises a stirring drum and a stirring assembly. The stirring drum is arranged on a supporting frame. A feeding pipe is arranged at the upper end of the stirring drum. A discharge pipe with a valve is arranged at the lower end of the stirring drum. The stirring assembly is arranged in the stirring drum and is used for stirring the raw materials.
优选的,所述搅拌组件包括电机及搅拌杆,所述电机安装于搅拌筒的顶部,所述搅拌杆设于搅拌筒中且其上端与电机的输出轴连接,搅拌杆上设有若干安装块,安装块的四周均设有倾斜设置的侧板,每个侧板均通过螺丝连接有搅拌板,沿搅拌杆下端的圆周均布有若干弧形刮板,弧形刮板与搅拌筒的内底壁相配合。Preferably, the stirring assembly includes a motor and a stirring rod, the motor is installed on the top of the stirring drum, the stirring rod is arranged in the stirring drum and the upper end of the stirring rod is connected to the output shaft of the motor, a plurality of mounting blocks are provided on the stirring rod, and inclined side panels are provided around the mounting blocks, each side panel is connected to a stirring plate by screws, and a plurality of arc scrapers are evenly distributed along the circumference of the lower end of the stirring rod, and the arc scrapers cooperate with the inner bottom wall of the stirring drum.
优选的,沿搅拌筒圆周外侧均布有若干连接支板,连接支板通过螺栓与支撑架连接。Preferably, a plurality of connecting support plates are evenly distributed along the outer side of the circumference of the mixing drum, and the connecting support plates are connected to the support frame by bolts.
一种制备环氧树脂基阻燃复合材料的方法,使用上述的搅拌装置进行制备,所述制备方法包括以下步骤:A method for preparing an epoxy resin-based flame-retardant composite material, using the above-mentioned stirring device for preparation, the preparation method comprises the following steps:
步骤一、树脂组分:双酚A环氧树脂15-40份、二丙二醇二缩水甘油醚活性稀释剂5-15份通过搅拌装置搅拌均匀后加入无机阻燃填料20-40份、磷酸三苯酯20-30份、抗沉淀分散剂 0.5-3份;Step 1, resin component: 15-40 parts of bisphenol A epoxy resin, 5-15 parts of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20-40 parts of inorganic flame retardant filler, 20-30 parts of triphenyl phosphate, and 0.5-3 parts of anti-precipitation dispersant are added;
步骤二、固化剂组分:聚醚胺40-55份,脂环胺50-60份;Step 2, curing agent component: 40-55 parts of polyetheramine, 50-60 parts of alicyclic amine;
步骤三、复合材料:树脂、固化剂按照100 :18-20比例混合均匀后取30-45份,真空导入增强纤维50-70份;Step 3, composite material: mix the resin and curing agent in a ratio of 100:18-20, take 30-45 parts, and vacuum introduce 50-70 parts of reinforcing fiber;
步骤四、导入工艺:按照树脂45℃预热、固化剂不预热搅拌混合,模具预热至40℃,在铺覆有纤维织物的模具上铺覆真空袋,并密封真空袋与模具之间形成的模腔,对所述模腔抽真空,以压实其中的纤维织物,并对抽真空后的模腔进行真空检漏,检漏合格后,40℃向模腔中导入复合材料;Step 4, introduction process: preheat the resin at 45°C, stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with the fiber fabric with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;
步骤五、固化工艺:40-50℃固化4h、5-10℃固化2h、70-80℃固化4h,固化完全后揭去真空袋材料,即得到阻燃复合材料。Step 5, curing process: curing at 40-50°C for 4h, curing at 5-10°C for 2h, curing at 70-80°C for 4h. After curing is complete, remove the vacuum bag material to obtain a flame retardant composite material.
优选的,所述抗沉淀分散剂为羧甲基纤维素/酒石酸,其制备方法为:把30份羧甲基纤维素加入到适量的去离子水中,常温搅拌至完全溶解;用10%的醋酸溶液调节溶液的pH为5-6,再加入1份二茂铁和20份酒石酸,升温至70-80℃搅拌2-3h,反应体系出现油状物;降温至30-40℃,加入3份氯化钠和3份甘氨胆酸钠搅拌0.5-1h;冷却至室温,分离出油状物,蒸发、结晶即得到羧甲基纤维素/酒石酸。Preferably, the anti-precipitation dispersant is carboxymethyl cellulose/tartaric acid, and its preparation method is as follows: add 30 parts of carboxymethyl cellulose to an appropriate amount of deionized water, and stir at room temperature until it is completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1 part of ferrocene and 20 parts of tartaric acid, heat to 70-80°C and stir for 2-3h, and an oily substance appears in the reaction system; cool to 30-40°C, add 3 parts of sodium chloride and 3 parts of sodium glycocholate and stir for 0.5-1h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
优选的,所述增强纤维选自碳纤维或玻璃纤维。Preferably, the reinforcing fibers are selected from carbon fibers or glass fibers.
