CN103467966A - Inflaming retarding PPE/PS/ABS alloy plastic as well as preparation method and application thereof - Google Patents
Inflaming retarding PPE/PS/ABS alloy plastic as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an inflaming retarding PPE/PS/ABS alloy plastic as well as a preparation method and the application thereof. The inflaming retarding PPE/PS/ABS alloy plastic comprises the following components: 30-60% of PPE, 20-40% of PS, 2-15% of ABS, 1-8% of flexibilizer, 1-10% of compatilizer, 8-18% of flame retardant, 0.1-1% of antioxidant, and 0.1-1% of lubricant, wherein the compatilizer is maleic anhydride graft PPE, and/or the flexibilizer is a compound of SEBS and SBS. The inflaming retarding PPE/PS/ABS alloy plastic, provided by the invention, has excellent inflaming retarding performance while having excellent chemical resistance and surface gloss. The preparation method of the inflaming retarding PPE/PS/ABS alloy plastic adopts matured smelting extrusion technology to prepare, the technology is simple, the technology conditions are easy to control, and the prepared inflaming retarding PPE/PS/ABS alloy plastic is stable in performance.
Description
Technical field
The invention belongs to technical field of polymer composite materials, particularly a kind of fire-retardant PPE/PS/ABS alloy plastic and preparation method thereof and application.
Background technology
Polyphenylene oxide (PPE) is that resin is the engineering plastics of thermotolerance, electrical characteristic, chemical reagent resistance excellence, but then, itself while using separately, has the shortcoming of poor fluidity, shaping difficulty and so on.In addition, the Polyphony Ether resin taken out from poly-unit is generally powdery, and slide in its screw surface place at forcing machine etc. easy ten, metering property is unstable, aspect shaping processability, is disadvantageous.For this reason, shaping processability, mobility, the shock-resistance of improving polyphenylene oxide of take is purpose, and having developed and being combined with polystyrene (PS) is the material of resin, and it uses in various fields as a kind of engineering plastics.
On the other hand, generally as by the thermoplastic resin formed raw material form that adds man-hour, usually with the form supply of the granule resin mass that is known as pellet.In order to coordinate polystyrene resin to form pellet in the Polyphony Ether resin; Polyphony Ether resin (being generally Powdered) and polystyrene resin are supplied in forcing machine; form with the molten resin of strand form is extruded; after cooling in tank etc.; the use tablets press cuts off, and forms pellet.
Yet, while in coordinating polystyrene resin and be supplied to forcing machine in the Polyphony Ether toner, carrying out extrusion molding, air is easily along with pulverous resin enters, because such powder that contains air easily slides at the screw rod transmission face place of forcing machine, thereby the conveying that makes screw rod becomes unstable, the residence time in forcing machine is elongated, easily makes Polyphony Ether resin oxidative degradation.In order to prevent oxidative degradation, the method for adding antioxidant in raw material is arranged usually.
Solve the oxidisability problem although add antioxidant energy branch, but in practical application, particularly at relative characteristic, require as find in the application of the fields such as electrical equipment, auto parts, solar junction box, this Polyphony Ether resin that is combined with polystyrene resin that is to say the PPE/PS alloy plastic, and there are the following problems: its chemical resistant properties, surface gloss are poor.Therefore, how to solve this technical problem of PPE/PS alloy plastic, expand its range of application particularly the application in the fields such as electrical equipment, auto parts, solar junction box be the realistic problem need solved.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of fire-retardant PPE/PS/ABS alloy plastic and application thereof are provided, to solve existing PPE/PS matrix material chemical resistant properties and the poor technical problem of surface gloss.
Another object of the present invention is to provide the easily preparation method with chemical resistant properties and the good fire-retardant PPE/PS/ABS alloy plastic of surface gloss of control of a kind of condition.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of fire-retardant PPE/PS/ABS alloy plastic, it comprises the component of following weight percent:
Wherein, described compatilizer is maleic anhydride graft PPE, and/or described toughner is maleic anhydride graft SEBS and SBS mixture.
