CN104448684A - Reclaimed ABS flame-retardant modified material and preparation method thereof - Google Patents
Reclaimed ABS flame-retardant modified material and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention relates to the technical field of recycling of an ABS reclaimed material, and particularly relates to a reclaimed ABS flame-retardant modified material and a preparation method thereof. The reclaimed ABS flame-retardant modified material comprises the following substances: an ABS recycling material, a composite flame retardant, a flame-retardant synergist, a composite anti-aging agent, an antioxidant, a composite toughening agent and a coupling agent. The reclaimed ABS flame-retardant modified material prepared through the method disclosed by the invention has high flame-retardant grade as high as V-0 grade, is high in ageing resistance through the addition of the composite anti-aging agent, can be used for enhancing the tensile strength and the bending strength through the addition of the toughening agent, has the advantages of high anti-impact strength, good processing flowability, high glossiness of a finished product, stability in thermal deformation property, high char yield after combustion and no melting dropping and is greatly enhanced in flame retardance without being influenced in mechanical property. The preparation method disclosed by the invention has the advantages of high ABS purity, few impurities and simple preparation process of the obtained ABS recycling material and excellent property and easiness for industrialization realization of reclaimed ABS.
Description
Technical field
The present invention relates to the recovery and utilization technology field of ABS reworked material, be specifically related to a kind of regeneration ABS anti-flaming modified material and preparation method thereof.
Background technology
China Today has entered household electrical appliance and has discarded peak period, scraps household appliances every year by generation more than 3,000 ten thousand, and so huge waste household appliances certainly leads to a large amount of waste or used plastics.The recycling of waste or used plastics has sanitary landfill, burns heat-obtaining, and resource recycling three kinds of modes, and wherein landfill easily causes the wasting of resources and secondary pollution with burning, and this runs counter to the themes of the times of environmental protection.
Nowadays, the mode of regeneration is mainly taked in the recycling of waste or used plastics, mainly comprises Direct Regeneration, modification regeneration, gasification and oiling process.But the Mechanical Properties of Products of Direct Regeneration declines comparatively large, should not make high-grade goods; Plastics high-temperature gasification, oiling are high with the technical difficulty reclaiming the low component product such as monomer, fuel oil, equipment scale is large; And some mechanical property of the goods of modification regeneration can meet or exceed the performance of unmodified resin goods, there is very high added value.Therefore, the modification regeneration of waste or used plastics is the developing direction of resource utilization recycling.
ABS((vinyl cyanide-vinylbenzene-butadienecopolymer) resin is the engineering plastics that in household electric appliances, a class is important, is widely used in component and the shell of the industries such as automobile, electronics, electrical equipment, office equipment.There is a large amount of recuperable ABS resin due to scrapping of goods, the shortage along with oil and the attention to environment, the recycling of ABS resin receives publicity.But, for recovery ABS material, its mechanical property is significantly less than ABS fresh feed, if want, ABS reclaimed materials is used in electronics, electrical equipment, automobile and other industries through modified continuation, just must carry out effective modification to its flame retardant resistance, toughness and shock resistance, to reach the material performance requirement of different purposes.
Summary of the invention
The object of the invention is for deficiency of the prior art, provide a kind of regeneration ABS anti-flaming modified material, it has good flame retardation effect, greatly improves containing oxygen index, and after burning, charring rate is high, and material is excellent in cushion effect, and anti ageing property is excellent.
Another goal of the invention of the present invention is to provide a kind of preparation method regenerating ABS anti-flaming modified material, and it is high that it has the ABS reclaimed materials over-all properties obtained, and impurity is few, and preparation technology is easy, easily realizes the feature of industrialization.
Object of the present invention is achieved through the following technical solutions:
A kind of regeneration ABS anti-flaming modified material, is made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 20-30 part
Retardant synergist 20-25 part
Compound antiaging agent 0.8-2 part
Oxidation inhibitor 1-2 part
Composite toughing agent 5-15 part
Coupling agent 1-2 part.
Further, a kind of regeneration ABS anti-flaming modified material, is made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 20-25 part
Retardant synergist 20-23 part
Compound antiaging agent 0.8-1.3 part
Oxidation inhibitor 1-2 part
Composite toughing agent 6-10 part
Coupling agent 1-2 part.
Further, a kind of regeneration ABS anti-flaming modified material, is made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 23 parts
Retardant synergist 20 parts
Compound antiaging agent 1.1 parts
1 part, oxidation inhibitor
Composite toughing agent 9 parts
Coupling agent 1 part.