本发明具有如下优点:The present invention has the following advantages:
本发明在使用时,通过搅拌装置电机带动的搅拌组件的搅拌杆转动,通过搅拌杆上倾斜设置的搅拌板对搅拌筒中的双酚A环氧树脂E44及二丙二醇二缩水甘油醚活性稀释剂混合物进行充分的搅拌,当下料时,通过搅拌杆底部的弧形刮板使搅拌筒内底部上的原料充分的刮至出料管中,同时本制备方法中对双酚A环氧树脂进行改性,增强了双酚A环氧树脂的热稳定性和拉伸性能,降低粘度的同时增强了自身的阻燃性能;合成的抗沉淀分散剂能阻止树脂组分间的聚合、沉淀,降低了树脂体系的粘度;在常规固化工艺的基础上,添加低温固化,增强了树脂的固化效率和拉伸性能。When the present invention is in use, the stirring rod of the stirring assembly driven by the stirring device motor rotates, and the bisphenol A epoxy resin E44 and the dipropylene glycol diglycidyl ether active diluent mixture in the stirring drum are fully stirred by the stirring plate arranged obliquely on the stirring rod. When unloading, the raw materials on the bottom of the stirring drum are fully scraped into the discharge pipe by the arc-shaped scraper at the bottom of the stirring rod. At the same time, the bisphenol A epoxy resin is modified in the preparation method, so that the thermal stability and tensile properties of the bisphenol A epoxy resin are enhanced, and the flame retardant property of the bisphenol A epoxy resin is enhanced while the viscosity is reduced; the synthesized anti-precipitation dispersant can prevent polymerization and precipitation between resin components, and reduce the viscosity of the resin system; on the basis of the conventional curing process, low-temperature curing is added to enhance the curing efficiency and tensile properties of the resin.
图1为本发明整体三维的结构示意图。FIG1 is a schematic diagram of the overall three-dimensional structure of the present invention.
图2为本发明搅拌筒的正视图。FIG. 2 is a front view of the mixing drum of the present invention.
图3及图4为本发明搅拌组件的不同角度的结构示意图。3 and 4 are schematic structural diagrams of the stirring assembly of the present invention at different angles.
其中:1、搅拌筒;11、进料管;12、出料管;13、阀门;14、连接支板;15、螺栓;2、支撑架;3、搅拌组件;31、电机;32、搅拌杆;33、安装块;34、侧板;35、搅拌板;36、弧形刮板。Among them: 1. mixing drum; 11. feed pipe; 12. discharge pipe; 13. valve; 14. connecting support plate; 15. bolts; 2. support frame; 3. stirring assembly; 31. motor; 32. stirring rod; 33. mounting block; 34. side plate; 35. stirring plate; 36. arc scraper.
实施方式
Implementation
下面对照附图,通过对实施例的描述,对本发明具体实施方式作进一步详细的说明,以帮助本领域的技术人员对本发明的构思、技术方案有更完整、准确和深入的理解。The specific implementation methods of the present invention are further explained in detail below by describing the embodiments with reference to the accompanying drawings, so as to help those skilled in the art to have a more complete, accurate and in-depth understanding of the concept and technical solution of the present invention.
如图1-4所示,本发明提供了搅拌设备,包括搅拌筒1及搅拌组件3,所述搅拌筒1设于支撑架2上,沿搅拌筒1圆周外侧均布有若干连接支板14,连接支板14通过螺栓15与支撑架2连接,搅拌筒1上端设有进料管11,搅拌筒1的下端设有安装有阀门13的出料管12,搅拌组件3设于搅拌筒1中并用于对原料进行搅拌操作;As shown in FIGS. 1-4 , the present invention provides a stirring device, including a stirring drum 1 and a stirring assembly 3, wherein the stirring drum 1 is arranged on a support frame 2, and a plurality of connecting support plates 14 are evenly distributed along the outer side of the circumference of the stirring drum 1, and the connecting support plates 14 are connected to the support frame 2 by bolts 15, and a feed pipe 11 is arranged at the upper end of the stirring drum 1, and a discharge pipe 12 with a valve 13 is arranged at the lower end of the stirring drum 1, and the stirring assembly 3 is arranged in the stirring drum 1 and used for stirring the raw materials;
此外,所述搅拌组件3包括电机31及搅拌杆32,所述电机31安装于搅拌筒1的顶部,所述搅拌杆32设于搅拌筒1中且其上端与电机31的输出轴连接,搅拌杆32上设有若干安装块33,安装块33的四周均设有倾斜设置的侧板34,每个侧板34均通过螺丝连接有搅拌板35,沿搅拌杆32下端的圆周均布有若干弧形刮板36,弧形刮板36与搅拌筒1的内底壁相配合;In addition, the stirring assembly 3 includes a motor 31 and a stirring rod 32, wherein the motor 31 is installed on the top of the stirring drum 1, the stirring rod 32 is arranged in the stirring drum 1 and its upper end is connected to the output shaft of the motor 31, a plurality of mounting blocks 33 are arranged on the stirring rod 32, and inclined side plates 34 are arranged around the mounting blocks 33, each side plate 34 is connected to a stirring plate 35 by screws, and a plurality of arc scrapers 36 are evenly distributed along the circumference of the lower end of the stirring rod 32, and the arc scrapers 36 are matched with the inner bottom wall of the stirring drum 1;
