WO2016150142A1 - Ky-616作为顺丁橡胶组合物改性添加剂的应用 - Google Patents

Ky-616作为顺丁橡胶组合物改性添加剂的应用 Download PDF

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WO2016150142A1
WO2016150142A1 PCT/CN2015/091549 CN2015091549W WO2016150142A1 WO 2016150142 A1 WO2016150142 A1 WO 2016150142A1 CN 2015091549 W CN2015091549 W CN 2015091549W WO 2016150142 A1 WO2016150142 A1 WO 2016150142A1
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butadiene rubber
rubber composition
antioxidant
vulcanization
resistance
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French (fr)
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曹宏生
王宇
王忠冬
吴开赟
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江苏飞亚化学工业有限责任公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

  • the invention relates to the technical field of rubber preparation, in particular to the application of KY-616 as a modification additive of a butadiene rubber composition.
  • polymer materials are susceptible to heat, oxygen, ozone, mechanical force, etc., which change their structure and properties, and gradually lose their use value. This phenomenon is called aging of polymer materials.
  • aging of polymer materials In rubber, the problem of thermo-oxidative aging is more prominent because of the large number of double bonds in its molecular chain.
  • an antioxidant In order to suppress or retard the occurrence of an oxidation reaction, an antioxidant is usually added to the rubber.
  • the most commonly used main antioxidants are hindered phenols and aromatic amines, among which hindered phenols have the advantages of no discoloration, no toxicity and no pollution, and are widely used in polymer materials.
  • antioxidants should have good thermal stability, migration resistance and extractability in addition to good oxidation resistance.
  • most of the antioxidants currently used are small molecular substances, which have the disadvantages of being volatile, not migrating and extracting, which is disadvantageous for their long-term stability in the polymer, and thus it is difficult to meet the increasing resistance of materials. Aging requirements.
  • domestic and foreign scholars have done a lot of research on the preparation of macromolecular antioxidants and their application in polymer materials.
  • Macromolecular antioxidants have become An important direction in the development of antioxidants.
  • Butadiene rubber (BR) is currently the second largest synthetic rubber in the world after styrene-butadiene rubber (SBR). There are few studies on antioxidants for butadiene rubber.
  • Chinese invention patent 201310711836.8 discloses a novel butadiene rubber comprising: butadiene, polyisoprene, extender oil, carbon black powder and additives, the butadiene
  • the weight percentage of the new butadiene rubber is 43%
  • the weight percentage of the polyisoprene in the novel butadiene rubber is 9%
  • the weight of the filling oil in the novel butadiene rubber The percentage is 26%
  • the carbon black powder accounts for 6% by weight of the novel butadiene rubber
  • the additive accounts for 16% by weight of the novel butadiene rubber.
  • the additive includes a catalyst and terminates. And anti-aging agents.
  • the novel butadiene rubber disclosed in the invention adopts a plurality of high-quality raw materials, and the obtained new butadiene rubber improves the wet skid resistance and The processing property, the tear strength is high, the adhesiveness is good, and the application range is wide; however, the invention does not describe the related technical content of the antioxidant of the butadiene rubber.
  • Chinese invention patent 201410516405.0 discloses a butadiene rubber comprising the following components: 30-50 parts of cis-polybutadiene mixture, 5-9 parts of cyclohexane, cobalt oxide 1 -3 parts, 2-5 parts of zinc oxide, 3-7 parts of sulfur, 1-3 parts of stearic acid, 1-5 parts of nickel naphthenate, 5-9 parts of triisobutyl aluminum, boron trifluoride diethyl ether 2 -4 parts, 2-6 parts of heptane, 3-8 parts of hydrogen gasoline, NS15-19 parts of accelerator, HAF10-13 parts, 11-15 parts of ASTM type 103 oil, 2-8 parts of aluminum oxide clinker, chlorine 2-5 parts of m-xylenol.
  • the cis-polybutadiene mixture is a mixture of cis 1,4-polybutadiene and cis 1,3-polybutadiene.
  • the cis 1,4-polybutadiene and cis 1,3-polybutadiene accounted for 2:5 by weight of the mixture.
  • the butadiene rubber provided by the invention contains a mixture of cis-polybutadiene, which can effectively reduce the tear strength, improve the wet skid resistance and the adhesion, and has low heat build-up. Also, the invention does not disclose the relevant technical content of the antioxidant of the butadiene rubber.
  • Antioxidant KY-616 (or Wingstay L, Lowinox CPL, Vanox L, etc.) is a polymeric polyphenolic antioxidant with a chemical structural formula as shown in Figure 1.
