WO2017032283A1 - 一种软基固化处理构件用材料及其制备方法和应用 - Google Patents

一种软基固化处理构件用材料及其制备方法和应用 Download PDF

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WO2017032283A1
WO2017032283A1 PCT/CN2016/096123 CN2016096123W WO2017032283A1 WO 2017032283 A1 WO2017032283 A1 WO 2017032283A1 CN 2016096123 W CN2016096123 W CN 2016096123W WO 2017032283 A1 WO2017032283 A1 WO 2017032283A1
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antioxidant
light stabilizer
soft
member according
curing treatment
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PCT/CN2016/096123
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English (en)
French (fr)
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史先锋
陈曦
肖仕龙
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天津市顺康科技发展有限公司
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Publication of WO2017032283A1 publication Critical patent/WO2017032283A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the invention belongs to the field of soft base curing treatment component materials, in particular to a soft base curing treatment component material, a preparation method thereof and application thereof.
  • the main body of the material for the soft base curing member is made of a polypropylene base material.
  • Polypropylene (PP) is a kind of thermoplastic resin which can be obtained by polymerizing propylene. It has the advantages of good processing property, good toughness and good chemical stability, and is light in weight and low in cost. Such as can be used in the field of packaging.
  • polypropylene is very sensitive to ultraviolet light, and is insufficient in weather resistance and heat resistance. It is prone to aging degradation after ultraviolet light, heat and oxygen, resulting in performance degradation and discoloration.
  • the prior art generally improves the weatherability of polypropylene by adding a heat stabilizer and a light stabilizer.
  • the stabilizer used is generally a single hindered amine light stabilizer, a single antioxidant or a suitable amount of ultraviolet light. Absorbent, but often does not consider the synergistic effect between light stabilizers, the antagonistic effect between light stabilizers and some antioxidants, the compatibility of light stabilizers with resins, the effect of light stabilizers on the mechanical properties of PP And the effect of color on the weather resistance of the product.
  • the light stabilizer mixed with other materials will cause the light stabilizer and the antioxidant to be easily destroyed, thereby affecting the antioxidant and the light stabilizer to not exert the maximum effect, resulting in the weather resistance and heat resistance of the material. Performance has dropped dramatically.
  • the PP currently used in the packaging field in China generally requires short weather resistance, generally only meets the ASTM G-154 standard, that is, only meets the weathering UV aging for 200h, and the product strength is 50%, which is qualified, that is, It takes about a year to spend outdoors, which severely limits the scope of the product.
  • the problem to be solved by the present invention is to overcome the shortcomings of short weather resistance of polypropylene, and to provide a material for a soft base curing member having super weather resistance, that is, a polypropylene composition having super weather resistance.
  • the technical solution adopted by the present invention is: a material for a soft base curing treatment member, which is made of a raw material including the following parts by weight:
  • the polypropylene is a homopolypropylene having a melt flow rate of from 2 g/10 min to 5 g/10 min (230 ° C / 2.16 kg).
  • the composite light stabilizer comprises the following components by weight:
  • the sum of the weight percentages of the high molecular weight hindered amine light stabilizer, the low molecular weight hindered amine light stabilizer and the ultraviolet absorbent is 100%;
  • the composite antioxidant comprises the following weight percentage components:
  • the sum of the weight percentages of the hindered phenol primary antioxidant, the organic phosphite auxiliary antioxidant and the metal passivating agent is 100%;
  • the ultrafine carbon black is an ultrafine carbon black having a particle diameter of 20 to 50 Nm, preferably 20 to 30 Nm.
  • the present invention has made a particular choice in the compatibility and long-lasting weatherability of polypropylene products.
  • the composite light stabilizer is composed of a high molecular weight hindered amine light stabilizer and a low molecular weight hindered amine light stabilizer, and is compounded with a UV absorber.
  • high molecular weight hindered amine light stabilizers are long-acting light stabilizers, which exhibit excellent compatibility and extraction resistance in polymers.
  • One of the characteristics is that the molecular weight distribution is very narrow, which makes them in processing and use. Show consistent results fruit.
  • the high molecular weight hindered amine light stabilizer may be selected from light stabilizer 2020, light stabilizer 944 or Swiss CIBA (Swiss Ciba Fine Chemical Co., Ltd.) Chimassorb series, more preferably Chimassorb 2020 or Chimassorb 944.
  • Light Stabilizer 2020, Light Stabilizer 944 and Swiss CIBA Chimassorb Series combine the advantages of various high molecular weight HALS to provide high light/heat stability to polymers while improving their auxiliary properties, such as enhanced pigment chromaticity.