And a kind of preparation method of fire-retardant PPE/PS/ABS alloy plastic comprises the following steps:
Formula according to above-mentioned fire-retardant PPE/PS/ABS alloy plastic takes each component;
Each component taken is carried out being melt extruded granulation after mixing treatment.
And, the above-mentioned application of fire-retardant PPE/PS/ABS alloy plastic in preparing electric appliance casing, auto parts, sun power.
Above-mentioned fire-retardant PPE/PS/ABS alloy plastic adopts ABS to interact in the presence of the components such as toughner, compatilizer as one of matrix component and PPE, PS matrix component, make fire-retardant PPE/PS/ABS alloy plastic there is excellent chemical resistant properties, and the product surface glossiness that adopts this fire-retardant PPE/PS/ABS alloy plastic to prepare is good, also has good mechanical property, processing characteristics and higher heat-drawn wire simultaneously.Wherein, due to the participation of fire retardant, this fire-retardant PPE/PS/ABS alloy plastic also has excellent flame retardant resistance, environmental protection, safety.
Above-mentioned fire-retardant PPE/PS/ABS alloy plastic preparation method adopts the ripe technique that melt extrudes to be prepared, and its technique is simple, and processing condition are easily controlled, and the fire-retardant PPE/PS/ABS alloy plastic stable performance of preparing.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The fire-retardant PPE/PS/ABS alloy plastic that there is high heat-drawn wire when the embodiment of the present invention provides a kind of good flame resistance.
A kind of fire-retardant PPE/PS/ABS alloy plastic, it comprises the component of following weight percent:
Wherein, described compatilizer is maleic anhydride graft PPE, and/or described toughner is SEBS and SBS mixture.
Particularly, above-mentioned PPE(polyphenylene oxide, gather 2,6-dimethyl-1, the 4-phenylate) and the PS(polystyrene) with the ABS(acrylonitrile-butadiene-styrene copolymer) formed the matrix component of the fire-retardant PPE/PS/ABS alloy plastic of above-described embodiment together with the three, modification by ABS, PS to PPE, make fire-retardant PPE/PS/ABS alloy plastic have excellent chemical resistant properties and surface gloss.Better in order to make three matrix components interact, make fire-retardant PPE/PS/ABS alloy plastic chemical resistant properties and surface gloss better, therefore, PPE, PS, ABS have following preferred embodiment:
In a preferred embodiment, to select limiting viscosity be 40～45cm to PPE
3the PPE of/g.In specific embodiment, this PPE can be the polyphenylene oxide resin of the limiting viscosities 40～45 such as PX100F, PX100L of Mitsubishi's engineering plastics, can be maybe the limiting viscosity 40～45cm of the innovation plastics such as SABIC
3the polyphenylene oxide resin of/g.
In a preferred embodiment, PS selects high-impact injection grade HIPS.Therefore, in specific embodiment, this PS selects strange beautiful PH-88, the PH-888 produced, one or more mixtures in HP8250.Wherein, PH-88, PH-888 that this PH-88, PH-888 select Zhenjiang Qi Mei chemical company to produce, HP8250 selects the HIPS HP8250 of Taiwan man-made fiber stock company etc.
In a preferred embodiment, ABS selects general injection moulding rank, has high gloss, medium impact ABS, and therefore, in specific embodiment, this ABS selects one or both mixtures in the AG15A1 of PA-757K, platform of strange U.S..
In further preferred embodiment, it is 40～45cm that PPE selects limiting viscosity
3the PPE of/g, PS selects one or more mixtures in PH-88, PH-888, HP8250.
Or, in further preferred embodiment, it is 40～45cm that PPE selects limiting viscosity
3the PPE of/g, PS selects one or more mixtures in PH-88, PH-888, HP8250, and ABS selects the PA-757K of strange U.S., one or both mixtures in AG15A1.
In specific embodiment, above-mentioned PPE content can be 30%, 35%, 40%, 48%, 50%, 55%, 58%, 60% etc.; And/or PS content can be 20%, 22%, 25%, 30%, 35%, 40% etc.; And/or ABS content can be 2%, 4%, 6%, 9%, 10%, 12%, 15% etc.
