CN104962022A - Heat-resisting, scraping-resisting and high-transmittance PMMA alloy resin and preparation method thereof - Google Patents
Heat-resisting, scraping-resisting and high-transmittance PMMA alloy resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a heat-resisting, scraping-resisting and high-transmittance PMMA alloy resin composition. The PMMA alloy resin composition is prepared from the following raw materials in parts by weight: 10-95 parts of polymethyl methacrylate and 5-90 parts of a PMMA special heat-resisting agent, wherein the PMMA special heat-resisting agent is N-phenylmaleimide-styrene-methyl methacrylate terpolymer P (NPMI-St-MMA). The invention further provides a preparation method of the PMMA alloy resin composition. The preparation method has the advantages that the utilized N-phenylmaleimide-styrene-methyl methacrylate terpolymer has good compatibility with polymethyl methacrylate and is high in transparency after being blended, and the prepared alloy resin has the advantages of high transmittance, scraping resistance and heat resistance; the PMMA alloy resin composition can further contain processing aids including an impact modifier, a liquidity regulator, a lubricant and a demolding agent, and can be used for preparing PMMA alloy resin compositions for various purposes; the preparation process of the PMMA alloy resin is relatively simple and is beneficial to mass production.
Description
Technical field
The present invention relates to polymeric material field, specifically, is a kind of heat-resisting scrape resistant high permeability PMMA alloy resin and preparation method thereof.
Background technology
Polymethylmethacrylate has excellent scraping and wiping resistance performance and transparency, and dimensional stability is high, and creep resistant is good, can as good optical material.But its impact resistance and resistance toheat be not good limits its application in fields such as automobile, electronic apparatus, glass lens and medical apparatus.In order to improve the impact of PMMA and resistance to heat energy and keep its transparency simultaneously, investigators have done a large amount of trials.Direct acrylic elastomer toughened polymethyl methacrylate (PMMA) can improve its toughness on the basis retaining the transparency, but resistance toheat can obviously decline.Also be same by toughened polymethyl methacrylate (PMMA)/AS, MS, MSAN alloy result.Add conventional heat refractory agent α methyl-styrene, N-phenylmaleimide-styrol copolymer, N-phenylmaleimide-styrene-acrylonitrile copolymer can have a strong impact on its transparency.Although by add PC realize the impact of PMMA and heat-resisting raising can and keep its transparency to cause paying close attention to widely, when problems faced is high-temperature blending at present, both poor compatibility, mix uneven, cause final goods opaque.The PC/PMMA alloy that conventional blending technology is made, when PMMA addition exceedes certain proportion (generally more than 3%), namely product surface there will be the effect sending out mist pearly-lustre, if PMMA content continues to increase, goods are opaque.Prepare transparent PMMA/PC alloy and be still material circle a great problem.
A kind of method preparing transparent PMMA/PC alloy is provided in Chinese patent literature CN201410328787.4.But this method need pass into high-pressure inert gas after methacrylate resin melting, use high pressure syringe pump to feed mouth from the side of forcing machine and inject, control gaseous tension higher than 7.4MPa, and the forcing machine using length-to-diameter ratio larger, in processing requirement and strict, equipment is complicated, is unfavorable for a large amount of production.
Summary of the invention
The object of the invention is for deficiency of the prior art, a kind of heat-resisting scrape resistant high permeability PMMA alloy resin combination is provided.
The present invention again one object be that the preparation method of above-mentioned composition is provided.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of heat-resisting scrape resistant high permeability PMMA alloy resin combination, described composition is made up of the raw material of following weight part: polymethylmethacrylate 10-95 part, PMMA special heat-resistant agent 5-90 part.
Described polymethylmethacrylate weight-average molecular weight Mw is 40000-100000g/mol; The special heat-resistant agent of described PMMA is N-phenylmaleimide-styrene methyl methacrylate terpolymer P (NPMI-St-MMA), wherein the content of N-phenylmaleimide is 5 ~ 40%, and weight-average molecular weight is 40000-300000g/mol.
Described heat-resisting scrape resistant high permeability PMMA alloy resin combination also comprises processing aid 0.1-50 part, and described processing aid is selected from one or more in impact modifier, fluidity regulator, antioxidant, lubricant, photostabilizer, thermo-stabilizer, tinting material, releasing agent, static inhibitor.