  • Low-polymerity hindered amine light stabilizer has high thermal stability and low volatility, low water-borneness, resistance to extraction, low interaction with other processing aids, lower reactivity in acidic environment, better retention of product color Fastness.
  • the oligomeric hindered amine light stabilizer may be selected from light stabilizers 4050H, 5050H or the German BASF (BASF, Germany) Uvinul series, preferably BASF Uvinul's Uvinul 4050H or Uvinul 5050H.
  • the ultraviolet absorber selectively absorbs ultraviolet rays, particularly ultraviolet rays having a wavelength of 280-370 nm, and converts the absorbed light energy into heat energy to be emitted.
  • the ultraviolet absorber is a carboxybenzotriazole-based ultraviolet absorber, more preferably Tinuvin 234, Tinuvin 326 or Tinuvin 531.
  • the inventors of the present invention fully considered the synergistic effect between the light stabilizers, the antagonistic effect between the light stabilizer and some of the antioxidants, the compatibility of the light stabilizer with the resin, and the addition of the light stabilizer to the mechanical properties of the PP.
  • the influence of the influence and the color on the weather resistance of the product, etc., the synergistic components of the composite light stabilizer in the range of the addition amount of the invention can effectively improve the weather resistance of the product during outdoor use and avoid the degradation of mechanical properties. And the color changes.
  • the antioxidant agent of the invention is carefully screened, and finally the heat is prevented by the hindered phenolic primary antioxidant, the organic phosphite auxiliary antioxidant and the contact of the material with the metal.
  • the composite antioxidant compounded by the oxidatively degraded auxiliary antioxidant metal passivator has synergistic effect among the three antioxidants in the range of the addition amount of the invention, and has high antioxidant ability.
  • the hindered phenolic primary antioxidant may be selected from the antioxidant 4190, the antioxidant 412s or the antioxidant 3114, preferably Chemtura phenolic antioxidant 4190, Chemtura 412s, IRGANOX 3114.
  • the organic phosphite auxiliary antioxidant may be selected from the antioxidant AT10 or the antioxidant AT62, preferably ALBEMARLE AT10 or AT62 of ALBEMARLE (American Albemarle).
  • the metal deactivator is preferably IRGANOX MD1024.
  • Carbon black has high absorbance, so it can effectively prevent photooxidation degradation of plastics caused by sunlight.
  • Carbon black as an ultraviolet light stabilizer plays a role in plastics: converting light energy into heat energy; protecting plastic surface from radiation of a certain wavelength; intercepting atomic groups to produce anti-aging effect, thereby preventing catalytic degradation.
  • Ultraviolet rays are particularly harmful to polypropylene, and tests have shown that a certain degree of fineness of carbon black can achieve perfect UV shielding.
  • the protective effect of carbon black on the UV aging of plastics depends on the particle size, structure and surface chemistry of the carbon black.
  • the inventors have found through a large number of experiments that when the particle size of carbon black is small, the absorption of light or shading ability is increased due to an increase in surface area, so that the ultraviolet protection effect is enhanced, but the particle size is less than 20 nm, and the protective effect tends to the same level. The reason is that when the particle size is too small, the backscattering is reduced, and the light that continues to move forward threatens the stability of the polymer.
  • the particle size of the carbon black is larger than 50 nm, the uniformity of dispersion is affected, and the mechanics of the product is also affected. performance.
  • the ultrafine carbon black having a particle diameter of 20-50 Nm, especially 20-30 Nm has a large number of oxygen-containing groups on the surface, that is, when the volatile matter is high, the gene generated during decomposition of the polymer can be eliminated, and thus the protective effect is enhanced. And has an excellent ultraviolet absorption effect, which can convert ultraviolet rays into heat, which greatly reduces the damage of the chemical bond energy of polypropylene by ultraviolet rays.
  • the ultrafine carbon black of the present invention is preferably an ultrafine carbon black of the carbon black model special Black series of Evonik Degussa, Germany.
  • the coupling agent of the present invention mainly functions to solve the compatibility of each component with the polypropylene resin, in particular, the compatibility of the inorganic ultrafine carbon black with the resin, prevent the powder on the surface of the product from being precipitated, and reduce the mechanical properties of the resin.
  • the coupling agent is one of a titanate, an aluminate coupling agent, a silane coupling agent, or a mixture thereof.
  • the dispersant of the present invention has a primary function of improving the dispersibility of each component in processing and molding, particularly the uniformity of dispersion of ultrafine carbon black.