  • the antioxidant has a large molecular weight, good compatibility with a polymer, and has the characteristics of heat resistance and extraction resistance. It is a novel macromolecular antioxidant developed in recent years, and its application research in polymer materials is affected. The researcher's attention. Li Zhihong studied the anti-thermal aging properties of the antioxidant KY-616 in natural rubber, and found that it exhibited better stabilization effect in natural rubber, and its water extraction resistance was better than that of amine antioxidant-MB. .
  • antioxidant KY-616 in the production of condoms and found that the anti-aging performance of antioxidant KY-616 is better than that of antioxidant 264 and antioxidant fork in condom products made from natural latex. 4426-S.
  • antioxidant KY-616 in BR is rarely reported.
  • This study investigated the effect of antioxidant KY-616 on the vulcanization properties, mechanical properties and thermal aging resistance of butadiene rubber (BR) to evaluate the antioxidant effect of KY-616 in butadiene rubber.
  • the suitable amount of antioxidant KY-616 provides technical support for improving the performance of butadiene rubber (BR).
  • the present invention has been achieved by the following technical means, and relates to the use of KY-616 as a modification additive for a butadiene rubber composition.
  • the invention has the following beneficial effects: the addition of KY-616 can significantly improve the processing property of the prepared butadiene rubber composition, enhance the scorch resistance, prolong the vulcanization time, reduce the vulcanization rate, and vulcanize the rubber. Increased mechanical properties and resistance to thermal aging.
  • Antioxidant KY-616 achieved good anti-thermal aging effect; with the increase of KY-616 dosage, the mechanical properties and thermal aging resistance of vulcanizate increased, and the oxidation induction time first increased and then stabilized;
  • the suitable dosage of KY-616 in BR is 1 phr; the addition of antioxidant KY-616, the prepared butadiene rubber composition has significantly improved processing performance, enhanced scorch resistance, extended vulcanization time, reduced vulcanization rate, and mechanical properties of vulcanizate. And improved resistance to thermal aging.
  • Figure 1 is the chemical structural formula of the antioxidant KY-616
  • Figure 2 is an infrared spectrum of the antioxidant KY-616
  • Figure 3 is a graph showing the vulcanization curve of a BR rubber compound with different amounts of antioxidant KY-616;
  • Figure 4 is the effect of the amount of antioxidant KY-616 and aging time on the tensile strength of BR vulcanizate
  • Figure 5 shows the effect of the amount of antioxidant KY-616 and the aging time on the elongation at break of BR vulcanizate.
  • the butadiene rubber composition of the present invention is composed of the following components by weight, butadiene rubber 100, carbon black 56-64, stearic acid 1-4, zinc oxide 2-7, accelerator 1.1-4.2 , sulfur 1-4, rubber oil 3-7, antioxidant KY-616 0.1-5.
  • the accelerator is accelerator CZ, or accelerator DM, or a mixture of accelerator CZ and accelerator DM.
  • the promoter is a mixture of accelerator CZ and promoter DM, wherein promoters CZ 1-3, promoters DM 0.1-1.2.
  • the composition consists of the following components by weight: butadiene rubber 100, carbon black 60, stearic acid 2, zinc oxide 5, accelerator CZ 1.5, accelerator DM 0.5, sulfur 2, rubber Oil 6, antioxidant KY-616 0.8-4.
  • the composition consists of the following components by weight: butadiene rubber 100, carbon black 60, stearic acid 2, zinc oxide 5, accelerator CZ 1.5, accelerator DM 0.5, sulfur 2, rubber Oil 6, antioxidant KY-616 1.
  • the rubber oil is an environmentally friendly rubber oil.
  • the components of the butadiene rubber composition referred to in this embodiment are as follows: BR 100, carbon black 60, stearic acid 2, zinc oxide 5, accelerator CZ 1.5, accelerator DM 0.5, sulfur 2, environmentally friendly rubber oil 6, anti- Oxygen agent KY-616 1.
  • the butadiene rubber was masticated in an internal mixer for 2 min, and then carbon black, zinc oxide, stearic acid, and rubber oil were mixed for 8 minutes. The scrap was cleaned every 2 minutes, and the mixture was uniformly mixed. Then, according to the formula, the antioxidant, the accelerator, and the sulfur are added to the above-obtained rubber compound in an open mill according to a conventional method, and the mixture is obtained to obtain a rubber compound.
  • the rubber compound was vulcanized on the flat vulcanizate after being parked at room temperature for 24 hours.