Wherein, described composite flame-retardant agent is by 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazines (brominated triazine) and antimonous oxide is composite forms.Described composite toughing agent is made up of ABS high glue powder and zinc oxide.
Under normal circumstances, simple use 2, 4, 6-tri-(2, 4, 6-tribromophenoxy)-1, 3, the performance of the flame-proof ABS that 5-triazine (brominated triazine) and antimonous oxide obtain as compound flame retardant declines all to some extent, reason is rigid particles 2, 4, 6-tri-(2, 4, 6-tribromophenoxy)-1, 3, the interpolation of 5-triazine (brominated triazine) and antimonous oxide can produce certain constraint effect to the body of surrounding, and along with 2, 4, 6-tri-(2, 4, 6-tribromophenoxy)-1, 3, the consumption of 5-triazine (brominated triazine) increases, it can make the rigidity of flame-retardant system improve to increasing of surrounding matrix resin constraint effect, fragility increases, impact strength decreased, agglomeration between rigid particles can obviously become many, agglomerated particles can be prayed the effect of defect and cause stress concentration in matrix resin, cause the sharply decline of fire-retardant recovery ABS shock strength.
By adding the interpolation of ABS high glue powder and zinc oxide, the increase of its consumption is conducive to the shock strength of fire-retardant recovery ABS in continuing ascendant trend.ABS high glue powder is acrylonitrile-butadiene-phenylethene grafted copolymer, its rubber content is between 50%-70%, therefore the chemistry that ABS high glue powder is similar to ABS and physical structure allow itself and ABS have good consistency, so toughness and the tensile strength of material can be promoted, and be better than the elastomericss such as SBS.But the consumption of ABS high glue powder is too high, can be reduced it containing oxygen index.And zinc oxide is as a kind of supplementary additive, it can improve flowing property and the oilness of material, and fire-retardantly has certain synergistic effect to it.
Preferably, in described composite flame-retardant agent, 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazines (brominated triazines) are 3:1 with the weight ratio of antimonous oxide.。The massfraction of the glue content in described ABS high glue powder is 70%.
Preferably, in described composite toughing agent, the weight ratio of ABS high glue powder and zinc oxide is 6:3, and the over-all properties of its toughening effect, flame retardant effect and regeneration ABS fire retardant material is the most excellent.
Described compound antiaging agent is composited by titanium dioxide and hindered amine as light stabilizer, there is double bond in the polyhutadiene in ABS resin, easily destroy by the 300-380nm ultraviolet band in sunlight wave, produce free radical, cause double bond content less, cause shock strength obviously to reduce, easily catabiosis occurs.
The present invention is by adding titanium dioxide and hindered amine as light stabilizer to promote the anti ageing property regenerating ABS fire retardant material.Hindered amine as light stabilizer has the synergy certainly of broken excited state of going out, decomposition of hydrogen peroxide and scavenging free radicals; it can be consumed by volatilizing and move; even lose uv-protection function due to the photodegradation of self; hindered amine as light stabilizer shines owing to being subject to high energy UV width; himself is also partly consumed, and does not play complete provide protection to ABS resin matrix.And titanium dioxide, be preferably the titanium dioxide of rutile type nano structure, the small part ultraviolet in ABS can be fallen into by the large specific surface after super-refinement and interface diffuse scattering, and discharged to vibrate other form such as heat or fluorescence by the compound that electronics one hole is right again after absorbing most of ultraviolet energy by transition of electron, there is molecular rupture after the polyhutadiene disperse phase avoided containing double bond in ABS absorbs ultraviolet.On the other hand, rutile type nano titanic oxide protects hindered amine as light stabilizer effectively to ultraviolet sorption, can play usefulness within the longer time, thus formation superimposed effect impels the resistance of aging of ABS to be improved by a relatively large margin.
Preferably, in described compound antiaging agent, the weight ratio of titanium dioxide and hindered amine as light stabilizer is 6:5, its notched Izod impact strength conservation rate remains on more than 99%, substantially remain unchanged, and notched Izod impact strength improves 15%, therefore this compound proportion is best for ABS twice-laid stuff of the present invention.