  • the dispersing agent is a low molecular ester, a metal soap, a stearic acid complex ester, a amide or a mixture thereof, more preferably a high molecular polyethylene wax, calcium stearate, stearic acid. Zinc or ethylene bis stearamide.
  • the present invention also provides a preparation method for preparing the above-mentioned material for super weather resistant soft-based curing treatment member, comprising the following steps:
  • Step 1 Weigh each raw material by weight
  • Step 2 mixing the polypropylene, the composite light stabilizer, the composite antioxidant and the dispersing agent in a high speed mixer (rotation speed not lower than 900 RPM) for 3-8 minutes to obtain a mixture;
  • Step 3 stirring the ultrafine carbon black in a coupling agent mixer for 3-8 minutes to obtain a mixture
  • Step 4 The mixture in the step 2 and the mixture in the step 3 are separately extruded from the main feeding port and the side feeding port of the twin-screw extruder to obtain a product; the processing temperature is 185-225 ° C, The screw speed is 350-500RPM, the screw length to diameter ratio is greater than 40, the extruder temperature control zone is larger than 8 zones, and the side feed port is located in the 4th zone or the 5th zone.
  • the present invention also provides the use of the above-described material for a soft-based curing member in a packaged article, particularly an outdoor packaged article, for example, as a base fabric material in a soft-based curing engineering member.
  • the invention has the following characteristics:
  • the antioxidant and the light stabilizer in the formulation of the material for the soft-based curing treatment member of the present invention can exert the maximum effect, and cooperate with other raw materials in the formulation, and the prepared polypropylene composition is used as a packaging material thin product.
  • Excellent super weather resistance, UV aging for 1500 hours, polypropylene tensile strength and elongation at break remain above 80%, that is, 7-8 years in outdoor use, the mechanical properties of the product can still retain more than 80% Compared with the existing products in the market, it has been greatly improved in the outdoor use for about one year.
  • Example 1 Example 2
  • Example 3 Example 4
  • PP 98.8 92 92 93 Uvinul 5050H 0.375 0.6 0.525 Uvinul 4050H 0.7 Chimassorb 2020 0.75 0.8 Chimassorb 944 0.6 0.6 Chimassorb770 0.3 Tinuvin 531 0.2 0.375 0.7 0.6 0.375
  • Chemtura 4190 0.825 0.5
  • Chemtura 412s 0.5 IRGANOX 3114 0.75 ALBEMARLE AT10 0.6 0.6 ALBEMARLE AT62 0.45 0.45
  • the coupling agent is an aluminate coupling agent
  • the dispersing agent is a high molecular polyethylene wax
  • each raw material is a part by weight.
  • the ultrafine carbon black is a special black of the special black series of Evonik Degussa, and an ultrafine carbon black having a particle diameter of 30 Nm (nanometer).
  • the polypropylene (PP) is a homopolypropylene with a melt flow rate of 5 g/10 min (230 ° C / 2.16 kg)
  • the method for preparing a material for a soft base curing member according to the above embodiments 1-4 includes the following steps:
  • Step 1 Weigh each raw material by weight
  • Step 2 mixing the polypropylene, the composite light stabilizer, the composite antioxidant and the dispersing agent in a high speed mixer for 3 minutes to obtain a mixture;
  • Step 3 stirring the ultrafine carbon black in a coupling agent mixer for 5 minutes to obtain a mixture
  • Step 4 The mixture in the step 2 and the mixture in the step 3 are respectively extruded from the main feeding port and the side feeding port of the twin-screw extruder to obtain a product; the processing temperature is 200 ° C, and the screw speed is obtained. For 500 RPM, the screw length to diameter ratio is greater than 40, the extruder temperature control zone is greater than 8 zones, and the side feed port is located in Zone 4 or Zone 5.
  • Comparative Example 1 is a polypropylene composition formulation of the prior art.
  • the formulation of the material for the soft-based curing treatment member of the present invention that is, the antioxidant and the light stabilizer in the formulation of the polypropylene composition can exert the maximum effect, and interact with other raw materials in the formulation.