Described anti-impact modifier is selected from one in line style toughner or core-shell type toughner or its mixture; Described fluidity regulator be selected from acrylonitritrile-styrene resin AS, acrylic ester-acrylonitrile-styrol copolymer MSAN, acrylic styrene copolymer MS one or more; Described oxidation inhibitor is selected from the one in aromatic amine oxidation inhibitor, Hinered phenols antioxidant, auxiliary antioxidant; Described lubricant is selected from one or more in silicone oil, white mineral oil, fatty acid amide, barium stearate, Magnesium Stearate, paraffin, polyethylene wax, ethylene bis stearic acid amide, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer, aromatic phosphate acid ester; Described photostabilizer is selected from one or more in benzophenone UV absorption agent, benzotriazole uv absorbers, triazines UV absorption agent, hindered amine light stabilizer; Described thermo-stabilizer is selected from one or more in metal soap thermal stabilizers, organic tin thermo-stabilizer, rare-earth stabilizer, phosphite ester stabilizer, epoxy compounds; Described tinting material is selected from one or more in dye class tinting material, pigment dyestuff, mineral dye, white dyes.
Described line style toughner is selected from divinyl rubber, ethylene-propylene rubber(EPR), EPDM, styrene-butadiene copolymer, styrene-butadiene-styrene, styrene-isoprene copolymer, one in styrene-isoprene-styrene copolymer-and selective hydration product thereof or its mixture, or vinylformic acid-silicone rubber kinds toughner, ethylene-methyl acrylate, Ethylene-butyl acrylate, acrylonitrile-butadiene-styrene copolymer toughner, one in acrylonitrile-butadiene-acrylate copolymer or MBS or its mixture, described core-shell type toughner core part is polybutadiene rubber and multipolymer thereof, or polyacrylic rubber and multipolymer thereof, described core-shell type toughner shell sections is polyacrylic ester and multipolymer thereof or styrene-acrylonitrile copolymer, and described core-shell type toughner also comprises the various functionalization products of above-mentioned toughner.
For realizing above-mentioned second object, the technical scheme that the present invention takes is:
A preparation method for heat-resisting scrape resistant high permeability PMMA alloy resin combination, is characterized in that, comprise the following steps:
(1) get the raw materials ready according to described component and weight part;
(2) above-mentioned raw materials is placed in high-speed mixer by formula stirs, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product; Wherein extrusion temperature is 200 DEG C-270 DEG C.
The invention has the advantages that:
1. the present invention use N-phenylmaleimide-styrene methyl methacrylate terpolymer and polymethylmethacrylate have good consistency, blended rear transparency is high, and obtained alloy resin has that transmitance is high, scrape resistant, heat-resisting advantage.
2. PMMA alloy resin combination of the present invention can comprise the processing aids such as impact modifier, fluidity regulator, lubricant, releasing agent further, can prepare the PMMA alloy resin combination of various uses.
3. the preparation technology of PMMA alloy resin of the present invention is relatively simple, is conducive to a large amount of production.
Embodiment
The preparation (one) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 1 the present invention
Raw material: polymethylmethacrylate 95 parts, the special heat-resistant agent of PMMA 5 parts.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 5%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 200 DEG C.
The preparation (two) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 2 the present invention
Raw material: polymethylmethacrylate 10 parts, the special heat-resistant agent of PMMA 90 parts.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 20%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 240 DEG C.
The preparation (three) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 3 the present invention
Raw material: polymethylmethacrylate 70 parts, the special heat-resistant agent of PMMA 30 parts, flowing regulator 20 parts, lubricant 2 parts.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 40%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 270 DEG C.
The preparation (four) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 4 the present invention
Raw material: polymethylmethacrylate 70 parts, the special heat-resistant agent of PMMA 20 parts, impact modifier 20 parts, lubricant 2 parts, thermo-stabilizer 0.5 part.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 20%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 250 DEG C.
The preparation (five) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 5 the present invention
Raw material: polymethylmethacrylate 65 parts, the special heat-resistant agent of PMMA 25 parts, lubricant 2 parts, 1 part, oxidation inhibitor, photostabilizer 0.5 part, tinting material 0.5 part.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 20%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 220 DEG C.
The preparation (six) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 6 the present invention
Raw material: polymethylmethacrylate 35 parts, the special heat-resistant agent of PMMA 65 parts, impact modifier 10 parts, lubricant 0.5 part, 0.5 part, oxidation inhibitor.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 10%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 250 DEG C.
The preparation (seven) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 7 the present invention
Raw material: polymethylmethacrylate 80 parts, the special heat-resistant agent of PMMA 20 parts, lubricant 2 parts, photostabilizer 0.5 part, thermo-stabilizer 0.5 part, tinting material 0.1 part.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 20%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 240 DEG C.
The preparation (eight) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 8 the present invention
Raw material: polymethylmethacrylate 80 parts, the special heat-resistant agent of PMMA 20 parts, fluidity regulator 10 parts, photostabilizer 2 parts, tinting material 0.5 part.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 30%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 240 DEG C.