  • the vulcanization temperature was 160 ° C
  • the vulcanization time was the positive vulcanization time (T 90 ) measured by the rotorless vulcanizer.
  • IR tested by KBr tablet method the test range of 4000-400cm -1, with a resolution of 4cm -1, scan number of 16.
  • the vulcanization property test was carried out in accordance with GB/T 16584-1996, and the temperature was 160 °C.
  • the tensile properties were measured in accordance with GB/T 528-2009, and the stretching rate was 500 mm/min.
  • the heat aging resistance is measured according to GB/T 3512-2001, and the aging condition is 100 ° C ⁇ (24, 48, 72, 96, 120) h.
  • the oxidation induction time was carried out by DSC according to GB/T 19466.6-2009.
  • the sample was kept at 60 ° C, 50 mL/min nitrogen flow rate for 5 min, then increased to 170 ° C at a temperature increase rate of 20 ° C / min, and kept for 5 min.
  • OIT oxidation induction time
  • the infrared spectrum of the antioxidant KY-616 is shown in Figure 2.
  • 3611 cm -1 is a stretching vibration absorption peak of a phenolic hydroxyl group
  • 3485 cm -1 is a partial phenolic hydroxyl group which generates a stretching vibration absorption peak after association.
  • 2950cm -1 and 2870cm -1 are the asymmetric stretching vibration and the symmetrical stretching vibration absorption peak of the methyl group, respectively.
  • 1465cm -1 and 1447cm -1 are the bending vibration absorption peaks of methylene and methyl respectively. Because the methyl absorption peak is strong, the absorption peak positions are relatively close, so that the absorption peaks of the two overlap partially.
  • 1395 cm -1 and 1361 cm -1 are the bending vibration absorption peaks of t-butyl groups
  • 1170 cm -1 is the CO stretching vibration absorption peak of phenolic hydroxyl groups
  • 858 cm -1 and 766 cm -1 are the out-of-plane bending vibration absorption peaks of the benzene rings.
  • the vulcanization characteristics and vulcanization parameters of the KY-616 mixed rubber with different amounts of antioxidants are shown in Figure 3 and Table 1, respectively. It can be seen that with the increase of the amount of antioxidant KY-616, on the one hand, the lowest torque and the highest torque of the rubber compound in the vulcanization process tend to decrease, indicating that the antioxidant KY-616 is mixed.
  • the rubber compound has a certain softening ability and can improve the processing performance of the rubber compound [8] .
  • the scorch time and the positive vulcanization time increase slowly, and the vulcanization rate decreases, indicating that the antioxidant KY-616 can prevent scorch and delay.
  • the vulcanization of rubber may be due to the fact that the antioxidant captures the free radicals generated by the rubber during the vulcanization process.
  • OIT oxidation induction time
  • DSC curve Testing the oxidation induction time (OIT) of vulcanizates by DSC curve is one of the simplest methods to evaluate the antioxidant effect of antioxidants on polymers. It can be seen from Table 2 that the OIT value of the BR added with the antioxidant KY-616 is significantly increased compared with the BR vulcanizate without any antioxidant added, indicating that the antioxidant KY-616 has good BR. Antioxidant effect. When the dosage of antioxidant KY-616 increased from 0 to 1 and 2 phr, the OIT value increased significantly from 45 min to 96.7 min and 107.4 min, respectively, and as the amount of antioxidant KY-616 continued to increase, BR vulcanizate The OIT value has declined slightly. Therefore, the antioxidant KY-616 is suitable in the butadiene rubber The dosage should be about 1-2 phr.
  • the tensile strength and elongation at break of the butadiene rubber vulcanizate with different amounts of antioxidant KY-616 added are shown in Fig. 4 and Fig. 5, respectively. It can be seen from the figure that the tensile strength and elongation at break of the vulcanizate increase with the increase of the amount of the antioxidant KY-616 without aging. This indicates that the antioxidant KY-616 is beneficial to improve the mechanical properties of the BR vulcanizate. The reason may be that in the process of mixing and vulcanization of BR, the antioxidant KY-616 effectively inhibits the occurrence of BR aging. The more the antioxidant KY-616 is used, the smaller the probability of aging during the preparation of vulcanizate. .
  • the effect of thermal aging is improved, but when the amount of KY-616 exceeds 1 phr, the increase is not large. Therefore, when the amount of the antioxidant KY-616 is more than 1 phr, the vulcanized rubber can achieve a better anti-thermal aging effect. However, considering the cost factor, the appropriate amount of KY-616 is 1 phr.