  • the prepared soft-based curing treatment member is made of packaging material, and the thin product has excellent super weather resistance. It can be UV-aged for 1500 hours, and the tensile strength and elongation at break of polypropylene remain above 80%, that is, After 7-8 years of outdoor use, the mechanical properties of the product can be retained for more than 80%, which is an obvious improvement over the existing products in the market for about one year.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

提供一种软基固化处理构件材料的制备方法和应用，所述软基固化处理构件材料为聚丙烯组合物，所述聚丙烯组合物由包括如下重量份数的原料制成：90-95份聚丙烯、1.5-2份复合光稳定剂、1-2份复合抗氧剂、2-3份超细炭黑、0.3-0.5份偶联剂和1-2份分散剂。聚丙烯组合物的配方中抗氧剂以及光稳定剂能够发挥最大的功效，制备的聚丙烯组合物做包装材料薄制品具有优秀的超耐候性，可以在UVB紫外老化1500小时，聚丙烯拉伸强度和断裂伸长率保留在80％以上，也就是在户外使用7-8年，制品的力学性能还可以保留80％以上，比市场现有的产品在户外大约使用1年的时间有了大幅度的提高。

Description

一种软基固化处理构件用材料及其制备方法和应用 技术领域
本发明属于软基固化处理构件材料领域，特别是涉及一种软基固化处理构件用材料及其制备方法和应用。
背景技术
软基固化处理构件用材料的主体构造为聚丙烯基布材质。聚丙烯(Polypropylene，简称PP)是一种可由丙烯聚合而制得的热塑性树脂，其不但具有加工性能好，韧性好，化学稳定性好的等优点，而且质轻，低廉，因而其应用广泛，如可用于包装领域。但是聚丙烯对紫外线很敏感，在耐候性和耐热性等方面较为不足，在紫外线，热，氧作用后易发生老化降解而导致性能下降及变色问题，这些缺点都限制了PP的使用，尤其限制PP在户外包装制品的应用，特别是针对长期在户外放置有耐候性要求的产品，必须改善PP的耐候性才能拓展PP的应用领域。
现有技术一般通过采取添加热稳定剂，光稳定剂来改善聚丙烯的耐候性，所选的使用的稳定剂一般为单一的受阻胺光稳定剂，单一的抗氧剂或者复配适量的紫外线吸收剂，但往往没有考虑光稳定剂之间的协同效应，光稳定剂和部分抗氧剂之间的对抗效应，光稳定剂与树脂的相容性，光稳定剂添加对PP力学性能的影响以及颜色对制品耐候性能的影响等。如果选择不合适，光稳定剂与其他物料一起混合，会导致光稳定剂和抗氧剂容易被破坏，从而影响抗氧剂以及光稳定剂不能发挥最大的功效，导致材料的耐候性和耐热性能大幅下降。此外，国内目前用在包装领域的PP，耐候性一般要求比较短，一般只在满足ASTM G-154的标准，也就是只满足耐候性紫外老化200h,产品强度保留50％即为合格，也就是在户外大约使用1年的时间，这严重的限制了产品更大的使用范围。
发明内容
本发明要解决的问题是克服聚丙烯的耐候性时间较短之缺点，提供一种具有超耐候性的软基固化处理构件用材料，即一种具有超耐候性的聚丙烯组合物。
为解决上述技术问题，本发明采用的技术方案是：一种软基固化处理构件用材料，由包括如下重量份数的原料制成：
Figure PCTCN2016096123-appb-000001
优选的，所述聚丙烯为均聚聚丙烯，熔体流动速为2g/10min-5g/10min(230℃/2.16kg)。
所述复合光稳定剂包括如下重量百分比的组分：
高分子量的受阻胺光稳定剂  30-50％；
低分子量的受阻胺光稳定剂  25-35％；
紫外线吸收剂              25-35％；
高分子量的受阻胺光稳定剂、低分子量的受阻胺光稳定剂和紫外线吸收剂的重量百分比之和为100％；
所述复合抗氧剂包括如下重量百分比的组分：
受阻酚类主抗氧剂          45-55％；
有机亚磷酸酯类辅助抗氧剂  40-45％；
金属钝化剂                5-10％；
受阻酚类主抗氧剂、有机亚磷酸酯类辅助抗氧剂和金属钝化剂的重量百分比之和为100％；
所述超细炭黑为粒径在20-50Nm，优选20-30Nm之间的超细炭黑。