阻燃复合材料的制备:Preparation of flame retardant composite materials:
(1)树脂组分:双酚A环氧树脂E44 20g、二丙二醇二缩水甘油醚活性稀释剂5g通过搅拌装置搅拌均匀后加入无机阻燃填料20g,磷酸三苯酯20g,抗沉淀分散剂0.5g,搅拌装置的电机31通过其输出轴带动搅拌杆32转动,搅拌杆32上的搅拌板35对搅拌筒1中的双酚A环氧树脂E44及二丙二醇二缩水甘油醚活性稀释剂混合物进行搅动,使其充分混合,当搅拌完成后,打开出料管12上的阀门,搅拌杆32上的弧形刮板36将搅拌筒1内底壁上的原料刮出搅拌筒1;(1) Resin component: 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added. The motor 31 of the stirring device drives the stirring rod 32 to rotate through its output shaft. The stirring plate 35 on the stirring rod 32 stirs the mixture of bisphenol A epoxy resin E44 and dipropylene glycol diglycidyl ether active diluent in the mixing drum 1 to make them fully mixed. After the stirring is completed, the valve on the discharge pipe 12 is opened, and the arc scraper 36 on the stirring rod 32 scrapes the raw materials on the inner bottom wall of the mixing drum 1 out of the mixing drum 1;
(2)固化剂组分:聚醚胺D-400 40g,TAC-900脂环胺50g;(2) Curing agent component: polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
(3)复合材料:树脂、固化剂按照100 :18比例混合均匀后取30g,真空导入50g玻璃纤维;(3) Composite material: Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
(4)导入工艺:按照树脂45℃预热、固化剂不预热搅拌混合,模具预热至40℃,在铺覆有玻璃纤维的模具上铺覆真空袋,并密封真空袋与模具之间形成的模腔,对所述模腔抽真空,以压实其中的纤维织物,并对抽真空后的模腔进行真空检漏,检漏合格后,40℃向模腔中导入复合材料;(4) Introduction process: preheat the resin at 45°C and stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with glass fiber with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;
(5)固化工艺:40℃固化4h、5℃固化2h、80℃固化4h,固化完全后揭去真空袋材料,即得到阻燃复合材料。(5) Curing process: Curing at 40°C for 4 h, 5°C for 2 h, and 80°C for 4 h. After complete curing, remove the vacuum bag material to obtain a flame-retardant composite material.
抗沉淀分散剂的制备:把30g羧甲基纤维素加入到适量的去离子水中,常温搅拌至完全溶解;用10%的醋酸溶液调节溶液的pH为5-6,再加入1g二茂铁和20g酒石酸,升温至70g℃搅拌2h,反应体系出现油状物;降温至30g℃,加入3g氯化钠和3g甘氨胆酸钠搅拌0.5h;冷却至室温,分离出油状物,蒸发、结晶即得到羧甲基纤维素/酒石酸。Preparation of anti-precipitation dispersant: Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium chloride and 3g of sodium glycocholate and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
使用与实施例1中相同的搅拌装置进行制备环氧树脂基阻燃复合材料。The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
一种基于上述任一实施例所述的搅拌设备及用该设备制备环氧树脂基阻燃复合材料的方法,其主要包括以下步骤:A stirring device according to any of the above embodiments and a method for preparing an epoxy resin-based flame-retardant composite material using the stirring device mainly comprises the following steps:
阻燃复合材料的制备:Preparation of flame retardant composite materials:
(1)树脂组分:双酚A环氧树脂E44 20g、二丙二醇二缩水甘油醚活性稀释剂5g通过搅拌装置搅拌均匀后加入无机阻燃填料20g,磷酸三苯酯20g,抗沉淀分散剂0.5g;(1) Resin component: 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
(2)固化剂组分:聚醚胺D-400 40g,TAC-900脂环胺50g;(2) Curing agent component: polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
(3)复合材料:树脂、固化剂按照100 :18比例混合均匀后取30g,真空导入50g玻璃纤维;(3) Composite material: Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
(4)导入工艺:按照树脂45℃预热、固化剂不预热搅拌混合,模具预热至40℃,在铺覆有玻璃纤维的模具上铺覆真空袋,并密封真空袋与模具之间形成的模腔,对所述模腔抽真空,以压实其中的纤维织物,并对抽真空后的模腔进行真空检漏,检漏合格后,40℃向模腔中导入复合材料;(4) Introduction process: preheat the resin at 45°C and stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with glass fiber with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;
(5)固化工艺:40℃固化4h、5℃固化2h、80℃固化4h,固化完全后揭去真空袋材料,即得到阻燃复合材料。(5) Curing process: Curing at 40°C for 4 h, 5°C for 2 h, and 80°C for 4 h. After complete curing, remove the vacuum bag material to obtain a flame-retardant composite material.