Described retardant synergist is magnesium sulfate crystal whisker.Common water and magnesium sulfate crystal whisker are commonly referred to as alkali magnesium sulfate (MgS0
45Mg (OH)
23H
20), be a kind of white needles single crystal fibre, there is excellent mechanical property, modulus is high, intensity is large and good electric property.Meanwhile, because its coefficient of expansion is suitable with plastics, good with most Compatibility in Plastics, after mixing, ABS twice-laid stuff can show excellent physical and mechanical property.In addition, magnesium sulfate crystal whisker also shows good flame retardant properties, and has nontoxic, that the amount of being fuming is little feature concurrently.When magnesium sulfate crystal whisker is used as strongthener of the present invention, not only there is good outward appearance, excellent rigidity, anti-impact force, high modulus in flexure, and there is extremely low volumetric shrinkage, higher size precision and heat impedance.
But crystal whisker materials adds the problem that there is dispersion and orientation in polymkeric substance to, if occur reuniting at polymkeric substance, the mechanical property of material can be reduced, also can cause " candle wick " effect, not reach fire-retardant object.Therefore, for improving whisker agglomeration phenomenon, to its surface treatment, its apparent activation energy need be reduced.
Therefore, the present invention is by adding coupling agent titanic acid ester.Just well can improve mechanical property and the thermal characteristics of material.Its addition is that the titanic acid ester that the magnesium sulfate crystal whisker of 20 parts adds 1 part can play good modifying properties.Excessive or the too small performance that all can affect integral material of addition.
Wherein, described oxidation inhibitor is antioxidant 1010 or irgasfos 168.
Regenerate a preparation method for ABS anti-flaming modified material, comprise the following steps:
Step one, ABS reclaimed materials is pulverized, cleaning, dry after for subsequent use, control water content lower than 0.01%;
Step 2, take material according to weight part, join in high-speed kneading machine, mediate discharging after 4-8min;
Step 3, the discharging of step 2 dropped in tablets press hopper, extruding pelletization obtains modified ABS regenerated granule; Tablets press forcing machine technological temperature is followed successively by from feeding section to die head: 220 DEG C, 230 DEG C, 240 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 210 DEG C.
Beneficial effect of the present invention: the regeneration ABS anti-flaming modified material prepared by the present invention, fire-retardant rank is high, can reach V-0 level, by adding compound antiaging agent, resistance to deterioration is strong, and the interpolation of toughner improves tensile strength and flexural strength, and excellent in cushion effect, processing fluidity is good, the glossiness of finished product is high, and thermal deformation behavior is stablized, and after burning, charring rate is high, dripping without melting, while not affecting its mechanical property, greatly strengthening its flame retardant resistance.The ABS purity that this preparation method has the ABS reclaimed materials obtained is high, and impurity is few, and preparation technology is simple and easy, and the regeneration ABS excellent performance obtained, easily realizes industrialization.
Embodiment
The invention will be further described with the following Examples.
embodiment 1
A kind of regeneration ABS anti-flaming modified material, is made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 20 parts
Retardant synergist 25 parts
Compound antiaging agent 0.8 part
2 parts, oxidation inhibitor
Composite toughing agent 5 parts
Coupling agent 1 part.
In described composite flame-retardant agent, 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazines (brominated triazines) are 3:1 with the weight ratio of antimonous oxide.
In described composite toughing agent, the weight ratio of ABS high glue powder and zinc oxide is 6:3.The massfraction of the glue content in described ABS high glue powder is 70%.
In described compound antiaging agent, the weight ratio of titanium dioxide and hindered amine as light stabilizer is 6:5
Described oxidation inhibitor is antioxidant 1010, and described coupling agent is titanic acid ester.
Regenerate a preparation method for ABS anti-flaming modified material, comprise the following steps:
Step one, ABS reclaimed materials is pulverized, cleaning, dry after for subsequent use, control water content lower than 0.01%.
Step 2, take material according to weight part, join in high-speed kneading machine, mediate discharging after 4min.
Step 3, the discharging of step 2 dropped in tablets press hopper, extruding pelletization obtains modified ABS regenerated granule; Tablets press forcing machine technological temperature is followed successively by from feeding section to die head: 220 DEG C, 230 DEG C, 240 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 210 DEG C.
embodiment 2
A kind of regeneration ABS anti-flaming modified material, is made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 30 parts
Retardant synergist 20 parts
Compound antiaging agent 2 parts
1 part, oxidation inhibitor
Composite toughing agent 15 parts
Coupling agent 2 parts.
In described composite flame-retardant agent, 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazines (brominated triazines) are 3:1 with the weight ratio of antimonous oxide.
In described composite toughing agent, the weight ratio of ABS high glue powder and zinc oxide is 6:3.The massfraction of the glue content in described ABS high glue powder is 70%.