The preparation (nine) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 9 the present invention
Raw material: polymethylmethacrylate 50 parts, the special heat-resistant agent of PMMA 30 parts, impact modifier 10 parts, 1 part, oxidation inhibitor, thermo-stabilizer 0.5 part.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 25%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 240 DEG C.
The preparation (ten) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 10 the present invention
Raw material: polymethylmethacrylate 60 parts, the special heat-resistant agent of PMMA 20 parts, fluidity regulator 10 parts, lubricant 2 parts, 1 part, oxidation inhibitor, photostabilizer 0.5 part, thermo-stabilizer 0.5 part, tinting material 0.1 part.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 20%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 240 DEG C.
The preparation (11) of a kind of heat-resisting scrape resistant high permeability PMMA alloy resin of embodiment 11 the present invention
Raw material: polymethylmethacrylate 65 parts, the special heat-resistant agent of PMMA 15 parts, fluidity regulator 20 parts, lubricant 1 part, 1 part, oxidation inhibitor, photostabilizer 0.5 part, thermo-stabilizer 0.5 part, tinting material 0.1 part.Wherein, in the special heat-resistant agent of described PMMA, the NPMI content of P (NPMI-St-MMA) is 10%.
Preparation technology: above-mentioned raw materials is placed in high-speed mixer by formula and mixes, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product.Wherein extrusion temperature is 240 DEG C.
It should be noted that, in embodiment 1-11, the starting material of employing: PMMA is the strange beautiful CM207G in Taiwan; The special heat-resistant agent of PMMA is N-phenylmaleimide-styrene methyl methacrylate terpolymer P (NPMI-St-MMA), wherein, in P (NPMI-St-MMA), the content of NPMI is 5 ~ 40%, and weight-average molecular weight is 40000-300000g/mol; The impact modifier adopted is the EM500 of LG; Described fluidity regulator is the acrylonitritrile-styrene resin SAN320 resin of Korea S's brocade lake petrochemical industry; The oxidation inhibitor adopted is the mixture of antioxidant 1010 and irgasfos 168; Described lubricant is pentaerythritol stearate series lubricant agent; Described photostabilizer is for being benzotriazole uv absorbers UV234; Described thermo-stabilizer is metal soap; Described tinting material is white dyes 184.
The performance test of embodiment 12 PMMA alloy resin of the present invention
One, experiment grouping
This test is divided into 8 groups, wherein test group 5 groups, control group 3 groups.
Test group adopts the PMMA alloy resin obtained by embodiment 1,3,6,9,10 respectively.
Control group 1: take following starting material by weight: PMMA95 part, PC 5 parts; Then be placed in high-speed mixer to mix, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, obtained PMMA alloy resin as a control group 1.
Control group 2: take following starting material by weight: PMMA95 part, MS-NI 5 parts; Then be placed in high-speed mixer to mix, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, obtained PMMA alloy resin as a control group 2.
Control group 3: take PMMA100 part by weight, then be placed in high-speed mixer to mix, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, obtained PMMA alloy resin as a control group 3.
It should be noted that, the PC that control group 1-3 adopts is Supreme Being people L1225WS, and N-phenylmaleimide-styrol copolymer is electrochemical MS-NI.
Two, testing method
By the alloy resin of each group at 80 DEG C of more than vacuum-drying 12h, then test its physicals.
1. transmission measurement
Be the specular plate of 3mm by the particle prepared injection moulding thickness at the temperature of 250 DEG C, carry out transmission measurement and hardness test.The concrete testing method of transmitance is shown in ASTM D1003-2007 transparent plastics transmittance and haze test method.
2. pencil hardness test
Be the specular plate of 3mm by the particle prepared injection moulding thickness at the temperature of 250 DEG C, carry out hardness test.Pencil hardness test is tested according to GB/T 6739-1996, the heavy 500g of counterweight.
3. heat resisting temperature test
Heat resisting temperature is tested according to the testing method of ASTMD1525-09 plastics dimension card (vicat) softening temperature, and test condition is 5kg, 50 DEG C/h.
Three, test result
Prepared by test group 1-5 and control group 1-3, the test result of the physicals of resin is shown in Table 1.
Table 1 test group 1-5 and control group 1-3 the performance test results
As shown in Table 1, the present invention adopts PMMA special heat-resistant agent N-phenylmaleimide-styrene methyl methacrylate terpolymer P (NPMI-St-MMA) can prepare the PMMA alloy resin of high-clarity, also have outstanding scratch resistance, heat resisting temperature is higher simultaneously.The PMMA alloy resin adopting PMMA and PC or MS-NI to prepare then has obvious pearly-lustre phenomenon, although single resin using PMMA to prepare has high transmission rate, its heat resisting temperature is lower.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the inventive method; can also make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.