双酚A环氧树脂的改性:将11g羟甲基磺酸钠溶解在适量60%的乙醇水溶液中,加入20g双酚A环氧树脂加热至回流状态,保温搅拌1-2h,趁热过滤,沉淀冷却至室温,用去离子水洗涤3次,再用无水乙醇洗涤2次,送入烘干机中干燥,将所得沉淀和16g对羟基苯甲醚溶解于DMSO中,加入3g碳酸钾,加热至100℃,保温搅拌2-3h,减压浓缩至溶剂剩余为30-35%,加入萃取剂,萃取2-3次,收集有机相蒸发浓缩即得到改性双酚A环氧树脂。Modification of bisphenol A epoxy resin: dissolve 11g of sodium hydroxymethyl sulfonate in an appropriate amount of 60% ethanol aqueous solution, add 20g of bisphenol A epoxy resin and heat to reflux state, keep warm and stir for 1-2h, filter while hot, cool the precipitate to room temperature, wash with deionized water 3 times, then wash with anhydrous ethanol 2 times, send it to a dryer for drying, dissolve the obtained precipitate and 16g of p-hydroxyanisole in DMSO, add 3g of potassium carbonate, heat to 100℃, keep warm and stir for 2-3h, concentrate under reduced pressure to a residual solvent of 30-35%, add an extractant, extract 2-3 times, collect the organic phase and evaporate and concentrate to obtain a modified bisphenol A epoxy resin.
萃取剂为乙酸乙酯和去离子水的混合液,体积比为3 :2。The extractant was a mixture of ethyl acetate and deionized water in a volume ratio of 3 :2.
抗沉淀分散剂的制备:把30g羧甲基纤维素加入到适量的去离子水中,常温搅拌至完全溶解;用10%的醋酸溶液调节溶液的pH为5-6,再加入1g二茂铁和20g酒石酸,升温至70g℃搅拌2h,反应体系出现油状物;降温至30g℃,加入3g氯化钠和3g甘氨胆酸钠搅拌0.5h;冷却至室温,分离出油状物,蒸发、结晶即得到羧甲基纤维素/酒石酸。Preparation of anti-precipitation dispersant: Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium chloride and 3g of sodium glycocholate and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
对照例1Comparative Example 1
使用与实施例1中相同的搅拌装置进行制备环氧树脂基阻燃复合材料。The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
一种基于上述任一实施例所述的搅拌设备及用该设备制备环氧树脂基阻燃复合材料的方法,其主要包括以下步骤:A stirring device according to any of the above embodiments and a method for preparing an epoxy resin-based flame-retardant composite material using the stirring device mainly comprises the following steps:
阻燃复合材料的制备:Preparation of flame retardant composite materials:
(1)树脂组分:双酚A环氧树脂E44 20g、二丙二醇二缩水甘油醚活性稀释剂5g通过搅拌装置搅拌均匀后加入无机阻燃填料20g,磷酸三苯酯20g,抗沉淀分散剂0.5g;(1) Resin component: 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
(2)固化剂组分:聚醚胺D-400 40g,TAC-900脂环胺50g;(2) Curing agent component: polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
(3)复合材料:树脂、固化剂按照100 :18比例混合均匀后取30g,真空导入50g玻璃纤维;(3) Composite material: Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
(4)导入工艺:按照树脂45℃预热、固化剂不预热搅拌混合,模具预热至40℃,在铺覆有玻璃纤维的模具上铺覆真空袋,并密封真空袋与模具之间形成的模腔,对所述模腔抽真空,以压实其中的纤维织物,并对抽真空后的模腔进行真空检漏,检漏合格后,40℃向模腔中导入复合材料;(4) Introduction process: preheat the resin at 45°C and stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with glass fiber with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;
(5)固化工艺:40℃固化4h、5℃固化2h、80℃固化4h,固化完全后揭去真空袋材料,即得到阻燃复合材料。(5) Curing process: Curing at 40°C for 4 h, 5°C for 2 h, and 80°C for 4 h. After complete curing, remove the vacuum bag material to obtain a flame-retardant composite material.