In the above-described embodiments, ABS and PPO and PS are incompatible, and therefore, above-mentioned compatilizer is selected from the compatilizer into maleic anhydride graft PPE, and the existence of this specific compatilizer has effectively overcome this difficult problem, make ABS and PPO and PS obtain well.In specific embodiment, the PPE in this maleic anhydride graft PPE compatilizer can select above-mentioned PPE.In another specific embodiment, this toughner content can be 1%, 2%, 2.5%, 3.0%, 4%, 5%, 6%, 7%, 8%, 9%, 10% etc.
In a preferred embodiment, this maleic anhydride graft PPE compatilizer is prepared as follows:
PPE is extruded to cooling and dicing with dual-screw pelletizer through 240～300 ℃ of melt kneading after as PX100F and maleic anhydride, initiator batch mixing to be formed.Wherein, PPE, maleic anhydride and initiator three materials are than being 100:(2～4): (0.05～0.08).Wherein, initiator can be selected conventional grafting initiator.
One of effect of above-mentioned toughner is to play the anti-impact modifier function, and it selects SEBS and SBS mixture.In this SEBS and SBS mixture, the weight ratio of this SEBS and SBS is 1:1～2.
In specific embodiment, this SEBS can select the SBES of molecular weight in linearity or high molecular, as SEBS YH-503, the YH-502 etc. of Sinopec Ba Ling branch office; SBS can select the B/S(Butadiene/Styrene)=type SBS of 70/30or60/40, as SBS1401, the SBS1301 etc. of Sinopec Ba Ling branch office.In another specific embodiment, this toughner content can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% etc.
Above-mentioned specific toughner or toughner, together with compatilizer, make above-mentioned fire-retardant PPE/PS/ABS alloy plastic have excellent shock resistance, and have excellent chemical resistance.Wherein, the compatilizer of this characteristic can make between ABS and PPE, PS compatible, makes PPE/PS/ABS alloy plastic chemical resistant properties strong, has excellent surface gloss.
Above-mentioned fire retardant is preferably a kind of or both mixtures in tetraphenyl (bisphenol-A) bisphosphate (BDP), tetraphenyl resorcinol diphosphate (RDP).Its consumption can be 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 18% etc.Certainly, this fire retardant also can be selected other fire retardants, makes fire-retardant PPE/PS/ABS alloy plastic have flame retardant properties.
Above-mentioned lubricant can make each component be uniformly dispersed in melt extruding process, improves the stability of above-mentioned fire-retardant PPE/PS/ABS alloy plastic, makes fire-retardant PPE/PS/ABS alloy plastic have smooth surface simultaneously.In a preferred embodiment, this lubricant be that PETS, E are cured, at least one or two the above mixtures in the type siloxane lubricant.In specific embodiment, its consumption can be the percentage composition such as 0%, 0.3%, 1%.
The existence of above-mentioned antioxidant component, can improve the ageing resistance of above-mentioned fire-retardant PPE/PS/ABS alloy plastic, as ageing resistance such as heat-resisting, oxygen, Weather, static-agings, can the effect between above-mentioned fire retardant and matrix component not impacted simultaneously, guaranteed the characteristics such as the flame retardant resistance of the fire-retardant PPE/PS/ABS alloy plastic of above-described embodiment and high heat distortion temperature.Therefore, in preferred embodiment, oxidation inhibitor is one or more mixtures in three (2,4-DTBP) phosphorous acid ester, β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl alcohol ester, zinc oxide.That concrete can be the Chinox168 of two key chemical industry shares.
Above-mentioned fire-retardant PPE/PS/ABS alloy plastic owing to introducing ABS in the PPE/PS alloy on the vinyl cyanide segment in ABS-CN be a polar group just this polar group be given to alloy material with chemical resistant properties, improved PPE/PS/ABS alloy plastic surface gloss thereby the ABS selected is high-light ABS simultaneously.