现有技术为了解决市场现有的产品超耐候性，通常需要加入相对平时过量的抗氧剂和光稳定剂，而这势必会影响聚丙烯薄制品的后续加工，而且会严重的降低制品的力学性能。本发明的发明人付出了大量的精力，经过大量的试验，对配方中的各原料进行了筛选，尤其针对聚丙烯组合物中的光稳定剂和抗氧剂进行了细致的筛选，得到了超耐候性的聚丙烯组合物。
本发明在聚丙烯产品的相容性和长效耐候性上做了特别的选择。复合光稳定剂由高分子量的受阻胺光稳定剂与低分子量的受阻胺光稳定剂，同时复配紫外线吸收剂而成。其中高分子量受阻胺光稳定剂作为长效的光稳定剂，它在聚合物中表现出优异的相容性和抗萃取性，它特点之一是分子量分布非常窄，这使得在加工和使用中表现出一致的效 果。高分子量受阻胺光稳定剂可以选择光稳定剂2020、光稳定剂944或瑞士CIBA(瑞士汽巴精细化工有限公司)Chimassorb系列，更优选Chimassorb 2020或Chimassorb 944。光稳定剂2020、光稳定剂944和瑞士CIBA Chimassorb系列综合了各种高分子量HALS的优点，它为聚合物提供较高的光/热稳定性，同时改善其辅助性质，如增强颜料的色度，把非常高的光稳定性和长效热稳定性与其它辅助性质(如颜色干扰最小，改善熔体流动速率控制)完美地结合在一起，并且它对PP纤维、PP窄带、PE薄膜、PP和PE厚制品提供优异的光稳定性，它还对填充PP制品和碳黑填充体系表现出独特的长效热稳定性。低聚受阻胺光稳定剂具有高热稳定性和低挥发性，低带水性，耐抽提，与其它加工助剂较低的相互作用，在酸性环境较低反应性，更好的保持产品的色牢度。低聚受阻胺光稳定剂可以选择光稳定剂4050H、5050H或德国BASF(德国巴斯夫公司)Uvinul系列，优选BASF Uvinul的Uvinul 4050H或Uvinul 5050H。紫外线吸收剂可以选择性吸收紫外线，特别是波长280-370nm波段的紫外线，同时将吸收的光能转化成热能散发掉。优选的，紫外线吸收剂为羧基苯并三唑类紫外线吸收剂，更优选Tinuvin 234、Tinuvin 326或Tinuvin 531。本发明的发明人充分考虑到了光稳定剂之间的协同效应，光稳定剂和部分抗氧剂之间的对抗效应，光稳定剂与树脂的相容性，光稳定剂添加对PP力学性能的影响以及颜色对制品耐候性能的影响等，在本发明添加量范围内的复合光稳定剂各组分之间彼此协同，能够有效提高了产品在户外使用过程中耐候性，避免力学性能发生下降，以及色泽发生变化。
针对聚丙烯产品的超耐候性时间要求，本发明对抗氧剂进行了细致的筛选，最终得到由受阻酚类主抗氧剂、有机亚磷酸酯类辅助抗氧剂和防止材料与金属接触导致热氧化降解的辅抗氧剂类的金属钝化剂复配而成的复合抗氧剂，在本发明添加量范围内的这三种抗氧剂之间的彼此协同，具有高的抗氧化能力，与树脂相容性好，不析出，加工时不挥发，不分解，耐抽出性好，不溶于水和油中，环境友好的性质，提高加工和使用过程中的热稳定性，避免力学性能和色泽发生变化，解决了聚丙烯在加工和长期使用中的热氧老化的问题。所述受阻酚类主抗氧剂可以选择抗氧剂4190、抗氧剂412s或抗氧剂3114，优选Chemtura(科聚亚公司)酚类抗氧剂4190、Chemtura 412s、IRGANOX 3114。所述有机亚磷酸酯类辅助抗氧剂可以选择抗氧剂AT10或抗氧剂AT62，优选美国ALBEMARLE(美国雅宝公司)的ALBEMARLE AT10或AT62。所述金属钝化剂优选IRGANOX MD1024。
炭黑有较高的吸光性，因而能有效的防止塑料受阳光照射而产生光氧化降解。炭黑作为紫外光稳定剂在塑料中所起的作用有：把光能转化为热能；保护塑料表面而免遭一定波长的射线照射；截取原子团而产生防老化作用，从而阻止催化降解。紫外线对聚丙烯特别有害，试验证明当一定细度的炭黑的浓度可以达到完美的紫外线屏蔽作用。炭黑对塑料的紫外线老化的防护作用，取决于炭黑的粒径、结构和表面化学性。本发明人经过大量实验后发现，炭黑的粒径较小时，因表面积增大，其吸收光或遮光能力增加，故紫外线防护作用增强，但粒径小于20nm，其防护作用趋于同一水平，原因是当粒径过小时，逆向散射减小，而继续向前的光会威胁聚合物的稳定性，而当炭黑粒径大于50nm时，会影响分散的均匀度，也会影响产品的力学性能。粒径在20-50Nm，尤其是20-30Nm之间的超细炭黑的表面含氧基团较多，即挥发份较高时，能消除聚合物分解时产生的基因，因此防护作用也增强，并且具有极佳的紫外线吸收作用，可以把紫外线转化成热量，大大降低了紫外线对聚丙烯化学键能的破坏。本发明的超细炭黑优选德国Evonik Degussa(赢创德固赛公司)的炭黑型号special Black系列的超细炭黑。
本发明中的偶联剂其主要作用是解决各组分与聚丙烯树脂的相容性，特别是无机超细炭黑与树脂的相容性，防止产品表面粉末析出，减少引起树脂的力学性能的降低，优选的，所述的偶联剂为钛酸酯，铝酸酯偶联剂，硅烷偶联剂中的一种或其混合物。