抗沉淀分散剂的制备:把30g羧甲基纤维素加入到适量的去离子水中,常温搅拌至完全溶解;用10%的醋酸溶液调节溶液的pH为5-6,再加入1g二茂铁和20g酒石酸,升温至70g℃搅拌2h,反应体系出现油状物;降温至30g℃,加入3g氯化钠搅拌0.5h;冷却至室温,分离出油状物,蒸发、结晶即得到羧甲基纤维素/酒石酸。Preparation of anti-precipitation dispersant: Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium chloride and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
使用与实施例1中相同的搅拌装置进行制备环氧树脂基阻燃复合材料。The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
一种基于上述任一实施例所述的搅拌设备及用该设备制备环氧树脂基阻燃复合材料的方法,其主要包括以下步骤:A stirring device according to any of the above embodiments and a method for preparing an epoxy resin-based flame-retardant composite material using the stirring device mainly comprises the following steps:
阻燃复合材料的制备:Preparation of flame retardant composite materials:
(1)树脂组分:双酚A环氧树脂E44 20g、二丙二醇二缩水甘油醚活性稀释剂5g通过搅拌装置搅拌均匀后加入无机阻燃填料20g,磷酸三苯酯20g,抗沉淀分散剂0.5g;(1) Resin component: 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
(2)固化剂组分:聚醚胺D-400 40g,TAC-900脂环胺50g;(2) Curing agent component: polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
(3)复合材料:树脂、固化剂按照100 :18比例混合均匀后取30g,真空导入50g玻璃纤维;(3) Composite material: Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
(4)导入工艺:按照树脂45℃预热、固化剂不预热搅拌混合,模具预热至40℃,在铺覆有玻璃纤维的模具上铺覆真空袋,并密封真空袋与模具之间形成的模腔,对所述模腔抽真空,以压实其中的纤维织物,并对抽真空后的模腔进行真空检漏,检漏合格后,40℃向模腔中导入复合材料;(4) Introduction process: preheat the resin at 45°C and stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with glass fiber with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;
(5)固化工艺:40℃固化4h、5℃固化2h、80℃固化4h,固化完全后揭去真空袋材料,即得到阻燃复合材料。(5) Curing process: Curing at 40°C for 4 h, 5°C for 2 h, and 80°C for 4 h. After complete curing, remove the vacuum bag material to obtain a flame-retardant composite material.
抗沉淀分散剂的制备:把30g羧甲基纤维素加入到适量的去离子水中,常温搅拌至完全溶解;用10%的醋酸溶液调节溶液的pH为5-6,再加入1g二茂铁和20g酒石酸,升温至70g℃搅拌2h,反应体系出现油状物;降温至30g℃,加入3g甘氨胆酸钠搅拌0.5h;冷却至室温,分离出油状物,蒸发、结晶即得到羧甲基纤维素/酒石酸。Preparation of anti-precipitation dispersant: Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium glycocholate and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
对照例3Comparative Example 3
使用与实施例1中相同的搅拌装置进行制备环氧树脂基阻燃复合材料。The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
一种基于上述任一实施例所述的搅拌设备及用该设备制备环氧树脂基阻燃复合材料的方法,其主要包括以下步骤:A stirring device according to any of the above embodiments and a method for preparing an epoxy resin-based flame-retardant composite material using the stirring device mainly comprises the following steps:
阻燃复合材料的制备:Preparation of flame retardant composite materials:
(1)树脂组分:双酚A环氧树脂E44 20g、二丙二醇二缩水甘油醚活性稀释剂5g通过搅拌装置搅拌均匀后加入无机阻燃填料20g,磷酸三苯酯20g,抗沉淀分散剂0.5g;(1) Resin component: 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
(2)固化剂组分:聚醚胺D-400 40g,TAC-900脂环胺50g;(2) Curing agent component: polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
(3)复合材料:树脂、固化剂按照100 :18比例混合均匀后取30g,真空导入50g玻璃纤维;(3) Composite material: Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
(4)导入工艺:按照树脂45℃预热、固化剂不预热搅拌混合,模具预热至40℃,在铺覆有玻璃纤维的模具上铺覆真空袋,并密封真空袋与模具之间形成的模腔,对所述模腔抽真空,以压实其中的纤维织物,并对抽真空后的模腔进行真空检漏,检漏合格后,40℃向模腔中导入复合材料;(4) Introduction process: preheat the resin at 45°C and stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with glass fiber with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;
(5)固化工艺:40℃固化4h、5℃固化2h、80℃固化4h,固化完全后揭去真空袋材料,即得到阻燃复合材料。(5) Curing process: Curing at 40°C for 4 h, 5°C for 2 h, and 80°C for 4 h. After complete curing, remove the vacuum bag material to obtain a flame-retardant composite material.
抗沉淀分散剂为ZW-2抗沉淀分散剂。The anti-precipitation dispersant is ZW-2 anti-precipitation dispersant.
对照例4Comparative Example 4
使用与实施例1中相同的搅拌装置进行制备环氧树脂基阻燃复合材料。The same stirring device as in Example 1 was used to prepare the epoxy resin-based flame retardant composite material.