Above-mentioned fire-retardant PPE/PS/ABS alloy plastic adopts ABS, PPE, PS as matrix component, this ABS and PPE, PS matrix component interact in the presence of the components such as toughner, compatilizer, make fire-retardant PPE/PS/ABS alloy plastic chemical resistant properties strong, and the product surface glossiness that adopts this fire-retardant PPE/PS/ABS alloy plastic to prepare is good, also there is good mechanical property, processing characteristics and higher heat-drawn wire simultaneously, concrete as shown in hereinafter table.Wherein, due to the participation of fire retardant, this fire-retardant PPE/PS/ABS alloy plastic also has excellent flame retardant resistance, environmental protection, safety.The existence of oxidation inhibitor, give this fire-retardant PPE/PS/ABS alloy plastic and have good ageing resistance, and the existence of lubricant, make each component be uniformly dispersed, the stable performance of fire-retardant PPE/PS/ABS alloy plastic, and preparation has strengthened the full glossiness of its preparation table.In addition, can also be to the kind of each component in above-mentioned fire-retardant PPE/PS/ABS alloy plastic embodiment and the further optimal control of content, realize the optimization of the performances such as chemical resistant properties to fire-retardant PPE/PS/ABS alloy plastic, its product surface glossiness.
Correspondingly, the embodiment of the present invention also provides the easily preparation method with chemical resistant properties and the good fire-retardant PPE/PS/ABS alloy plastic of surface gloss of control of a kind of condition.The method can be used for preparing above-mentioned fire-retardant PPE/PS/ABS alloy plastic, and particularly, the method comprises the steps:
S01. take recipe ingredient: the formula according to above-mentioned fire-retardant PPE/PS/ABS alloy plastic takes each component;
S02. melt extrude processing after mixing treatment: each component that will take carries out being melt extruded granulation after mixing treatment.
Particularly, each component preferred content in the formula of the fire-retardant PPE/PS/ABS alloy plastic in above-mentioned steps S01 and formula and kind as described above, in order to save length, do not repeat them here.
In above-mentioned steps S02, the mixing treatment of each component can be carried out according to existing conventional method for mixing, as directly each component mixed and carried out stirring and evenly mixing, can adopt mixer to realize mixing treatment, raises the efficiency.
In this step S02 melt extrude processing can adopt this area routine melt extrude equipment and the expressing technique condition is carried out, for flame retardant properties, heat-drawn wire and the mechanical property of the fire-retardant PPE/PS/ABS alloy plastic that makes preparation more excellent, in a preferred embodiment, this temperature that melt extrudes processing is 200～260 ℃.It melt extrudes equipment and is preferably twin screw extruder.
Above-mentioned fire-retardant PPE/PS/ABS alloy plastic preparation method adopts the ripe technique that melt extrudes to be prepared, and its technique is simple, and processing condition are easily controlled, and the fire-retardant PPE/PS/ABS alloy plastic stable performance of preparing.In addition, the characteristics that its preparation method is low for equipment requirements, be suitable for suitability for industrialized production.
There is excellent chemical resistant properties and good and good mechanical property, processing characteristics and the high heat distortion temperature of surface gloss just because of above-mentioned fire-retardant PPE/PS/ABS alloy plastic, and but adopting process simply, easily controls and ripe preparation method prepares, therefore, this fire-retardant PPE/PS/ABS alloy plastic application in preparing electric appliance casing, auto parts, sun power.
Embodiment 1
A kind of fire-retardant PPE/PS/ABS alloy plastic and preparation method thereof, this fire-retardant PPE/PS/ABS alloy plastic comprises the component as weight percent in the embodiment 1 of table 1.Its preparation method is as follows:
Each component in table 1 embodiment 1 is proportionally carried out to mixing treatment, until each component mixes, then mixture is melt extruded to rear granulation from spout feeding dual-screw-stem machine, wherein, in extrusion, the temperature of each section is 200 ℃, 220 ℃, 230 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, the head end is 250 ℃, extrusion screw rod rotation speed n=400rpm.