In described compound antiaging agent, the weight ratio of titanium dioxide and hindered amine as light stabilizer is 6:5
Described oxidation inhibitor is irgasfos 168, and described coupling agent is titanic acid ester.
Regenerate a preparation method for ABS anti-flaming modified material, comprise the following steps:
Step one, ABS reclaimed materials is pulverized, cleaning, dry after for subsequent use, control water content lower than 0.01%.
Step 2, take material according to weight part, join in high-speed kneading machine, mediate discharging after 4-8min.
Step 3, the discharging of step 2 dropped in tablets press hopper, extruding pelletization obtains modified ABS regenerated granule; Tablets press forcing machine technological temperature is followed successively by from feeding section to die head: 220 DEG C, 230 DEG C, 240 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 210 DEG C.
embodiment 3
A kind of regeneration ABS anti-flaming modified material, is made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 25 parts
Retardant synergist 22 parts
Compound antiaging agent 1.5 parts
1.5 parts, oxidation inhibitor
Composite toughing agent 10 parts
Coupling agent 2 parts.
In described composite flame-retardant agent, 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazines (brominated triazines) are 3:1 with the weight ratio of antimonous oxide.
In described composite toughing agent, the weight ratio of ABS high glue powder and zinc oxide is 6:3.The massfraction of the glue content in described ABS high glue powder is 70%.
In described compound antiaging agent, the weight ratio of titanium dioxide and hindered amine as light stabilizer is 6:5
Described oxidation inhibitor is antioxidant 1010, and described coupling agent is titanic acid ester.
Regenerate a preparation method for ABS anti-flaming modified material, comprise the following steps:
Step one, ABS reclaimed materials is pulverized, cleaning, dry after for subsequent use, control water content lower than 0.01%.
Step 2, take material according to weight part, join in high-speed kneading machine, mediate discharging after 8min.
Step 3, the discharging of step 2 dropped in tablets press hopper, extruding pelletization obtains modified ABS regenerated granule; Tablets press forcing machine technological temperature is followed successively by from feeding section to die head: 220 DEG C, 230 DEG C, 240 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 210 DEG C.
embodiment 4
A kind of regeneration ABS anti-flaming modified material, is made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 20 parts
Retardant synergist 23 parts
Compound antiaging agent 1.3 parts
2 parts, oxidation inhibitor
Composite toughing agent 6 parts
Coupling agent 1 part.
In described composite flame-retardant agent, 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazines (brominated triazines) are 3:1 with the weight ratio of antimonous oxide.
In described composite toughing agent, the weight ratio of ABS high glue powder and zinc oxide is 6:3.The massfraction of the glue content in described ABS high glue powder is 70%.
In described compound antiaging agent, the weight ratio of titanium dioxide and hindered amine as light stabilizer is 6:5
Described oxidation inhibitor is irgasfos 168, and described coupling agent is titanic acid ester.
Regenerate a preparation method for ABS anti-flaming modified material, comprise the following steps:
Step one, ABS reclaimed materials is pulverized, cleaning, dry after for subsequent use, control water content lower than 0.01%.
Step 2, take material according to weight part, join in high-speed kneading machine, mediate discharging after 5min.
Step 3, the discharging of step 2 dropped in tablets press hopper, extruding pelletization obtains modified ABS regenerated granule; Tablets press forcing machine technological temperature is followed successively by from feeding section to die head: 220 DEG C, 230 DEG C, 240 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 210 DEG C.
embodiment 5
A kind of regeneration ABS anti-flaming modified material, is made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 23 parts
Retardant synergist 20 parts
Compound antiaging agent 1.1 parts
1 part, oxidation inhibitor
Composite toughing agent 9 parts
Coupling agent 1 part.
In described composite flame-retardant agent, 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazines (brominated triazines) are 3:1 with the weight ratio of antimonous oxide.
In described composite toughing agent, the weight ratio of ABS high glue powder and zinc oxide is 6:3.The massfraction of the glue content in described ABS high glue powder is 70%.
In described compound antiaging agent, the weight ratio of titanium dioxide and hindered amine as light stabilizer is 6:5
Described oxidation inhibitor is antioxidant 1010, and described coupling agent is titanic acid ester.
Regenerate a preparation method for ABS anti-flaming modified material, comprise the following steps:
Step one, ABS reclaimed materials is pulverized, cleaning, dry after for subsequent use, control water content lower than 0.01%.
Step 2, take material according to weight part, join in high-speed kneading machine, mediate discharging after 6min.