一种基于上述任一实施例所述的搅拌设备及用该设备制备环氧树脂基阻燃复合材料的方法,其主要包括以下步骤:A stirring device according to any of the above embodiments and a method for preparing an epoxy resin-based flame-retardant composite material using the stirring device mainly comprises the following steps:
阻燃复合材料的制备:Preparation of flame retardant composite materials:
(1)树脂组分:双酚A环氧树脂E44 20g、二丙二醇二缩水甘油醚活性稀释剂5g通过搅拌装置搅拌均匀后加入无机阻燃填料20g,磷酸三苯酯20g,抗沉淀分散剂0.5g;(1) Resin component: 20 g of bisphenol A epoxy resin E44 and 5 g of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20 g of inorganic flame retardant filler, 20 g of triphenyl phosphate, and 0.5 g of anti-precipitation dispersant are added;
(2)固化剂组分:聚醚胺D-400 40g,TAC-900脂环胺50g;(2) Curing agent component: polyetheramine D-400 40g, TAC-900 alicyclic amine 50g;
(3)复合材料:树脂、固化剂按照100 :18比例混合均匀后取30g,真空导入50g玻璃纤维;(3) Composite material: Mix the resin and curing agent in a ratio of 100:18, take 30g, and vacuum introduce 50g of glass fiber;
(4)导入工艺:按照树脂45℃预热、固化剂不预热搅拌混合,模具预热至40℃,在铺覆有玻璃纤维的模具上铺覆真空袋,并密封真空袋与模具之间形成的模腔,对所述模腔抽真空,以压实其中的纤维织物,并对抽真空后的模腔进行真空检漏,检漏合格后,40℃向模腔中导入复合材料;(4) Introduction process: preheat the resin at 45°C and stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with glass fiber with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;
(5)固化工艺:40℃固化4h、80℃固化4h,固化完全后揭去真空袋材料,即得到阻燃复合材料。(5) Curing process: Curing at 40°C for 4 hours and at 80°C for 4 hours. After complete curing, remove the vacuum bag material to obtain a flame-retardant composite material.
抗沉淀分散剂的制备:把30g羧甲基纤维素加入到适量的去离子水中,常温搅拌至完全溶解;用10%的醋酸溶液调节溶液的pH为5-6,再加入1g二茂铁和20g酒石酸,升温至70g℃搅拌2h,反应体系出现油状物;降温至30g℃,加入3g氯化钠和3g甘氨胆酸钠搅拌0.5h;冷却至室温,分离出油状物,蒸发、结晶即得到羧甲基纤维素/酒石酸。Preparation of anti-precipitation dispersant: Add 30g of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until completely dissolved; adjust the pH of the solution to 5-6 with 10% acetic acid solution, then add 1g of ferrocene and 20g of tartaric acid, heat to 70°C and stir for 2h, and an oily substance will appear in the reaction system; cool to 30°C, add 3g of sodium chloride and 3g of sodium glycocholate and stir for 0.5h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
利用实施例1-2制成真空导入环氧树脂基阻燃复合材料,并设置不添加甘氨胆酸钠的对照例1、不添加氯化钠的对照例2、采用ZW-2抗沉淀分散剂的对照例3、不添加低温固化工艺的对照例4,并对实施例1-2、对照例1-4进行性能测定,结果如表1所示。A vacuum-introduced epoxy resin-based flame-retardant composite material was prepared using Examples 1-2, and a control example 1 without adding sodium glycocholate, a control example 2 without adding sodium chloride, a control example 3 using a ZW-2 anti-precipitation dispersant, and a control example 4 without adding a low-temperature curing process were set up, and the performance of Examples 1-2 and Control Examples 1-4 was measured, and the results are shown in Table 1.
表1 复合材料的性能检测Table 1 Performance test of composite materials
检测项目 拉伸性能(MPa) 树脂组分粘度(Pa•s) 氧指数(%)Test items Tensile properties (MPa) Resin component viscosity (Pa•s) Oxygen index (%)
实施例1 35 6.1 36Example 1 35 6.1 36
实施例2 59 4.5 41Example 2 59 4.5 41
对照例1 32 6.9 34Comparative Example 1 32 6.9 34
对照例2 33 6.8 33Comparative Example 2 33 6.8 33
对照例3 34 6.6 32Comparative Example 3 34 6.6 32
对照例4 28 6.4 33Comparative Example 4 28 6.4 33
树脂组分粘度的测试条件为:压强101.32kPa、温度为20℃,测定方法参照GB/T 12007.4-1989;氧指数是指在规定的实验条件下、在室温下材料在O2、N2混合气体中刚好维持发焰燃烧时的最小氧浓度,以体积的百分率表示,氧指数越高其阻燃性能越高好。The test conditions for the viscosity of the resin component are: pressure 101.32 kPa, temperature 20°C, and the determination method refers to GB/T 12007.4-1989; the oxygen index refers to the minimum oxygen concentration when the material just maintains flame combustion in a mixture of O2 and N2 at room temperature under specified experimental conditions, expressed as a percentage of volume. The higher the oxygen index, the better the flame retardant performance.