本发明中的分散剂其主要作用是在加工和成型中提高各组分的分散性，特别是超细炭黑的分散均匀性。优选的，所述的分散剂为低分子酯类，金属皂类，硬脂酸复合酯类，酰胺类的一种或其混合物，更优选高分子聚乙烯蜡，硬脂酸钙，硬脂酸锌或乙撑双硬脂酰胺。
本发明还提供一种制备上述超耐候性软基固化处理构件用材料的制备方法，包括如下步骤：
第1步：按重量份数称取各原材料；
第2步：将聚丙烯、复合光稳定剂、复合抗氧剂和分散剂于高速混合机(转速不低于900RPM)中混合3-8分钟，获得混合物；
第3步：将超细炭黑，偶联剂混合机中搅拌3-8分钟，获得混合物；
第4步：将步骤2中的混合物和步骤3中的混合物分别从双螺杆挤出机的主加料口及侧加料口下料挤出造粒，最终得到产品；加工温度为185-225℃,螺杆转速为350-500RPM，螺杆长径比要大于40，挤出机温控区要大于8区，侧加料口位于第4区或第5区。
本发明还提供了上述软基固化处理构件用材料在包装制品，尤其是户外包装制品中的应用，例如作为软基固化工程构件中的基布材料。
与现有技术相比，本发明具有如下特点：
1、本发明的软基固化处理构件用材料的配方中抗氧剂以及光稳定剂能够发挥最大的功效，并且和配方中的其他原料相互配合，制备的聚丙烯组合物做包装材料薄制品具有优秀的超耐候性，可以在UVB紫外老化1500小时，聚丙烯拉伸强度和断裂伸长率保留在80％以上，也就是在户外使用7-8年，制品的力学性能还可以保留80％以上，比市场现有的产品在户外大约使用1年的时间有了大幅度的提高。
2、本发明的制备方法中，为了使本聚丙烯组合物可以混合均匀，有利挤出造粒，特别将超细炭黑从侧料口加入。这样有利于超细炭黑的单独计量喂料，而且在聚丙烯混合融化后喂料，可以防止炭黑吸收光稳定剂和抗氧剂的功效，同时更好的发挥偶联剂的功效，改善炭黑与树脂的相容性。
具体实施方式
下面结合具体实施例对本发明作进一步说明，但不限定本发明的保护范围。
对比例1以及实施例1-4的具体组成列于表1，常规性能列于表2。
表1
组分 对比例1 实施例1 实施例2 实施例3 实施例4
PP 98.8 92 92 93 94
Uvinul 5050H   0.375   0.6 0.525
Uvinul 4050H     0.7    
Chimassorb 2020   0.75   0.8  
Chimassorb 944     0.6   0.6
Chimassorb770 0.3        
Tinuvin 531 0.2 0.375 0.7 0.6 0.375
Chemtura 4190   0.825     0.5
Chemtura 412s     0.5    
IRGANOX 3114       0.75  
ALBEMARLE AT10   0.6   0.6  
ALBEMARLE AT62     0.45   0.45
抗氧剂B215 0.2        
IRGANOX MD1024   0.075 0.05 0.15 0.05
special Black 6   3 2.8 2 2
分散剂 0.5 1.5 1.7 1 1
偶联剂   0.5 0.5 0.5 0.5
表1中，所述的偶联剂为铝酸酯偶联剂，所述分散剂为高分子聚乙烯蜡，各原料均为重量份数。
所述超细炭黑为Evonik Degussa的special Black系列的special Black 6，粒径为30Nm(纳米)的超细炭黑。
所述聚丙烯(PP)为均聚聚丙烯，熔体流动速为5g/10min(230℃/2.16kg)
上述实施例1-4的软基固化处理构件用材料的制备方法，包括如下步骤：
第1步：按重量份数称取各原材料；
第2步：将聚丙烯、复合光稳定剂、复合抗氧剂和分散剂于高速混合机中混合3分钟，获得混合物；
第3步：将超细炭黑，偶联剂混合机中搅拌5分钟，获得混合物；
第4步：将步骤2中的混合物和步骤3中的混合物分别从双螺杆挤出机的主加料口及侧加料口下料挤出造粒，最终得到产品；加工温度为200℃,螺杆转速为500RPM，螺杆长径比要大于40，挤出机温控区要大于8区，侧加料口位于第4区或第5区。
表2
Figure PCTCN2016096123-appb-000002
表2中的实验方法是按照美国ASTM G-154UVB关于包装制品的检测方法进行检测，表中所表示的是PP拉伸强度的保留率。
对比例1为现有常规方案的聚丙烯组合物配方。从表2中可以看到，本发明的软基固化处理构件用材料的配方，即聚丙烯组合物的配方中抗氧剂以及光稳定剂能够发挥最大的功效，并且和配方中的其他原料相互配合，制备的软基固化处理构件用材料做包装材料薄制品具有优秀的超耐候性，可以在UVB紫外老化1500小时，聚丙烯拉伸强度和断裂伸长率保留在80％以上，也就是在户外使用7-8年，制品的力学性能还可以保留80％以上，比市场现有的产品在户外大约使用1年的时间有着显而易见的进步。