Embodiment 2
A kind of fire-retardant PPE/PS/ABS alloy plastic and preparation method thereof, this fire-retardant PPE/PS/ABS alloy plastic comprises the component as weight percent in the embodiment 2 of table 1.Its preparation method is as follows:
Each component in table 1 embodiment 2 is proportionally carried out to mixing treatment, until each component mixes, then mixture is melt extruded to rear granulation from spout feeding dual-screw-stem machine, wherein, in extrusion, the temperature of each section is 200 ℃, 220 ℃, 230 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, the head end is 250 ℃, extrusion screw rod rotation speed n=400rpm.
Embodiment 3
A kind of fire-retardant PPE/PS/ABS alloy plastic and preparation method thereof, this fire-retardant PPE/PS/ABS alloy plastic comprises the component as weight percent in the embodiment 3 of table 1.Its preparation method is as follows:
Each component in table 1 embodiment 3 is proportionally carried out to mixing treatment, until each component mixes, then mixture is melt extruded to rear granulation from spout feeding dual-screw-stem machine, wherein, in extrusion, the temperature of each section is 200 ℃, 220 ℃, 230 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, the head end is 250 ℃, extrusion screw rod rotation speed n=400rpm.
Embodiment 4
A kind of fire-retardant PPE/PS/ABS alloy plastic and preparation method thereof, this fire-retardant PPE/PS/ABS alloy plastic comprises the component as weight percent in the embodiment 4 of table 1.Its preparation method is as follows:
Each component in table 1 embodiment 4 is proportionally carried out to mixing treatment, until each component mixes, then mixture is melt extruded to rear granulation from spout feeding dual-screw-stem machine, wherein, in extrusion, the temperature of each section is 200 ℃, 220 ℃, 230 ℃, 230 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, the head end is 250 ℃, extrusion screw rod rotation speed n=400rpm.
Comparative Examples 1
Formula and existing PPE/PS alloy plastic preparation technology according to the Comparative Examples 1 in following table 1 directly obtain existing PPE/PS alloy plastic.
Table 1
Performance test:
The fire-retardant PPE/PS/ABS alloy plastic of above-described embodiment 1 to embodiment 4 preparation and the fire-retardant PPE/PS alloy plastic of Comparative Examples 1 are carried out to the correlated performance test in following table 2, and properties the results are shown in following table 2.
Table 2
Known by test data in table 2, in the embodiment of the present invention, the PPE/PS/ABS alloy plastic has excellent chemical resistance and surface gloss, and the surface luster of this PPE/PS/ABS alloy plastic increases along with the increase of ABS content, and ABS add the chemically-resistant stress cracking that can improve greatly material.Meanwhile, this PPE/PS/ABS alloy plastic also has excellent mechanical property.In addition, can find out that from embodiment 4 the toughner increase can cause the surface gloss of this PPE/PS/ABS alloy plastic to descend and descend to some extent.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a fire-retardant PPE/PS/ABS alloy plastic, it comprises the component of following weight percent:
Wherein, described compatilizer is maleic anhydride graft PPE, and/or described toughner is SEBS and SBS mixture.
2. fire-retardant PPE/PS/ABS alloy plastic according to claim 1, it is characterized in that: described ABS is one or both mixtures in PA-757K, AG15A1.
3. fire-retardant PPE/PS/ABS alloy plastic according to claim 1, it is characterized in that: it is 40～45cm that described PPE selects limiting viscosity
3/ g.
4. fire-retardant PPE/PS/ABS alloy plastic according to claim 1, is characterized in that: PH-88, the PH-888 that described PS selects strange U.S. to produce, one or more mixtures in HP8250.
5. according to the described fire-retardant PPE/PS/ABS alloy plastic of claim 1～4 any one, it is characterized in that: described fire retardant is a kind of or both mixtures in tetraphenyl (bisphenol-A) bisphosphate, tetraphenyl resorcinol diphosphate.
6. according to the described fire-retardant PPE/PS/ABS alloy plastic of claim 1～4 any one, it is characterized in that: described lubricant is that PETS, E are cured, at least one or two the above mixtures in the type siloxane lubricant.