上面结合附图对本发明进行了示例性描述,显然本发明具体实现并不受上述方式的限制,只要采用了本发明的构思和技术方案进行的各种非实质性的改进,或未经改进将本实用发明和技术方案直接应用于其它场合的,均在本发明保护范围之内。The present invention is described above by way of example in conjunction with the accompanying drawings. It is obvious that the specific implementation of the present invention is not limited to the above-mentioned method. As long as various non-substantial improvements are made using the concept and technical solution of the present invention, or the present utility invention and technical solution are directly applied to other occasions without improvement, they are all within the protection scope of the present invention.
Claims (6)
- 搅拌设备,其特征在于:包括搅拌筒(1)及搅拌组件(3),所述搅拌筒(1)设于支撑架(2)上,搅拌筒(1)上端设有进料管(11),搅拌筒(1)的下端设有安装有阀门(13)的出料管(12),搅拌组件(3)设于搅拌筒(1)中并用于对原料进行搅拌操作。A stirring device, characterized in that it comprises a stirring drum (1) and a stirring assembly (3), wherein the stirring drum (1) is arranged on a support frame (2), a feeding pipe (11) is arranged at the upper end of the stirring drum (1), a discharge pipe (12) equipped with a valve (13) is arranged at the lower end of the stirring drum (1), and the stirring assembly (3) is arranged in the stirring drum (1) and is used to stir the raw materials.
- 根据权利要求1所述的搅拌设备,其特征在于:所述搅拌组件(3)包括电机(31)及搅拌杆(32),所述电机(31)安装于搅拌筒(1)的顶部,所述搅拌杆(32)设于搅拌筒(1)中且其上端与电机(31)的输出轴连接,搅拌杆(32)上设有若干安装块(33),安装块(33)的四周均设有倾斜设置的侧板(34),每个侧板(34)均通过螺丝连接有搅拌板(35),沿搅拌杆(32)下端的圆周均布有若干弧形刮板(36),弧形刮板(36)与搅拌筒(1)的内底壁相配合。The stirring device according to claim 1 is characterized in that: the stirring assembly (3) comprises a motor (31) and a stirring rod (32), the motor (31) is installed on the top of the stirring drum (1), the stirring rod (32) is arranged in the stirring drum (1) and its upper end is connected to the output shaft of the motor (31), a plurality of mounting blocks (33) are arranged on the stirring rod (32), and the mounting blocks (33) are provided with inclined side plates (34) around them, each side plate (34) is connected to a stirring plate (35) by screws, and a plurality of arc scrapers (36) are evenly distributed along the circumference of the lower end of the stirring rod (32), and the arc scrapers (36) are matched with the inner bottom wall of the stirring drum (1).
- 根据权利要求1所述的搅拌设备,其特征在于:沿搅拌筒(1)圆周外侧均布有若干连接支板(14),连接支板(14)通过螺栓(15)与支撑架(2)连接。The mixing device according to claim 1 is characterized in that a plurality of connecting support plates (14) are evenly distributed along the outer side of the circumference of the mixing drum (1), and the connecting support plates (14) are connected to the support frame (2) by bolts (15).
- 一种制备环氧树脂基阻燃复合材料的方法,其特征在于,使用如权利要求1-3任一项所述的搅拌装置进行制备,所述制备方法包括以下步骤:A method for preparing an epoxy resin-based flame-retardant composite material, characterized in that the preparation is carried out using a stirring device as described in any one of claims 1 to 3, and the preparation method comprises the following steps:步骤一、树脂组分:双酚A环氧树脂15-40份、二丙二醇二缩水甘油醚活性稀释剂5-15份通过搅拌装置搅拌均匀后加入无机阻燃填料20-40份、磷酸三苯酯20-30份、抗沉淀分散剂 0.5-3份;Step 1, resin component: 15-40 parts of bisphenol A epoxy resin, 5-15 parts of dipropylene glycol diglycidyl ether active diluent are stirred evenly by a stirring device, and then 20-40 parts of inorganic flame retardant filler, 20-30 parts of triphenyl phosphate, and 0.5-3 parts of anti-precipitation dispersant are added;步骤二、固化剂组分:聚醚胺40-55份,脂环胺50-60份;Step 2, curing agent component: 40-55 parts of polyetheramine, 50-60 parts of alicyclic amine;步骤三、复合材料:树脂、固化剂按照100 :18-20比例混合均匀后取30-45份,真空导入增强纤维50-70份;Step 3, composite material: mix the resin and curing agent in a ratio of 100:18-20, take 30-45 parts, and vacuum introduce 50-70 parts of reinforcing fiber;步骤四、导入工艺:按照树脂45℃预热、固化剂不预热搅拌混合,模具预热至40℃,在铺覆有纤维织物的模具上铺覆真空袋,并密封真空袋与模具之间形成的模腔,对所述模腔抽真空,以压实其中的纤维织物,并对抽真空后的模腔进行真空检漏,检漏合格后,40℃向模腔中导入复合材料;Step 4, introduction process: preheat the resin at 45°C, stir and mix the curing agent without preheating, preheat the mold to 40°C, cover the mold covered with the fiber fabric with a vacuum bag, and seal the mold cavity formed between the vacuum bag and the mold, evacuate the mold cavity to compact the fiber fabric therein, and perform vacuum leak detection on the vacuumed mold cavity. After the leak detection is qualified, introduce the composite material into the mold cavity at 40°C;步骤五、固化工艺:40-50℃固化4h、5-10℃固化2h、70-80℃固化4h,固化完全后揭去真空袋材料,即得到阻燃复合材料。Step 5, curing process: curing at 40-50°C for 4h, curing at 5-10°C for 2h, curing at 70-80°C for 4h. After curing is complete, remove the vacuum bag material to obtain a flame retardant composite material.