Claims (6)
1. a heat-resisting scrape resistant high permeability PMMA alloy resin combination, it is characterized in that, described composition is made up of the raw material of following weight part: polymethylmethacrylate 10-95 part, PMMA special heat-resistant agent 5-90 part.
2. heat-resisting scrape resistant high permeability PMMA alloy resin combination according to claim 1, it is characterized in that, described polymethylmethacrylate weight-average molecular weight Mw is 40000-100000g/mol; The special heat-resistant agent of described PMMA is N-phenylmaleimide-styrene methyl methacrylate terpolymer P (NPMI-St-MMA), wherein the content of N-phenylmaleimide is 5 ~ 40%, and weight-average molecular weight is 40000-300000g/mol.
3. heat-resisting scrape resistant high permeability PMMA alloy resin combination according to claim 1 and 2, it is characterized in that, also comprise processing aid 0.1-50 part, described processing aid is selected from one or more in impact modifier, fluidity regulator, antioxidant, lubricant, photostabilizer, thermo-stabilizer, tinting material, releasing agent, static inhibitor.
4. heat-resisting scrape resistant high permeability PMMA alloy resin combination according to claim 3, is characterized in that, described anti-impact modifier is selected from one in line style toughner or core-shell type toughner or its mixture; Described fluidity regulator be selected from acrylonitritrile-styrene resin AS, acrylic ester-acrylonitrile-styrol copolymer MSAN, acrylic styrene copolymer MS one or more; Described oxidation inhibitor is selected from the one in aromatic amine oxidation inhibitor, Hinered phenols antioxidant, auxiliary antioxidant; Described lubricant is selected from one or more in silicone oil, white mineral oil, fatty acid amide, barium stearate, Magnesium Stearate, paraffin, polyethylene wax, ethylene bis stearic acid amide, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer, aromatic phosphate acid ester; Described photostabilizer is selected from one or more in benzophenone UV absorption agent, benzotriazole uv absorbers, triazines UV absorption agent, hindered amine light stabilizer; Described thermo-stabilizer is selected from one or more in metal soap thermal stabilizers, organic tin thermo-stabilizer, rare-earth stabilizer, phosphite ester stabilizer, epoxy compounds; Described tinting material is selected from one or more in dye class tinting material, pigment dyestuff, mineral dye, white dyes.
5. heat-resisting scrape resistant high permeability PMMA alloy resin combination according to claim 4, it is characterized in that, described line style toughner is selected from divinyl rubber, ethylene-propylene rubber(EPR), EPDM, styrene-butadiene copolymer, styrene-butadiene-styrene, styrene-isoprene copolymer, one or more in styrene-isoprene-styrene copolymer-and selective hydration product thereof, or vinylformic acid-silicone rubber kinds toughner, ethylene-methyl acrylate, Ethylene-butyl acrylate, acrylonitrile-butadiene-styrene copolymer toughner, one or more in acrylonitrile-butadiene-acrylate copolymer or MBS, described core-shell type toughner core part is polybutadiene rubber and multipolymer thereof, or polyacrylic rubber and multipolymer thereof, described core-shell type toughner shell sections is polyacrylic ester and multipolymer thereof or styrene-acrylonitrile copolymer, and described core-shell type toughner also comprises the various functionalization products of above-mentioned toughner.
6. the preparation method of the arbitrary described heat-resisting scrape resistant high permeability PMMA alloy resin of claim 1-2, is characterized in that, comprise the following steps:
(1) get the raw materials ready according to described component and weight part;
(2) above-mentioned raw materials is placed in high-speed mixer by formula stirs, send in twin screw extruder through measuring apparatus after mixing, the conveying of screw rod, shearing and mixing under, by material melting, compound, then through extruding, tie rod, cooling, pelletizing step, to obtain final product; Wherein extrusion temperature is 200 DEG C-270 DEG C.
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| CN106009453A (en) * | 2016-08-16 | 2016-10-12 | 苏州市云林电子有限公司 | Thermal-stability modified PMMA rubber |
| CN107118482A (en) * | 2017-05-03 | 2017-09-01 | 阜南县邰氏宇崴运动器材有限公司 | It is a kind of for elastomeric material of roller-skates pulley and preparation method thereof |
| CN107936436A (en) * | 2017-12-22 | 2018-04-20 | 鄢海军 | A kind of PMMA materials of scratch-resistant and preparation method thereof |
| CN108822498A (en) * | 2018-07-11 | 2018-11-16 | 望江县天长光学仪器有限公司 | A kind of polymethyl methacrylate lens material |
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| CN106009453A (en) * | 2016-08-16 | 2016-10-12 | 苏州市云林电子有限公司 | Thermal-stability modified PMMA rubber |
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