Step 3, the discharging of step 2 dropped in tablets press hopper, extruding pelletization obtains modified ABS regenerated granule; Tablets press forcing machine technological temperature is followed successively by from feeding section to die head: 220 DEG C, 230 DEG C, 240 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 210 DEG C.
Embodiment 1-5 is carried out aptitude test, and performance is as shown in the table:
| Performance index | Testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Izod notched impact strength (kJ/m 2） | ISO 180 | 11 | 11 | 13 | 16 | 14 |
| Tensile strength (MPa) | ISO 527 | 40 | 40 | 39 | 41 | 43 |
| Elongation at break (%) | ISO 527 | 12 | 12 | 11 | 13 | 14 |
| Flexural strength (MPa) | ISO 178 | 61 | 59 | 57 | 60 | 63 |
| Oxygen index (%) | ISO 4589 | 28 | 25 | 26 | 27 | 30 |
| Testing vertical flammability | UL 94 | V-0 | V-0 | V-0 | V-0 | V-0 |
Can find out according to upper table, the comprehensive mechanical property of regeneration ABS prepared by the present invention and excellent fireproof performance.This regeneration ABS fire retardant material can be applied to and require higher field to motor, hair dryer, power pack, microwave oven, electric cooker, ups power, socket etc. to thermotolerance, flame retardant properties.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. regenerate an ABS anti-flaming modified material, it is characterized in that: be made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 20-30 part
Retardant synergist 20-25 part
Compound antiaging agent 0.8-2 part
Oxidation inhibitor 1-2 part
Composite toughing agent 5-15 part
Coupling agent 1-2 part,
Wherein, described composite flame-retardant agent is by 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazines (brominated triazine) and antimonous oxide is composite forms; Described retardant synergist is magnesium sulfate crystal whisker, and described compound antiaging agent is composited by titanium dioxide and hindered amine as light stabilizer, and described composite toughing agent is made up of ABS high glue powder and zinc oxide.
2. one regeneration ABS anti-flaming modified material according to claim 1, is characterized in that: be made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 20-25 part
Retardant synergist 20-23 part
Compound antiaging agent 0.8-1.3 part
Oxidation inhibitor 1-2 part
Composite toughing agent 6-10 part
Coupling agent 1-2 part.
3. one regeneration ABS anti-flaming modified material according to claim 1, is characterized in that: be made up of the material of following weight part:
ABS reclaimed materials 100 parts
Composite flame-retardant agent 23 parts
Retardant synergist 20 parts
Compound antiaging agent 1.1 parts
1 part, oxidation inhibitor
Composite toughing agent 9 parts
Coupling agent 1 part.
4. one regeneration ABS anti-flaming modified material according to claim 1, is characterized in that: in described composite flame-retardant agent 2,4,6-tri-(2,4,6-tribromophenoxy)-1,3,5-triazine (brominated triazine) is 3:1 with the weight ratio of antimonous oxide.
5. one regeneration ABS anti-flaming modified material according to claim 1, is characterized in that: in described composite toughing agent, the weight ratio of ABS high glue powder and zinc oxide is 6:3.
6. one regeneration ABS anti-flaming modified material according to claim 1, is characterized in that: in described composite toughing agent, ABS high glue powder is 70% containing glue massfraction.
7. one regeneration ABS anti-flaming modified material according to claim 1, is characterized in that: in described compound antiaging agent, the weight ratio of titanium dioxide and hindered amine as light stabilizer is 6:5.
8. one regeneration ABS anti-flaming modified material according to claim 1, is characterized in that: described coupling agent is titanic acid ester.
9. one regeneration ABS anti-flaming modified material according to claim 1, is characterized in that: described oxidation inhibitor is antioxidant 1010 or irgasfos 168.
10. a kind of preparation method regenerating ABS anti-flaming modified material described in any one of claim 1-9, is characterized in that: comprise the following steps:
Step one, ABS reclaimed materials is pulverized, cleaning, dry after for subsequent use, control water content lower than 0.01%;
Step 2, take material according to weight part, join in high-speed kneading machine, mediate discharging after 4-8min;
Step 3, the discharging of step 2 dropped in tablets press hopper, extruding pelletization obtains modified ABS regenerated granule; Tablets press forcing machine technological temperature is followed successively by from feeding section to die head: 220 DEG C, 230 DEG C, 240 DEG C, 220 DEG C, 220 DEG C, 210 DEG C, 210 DEG C.
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