- 根据权利要求4所述真空导入环氧树脂基无卤阻燃复合材料的制备方法,其特征在于,所述抗沉淀分散剂为羧甲基纤维素/酒石酸,其制备方法为:把30份羧甲基纤维素加入到适量的去离子水中,常温搅拌至完全溶解;用10%的醋酸溶液调节溶液的pH为5-6,再加入1份二茂铁和20份酒石酸,升温至70-80℃搅拌2-3h,反应体系出现油状物;降温至30-40℃,加入3份氯化钠和3份甘氨胆酸钠搅拌0.5-1h;冷却至室温,分离出油状物,蒸发、结晶即得到羧甲基纤维素/酒石酸。According to claim 4, the method for preparing a vacuum-introduced epoxy resin-based halogen-free flame-retardant composite material is characterized in that the anti-precipitation dispersant is carboxymethyl cellulose/tartaric acid, and the preparation method is: add 30 parts of carboxymethyl cellulose to an appropriate amount of deionized water and stir at room temperature until it is completely dissolved; adjust the pH of the solution to 5-6 with a 10% acetic acid solution, then add 1 part of ferrocene and 20 parts of tartaric acid, heat to 70-80°C and stir for 2-3h, and an oily substance appears in the reaction system; cool to 30-40°C, add 3 parts of sodium chloride and 3 parts of sodium glycocholate and stir for 0.5-1h; cool to room temperature, separate the oily substance, evaporate and crystallize to obtain carboxymethyl cellulose/tartaric acid.
- 根据权利要求4所述真空导入环氧树脂基无卤阻燃复合材料的制备方法,其特征在于:所述增强纤维选自碳纤维或玻璃纤维。The method for preparing a vacuum-introduced epoxy resin-based halogen-free flame-retardant composite material according to claim 4 is characterized in that the reinforcing fiber is selected from carbon fiber or glass fiber.
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CN218924599U (en) * | 2022-10-31 | 2023-04-28 | 上海烯纺新材料科技有限公司 | Graphene production temperature regulation and control device |
CN218981227U (en) * | 2022-12-01 | 2023-05-09 | 佛山市顺德区旺海饲料实业有限公司 | Fodder dosing unit |
CN219043998U (en) * | 2022-12-20 | 2023-05-19 | 河北建设集团股份有限公司 | Mixer for building |
-
2023
- 2023-07-07 WO PCT/CN2023/106218 patent/WO2024074069A1/en unknown
- 2023-07-07 LU LU506888A patent/LU506888B1/en active
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AU1610188A (en) * | 1987-05-19 | 1988-11-24 | Mitsubishi Jukogyo Kabushiki Kaisha | Stirring apparatus and stirring tower type apparatus for polymerization reactions |
CN108948662A (en) * | 2018-06-25 | 2018-12-07 | 安徽众博新材料有限公司 | Preparation method of vacuum-introduced epoxy resin-based halogen-free flame-retardant composite material |
CN113480832A (en) * | 2021-08-03 | 2021-10-08 | 安徽众博新材料有限公司 | 180 ℃ vacuum infusion epoxy resin-based composite material with TG of 170- |
CN113881192A (en) * | 2021-10-18 | 2022-01-04 | 广东华彩复合材料有限公司 | Low-smoke flame-retardant epoxy resin composite material and preparation method thereof |
CN218924599U (en) * | 2022-10-31 | 2023-04-28 | 上海烯纺新材料科技有限公司 | Graphene production temperature regulation and control device |
CN218981227U (en) * | 2022-12-01 | 2023-05-09 | 佛山市顺德区旺海饲料实业有限公司 | Fodder dosing unit |
CN219043998U (en) * | 2022-12-20 | 2023-05-19 | 河北建设集团股份有限公司 | Mixer for building |
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