以上对本发明的较佳实施例进行了详细说明，但所述内容仅为本发明的较佳实施例，不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进等，均应仍归属于本发明的专利涵盖范围之内。

Claims (10)

  1. 一种软基固化处理构件用材料，其特征在于：由包括如下重量份数的原料制成：
    Figure PCTCN2016096123-appb-100001
    所述复合光稳定剂包括如下重量百分比的组分：
    高分子量的受阻胺光稳定剂  30-50％；
    低分子量的受阻胺光稳定剂  25-35％；
    紫外线吸收剂              25-35％；
    高分子量的受阻胺光稳定剂、低分子量的受阻胺光稳定剂和紫外线吸收剂的重量百分比之和为100％；
    所述复合抗氧剂包括如下重量百分比的组分：
    受阻酚类主抗氧剂         45-55％；
    有机亚磷酸酯类辅助抗氧剂 40-45％；
    金属钝化剂               5-10％；
    受阻酚类主抗氧剂、有机亚磷酸酯类辅助抗氧剂和金属钝化剂的重量百分比之和为100％；
    所述超细炭黑为粒径在20-50Nm，优选20-30Nm之间的超细炭黑，更优选Evonik Degussa的special Black系列超细炭黑。
  2. 根据权利要求1所述的软基固化处理构件用材料，其特征在于：所述聚丙烯为均聚聚丙烯，熔体流动速为2g/10min-5g/10min。
  3. 根据权利要求1或2所述的软基固化处理构件用材料，其特征在于：所述高分子量的受阻胺光稳定剂为光稳定剂2020或光稳定剂944，优选瑞士CIBA Chimassorb系列的Chimassorb 2020或Chimassorb 944；所述低分子量的受阻胺光稳定剂为光稳定剂4050H或5050H；优选德国BASF Uvinul系列的Uvinul 4050H或Uvinul 5050H。
  4. 根据权利要求1-3任一项所述的软基固化处理构件用材料，其特征在于：所述紫外线吸收剂为羧基苯并三唑类紫外线吸收剂，优选Tinuvin 234、Tinuvin 326或Tinuvin 531。
  5. 根据权利要求1-4任一项所述的软基固化处理构件用材料，其特征在于：所述受阻酚类主抗氧剂为抗氧剂4190、抗氧剂412s或抗氧剂3114；优选Chemtura酚类抗氧剂4190、Chemtura 412s或IRGANOX 3114；所述有机亚磷酸酯类辅助抗氧剂为抗氧剂AT10或抗氧剂AT62；优选美国ALBEMARLE的ALBEMARLE AT10或AT62。
  6. 根据权利要求1-5任一项所述的软基固化处理构件用材料，其特征在于：所述金属钝化剂为IRGANOX MD1024。
  7. 根据权利要求1-6任一项所述的软基固化处理构件用材料，其特征在于：所述的偶联剂为钛酸酯，铝酸酯偶联剂，硅烷偶联剂中的一种或其混合物。
  8. 根据权利要求1-7任一项所述的软基固化处理构件用材料，其特征在于：所述分散剂为低分子酯类、金属皂类、硬脂酸复合酯类、酰胺类的一种或其混合物；优选高分子聚乙烯蜡，硬脂酸钙，硬脂酸锌或乙撑双硬脂酰胺中的一种或其混合物。
  9. 一种制备权利要求1-8任一项所述的软基固化处理构件用材料的方法，其特征在 于：包括如下步骤：
    第1步：按重量份数称取各原材料；
    第2步：将聚丙烯、复合光稳定剂、复合抗氧剂和分散剂于高速混合机中混合3-8分钟，获得混合物；
    第3步：将超细炭黑，偶联剂混合机中搅拌3-8分钟，获得混合物；
    第4步：将步骤2中的混合物和步骤3中的混合物分别从双螺杆挤出机的主加料口及侧加料口下料挤出造粒，最终得到产品；加工温度为185-225℃,螺杆转速为350-500RPM，螺杆长径比要大于40，挤出机温控区要大于8区，侧加料口位于第4区或第5区。
  10. 权利要求1-9任一项所述的软基固化处理构件用材料在包装制品，尤其是户外包装制品中的应用。
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CN114605687A (zh) * 2022-05-13 2022-06-10 河南银金达新材料股份有限公司 一种抗老化聚酯膜材料的制备方法

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CN113736181A (zh) * 2020-05-28 2021-12-03 广州合成材料研究院有限公司 一种碳材料增强户外地板聚丙烯专用料及其制备方法