7. according to the described fire-retardant PPE/PS/ABS alloy plastic of claim 1～4 any one, it is characterized in that: described oxidation inhibitor is three (2, the 4-DI-tert-butylphenol compounds) one or more mixtures in phosphorous acid ester, β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl alcohol ester, zinc oxide.
8. the preparation method of a fire-retardant PPE/PS/ABS alloy plastic comprises the following steps:
Formula according to the described fire-retardant PPE/PS/ABS alloy plastic of claim 1～7 any one takes each component;
Each component taken is carried out being melt extruded granulation after mixing treatment.
9. the preparation method of fire-retardant PPE/PS/ABS alloy plastic according to claim 8, it is characterized in that: the described temperature melt extruded is 200～280 ℃.
10. the application of the described fire-retardant PPE/PS/ABS alloy plastic of claim 1～8 any one in preparing electric appliance casing, auto parts, sun power.
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| CN103937222A (en) * | 2014-04-29 | 2014-07-23 | 贵州高塑环保新材料有限公司 | Reinforced polyphenyl ether by using grafted block elastomer (SEBS) modification and preparation method thereof |
| CN104262806A (en) * | 2014-09-17 | 2015-01-07 | 上海日之升新技术发展有限公司 | High-temperature-resistant platable polyphenylether alloy material and preparation method thereof |
| CN105968775A (en) * | 2016-05-31 | 2016-09-28 | 苏州市奎克力电子科技有限公司 | Polyphenyl ether-polyarylene ether ether nitriles alloy material and preparation method thereof |
| CN108841159A (en) * | 2018-06-12 | 2018-11-20 | 杨杰 | A kind of PPO composite material and preparation method |
| CN114395241A (en) * | 2021-12-01 | 2022-04-26 | 金发科技股份有限公司 | Halogen-free high-gloss flame-retardant polystyrene material and preparation method and application thereof |
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| CN103788626A (en) * | 2014-01-13 | 2014-05-14 | 惠州市沃特新材料有限公司 | PPO/PA/HIPS (polyphenylene oxide/polyamide/high impact polystyrene) composite material and preparation method thereof |
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| CN103937222A (en) * | 2014-04-29 | 2014-07-23 | 贵州高塑环保新材料有限公司 | Reinforced polyphenyl ether by using grafted block elastomer (SEBS) modification and preparation method thereof |
| CN104262806A (en) * | 2014-09-17 | 2015-01-07 | 上海日之升新技术发展有限公司 | High-temperature-resistant platable polyphenylether alloy material and preparation method thereof |
| CN105968775A (en) * | 2016-05-31 | 2016-09-28 | 苏州市奎克力电子科技有限公司 | Polyphenyl ether-polyarylene ether ether nitriles alloy material and preparation method thereof |
| CN105968775B (en) * | 2016-05-31 | 2018-10-12 | 马鞍山市恒达工模具材料有限公司 | A kind of polyphenylene ether-poly aryl oxide ether nitrile alloy material and preparation method thereof |
| CN108841159A (en) * | 2018-06-12 | 2018-11-20 | 杨杰 | A kind of PPO composite material and preparation method |
| WO2022228143A1 (en) * | 2021-04-29 | 2022-11-03 | 金发科技股份有限公司 | Halogen-free flame retardant abs alloy material and preparation method therefor |
| CN114395241A (en) * | 2021-12-01 | 2022-04-26 | 金发科技股份有限公司 | Halogen-free high-gloss flame-retardant polystyrene material and preparation method and application thereof |
| CN114605750A (en) * | 2022-03-31 | 2022-06-10 | 国高材高分子材料产业创新中心有限公司 | Plastic Vicat softening temperature standard sample and preparation method thereof |
| CN114605750B (en) * | 2022-03-31 | 2023-11-21 | 国高材高分子材料产业创新中心有限公司 | Plastic Vicat softening temperature standard sample and preparation method thereof |
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Application publication date: 20131225 |