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08239527A (ja) * 1995-03-01 1996-09-17 Toyoda Gosei Co Ltd 高光沢性樹脂組成物及び樹脂成形体
US20040220312A1 (en) * 2000-12-22 2004-11-04 In-Sik Jung Flame retardant polypropylene resin composition
US20050085574A1 (en) * 2002-02-27 2005-04-21 Pieter Gijsman Stabilized polypropylene resin composition
CN1916067A (zh) * 2006-09-07 2007-02-21 浙江俊尔新材料有限公司 一种改性耐候聚丙烯材料
CN101870784A (zh) * 2010-03-29 2010-10-27 金发科技股份有限公司 一种抗冲型耐候聚丙烯及其制备方法
CN102634113A (zh) * 2012-04-12 2012-08-15 杭州金州高分子科技有限公司 一种高耐热高耐候聚丙烯色母粒材料
CN103012970A (zh) * 2012-12-03 2013-04-03 合肥杰事杰新材料股份有限公司 一种耐候耐老化聚丙烯材料及其制备方法
CN103289195A (zh) * 2013-05-24 2013-09-11 杭州哈富化工技术有限公司 一种汽车散热器罩复合聚丙烯抗老化剂及其制备方法
CN104098832A (zh) * 2013-04-09 2014-10-15 合肥杰事杰新材料股份有限公司 一种聚丙烯耐热耐侯母粒、制备方法及其应用
CN105037944A (zh) * 2015-08-21 2015-11-11 天津市顺康科技发展有限公司 软基固化处理构件材料的制备方法及应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040767B (zh) * 2009-10-14 2012-07-25 中国石油化工股份有限公司 一种抗紫外线聚丙烯组合物及其制备方法
CN102108151A (zh) * 2009-12-25 2011-06-29 上海普利特复合材料股份有限公司 一种具有优异耐光照老化性能的聚丙烯组合物

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08239527A (ja) * 1995-03-01 1996-09-17 Toyoda Gosei Co Ltd 高光沢性樹脂組成物及び樹脂成形体
US20040220312A1 (en) * 2000-12-22 2004-11-04 In-Sik Jung Flame retardant polypropylene resin composition
US20050085574A1 (en) * 2002-02-27 2005-04-21 Pieter Gijsman Stabilized polypropylene resin composition
CN1916067A (zh) * 2006-09-07 2007-02-21 浙江俊尔新材料有限公司 一种改性耐候聚丙烯材料
CN101870784A (zh) * 2010-03-29 2010-10-27 金发科技股份有限公司 一种抗冲型耐候聚丙烯及其制备方法
CN102634113A (zh) * 2012-04-12 2012-08-15 杭州金州高分子科技有限公司 一种高耐热高耐候聚丙烯色母粒材料
CN103012970A (zh) * 2012-12-03 2013-04-03 合肥杰事杰新材料股份有限公司 一种耐候耐老化聚丙烯材料及其制备方法
CN104098832A (zh) * 2013-04-09 2014-10-15 合肥杰事杰新材料股份有限公司 一种聚丙烯耐热耐侯母粒、制备方法及其应用
CN103289195A (zh) * 2013-05-24 2013-09-11 杭州哈富化工技术有限公司 一种汽车散热器罩复合聚丙烯抗老化剂及其制备方法
CN105037944A (zh) * 2015-08-21 2015-11-11 天津市顺康科技发展有限公司 软基固化处理构件材料的制备方法及应用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605687A (zh) * 2022-05-13 2022-06-10 河南银金达新材料股份有限公司 一种抗老化聚酯膜材料的制备方法

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