  • the components of the butadiene rubber composition referred to in this embodiment are as follows: BR 100, carbon black 56, stearic acid 1, zinc oxide 2, accelerator CZ 1, accelerator DM 0.1, sulfur 1, environmentally friendly rubber oil 3, anti- Oxygen agent KY-616 0.1.
  • the preparation method is referred to in Example 1.
  • the components of the butadiene rubber composition referred to in this embodiment are as follows: BR 100, carbon black 64, stearic acid 4, zinc oxide 7, accelerator CZ 3, accelerator DM 1.2, sulfur 4, environmentally friendly rubber oil 7, anti- Oxygen agent KY-616 5.
  • the preparation method is referred to in Example 1.
  • the processing performance of the butadiene rubber composition prepared in the present embodiment is remarkably improved, the anti-scorch ability is enhanced, the vulcanization time is prolonged, the vulcanization rate is lowered, and the mechanical properties of the vulcanizate and the anti-heat aging property are improved.
  • the butadiene rubber composition of the present invention adds KY-616, and the antioxidant KY-616 achieves a good anti-thermal aging effect; with the increase of the amount of KY-616, the mechanical properties and resistance of the vulcanized rubber
  • the thermal aging performance is improved, the oxidation induction time first increases and then tends to a stable value; the suitable amount of KY-616 in BR is 1 phr, the processing property of the butadiene rubber composition of the invention is remarkably improved, the scorch resistance is enhanced, and the vulcanization is enhanced.
  • the time is prolonged, the vulcanization rate is lowered, and the mechanical properties of the vulcanizate and the resistance to thermal aging are improved.
  • the present invention also studies the preparation method of the butadiene rubber composition, and the preparation method of the butadiene rubber composition is composed of the following steps:
  • Step one take the butadiene rubber, and then put it into the internal mixer for mastication; after the second step, add carbon black, zinc oxide, stearic acid, rubber oil, and mix to obtain the mixed rubber; step three, take the antioxidant The accelerator and the sulfur are added to the mixed rubber to obtain a rubber compound; in step four, after standing and vulcanized, the butadiene rubber composition is obtained.
  • the mastication time is 1-3 min. Further preferably, in the first step, the mastication time is 2 min.
  • the mixing time is 5-9 min. Further preferably, in the second step, the mixing time is 8 min.
  • the standing is specifically parked at room temperature for 20-30 hours. Further preferably, in step four, the standing is specifically room temperature for 24 hours.
  • the vulcanization temperature is 150-165 °C. Further preferably, in the fourth step, the vulcanization temperature is 160 °C.
  • the vulcanization time is a positive vulcanization time measured by a rotorless vulcanizer.
  • the invention also relates to the use of KY-616 as a modification additive for a butadiene rubber composition.
  • the application is specifically: adding KY-616 to the butadiene rubber composition, and further Improve the processing properties of the butadiene rubber composition.
  • the application is specifically to add KY-616 to the butadiene rubber composition to improve the scorch resistance.
  • the application is specifically to add KY-616 to the butadiene rubber composition to further extend the vulcanization time and reduce the vulcanization rate.
  • the application is specifically to add KY-616 to the butadiene rubber composition to enhance the resistance to thermal oxygen aging.
  • the present invention proposes an excellent performance of a butadiene rubber composition, and systematically studies the preparation method of the butadiene rubber composition, and also proposes a new application of KY-616, and finds KY-616. It can be applied to the butadiene rubber composition to provide an unexpected technical effect of modifying and improving the rubber properties.
  • the processing properties of the butadiene rubber composition of the invention are remarkably improved, the scorch resistance is enhanced, the vulcanization time is prolonged, and the vulcanization rate is lowered.
  • Antioxidant KY-616 has good resistance to thermal aging in BR.
  • a suitable amount of KY-616 in BR is 1 phr.
  • methylphenol-dicyclopentadiene-isobutylated resin (KY-616) can produce an unexpected technical effect in the preparation of a butadiene rubber composition.
  • p-Methylphenol-dicyclopentadiene-isobutylated resin (KY-616) is a novel macromolecular polyphenolic antioxidant with high activity, low volatility and excellent migration resistance;
  • the applicants used infrared spectroscopy (FT-IR) to characterize the structure of KY-616, and studied its effect on the vulcanization properties, mechanical properties and thermal aging properties of butadiene rubber (BR).
  • the antioxidant KY-616 has the function of preventing scorch and improving the processing property of the rubber; with the increase of the amount of the antioxidant KY-616, the mechanical properties of the BR vulcanizate and the aging resistance of the heat-resistant oxygen are improved, and oxidation The induction time (OIT) first increased and then became unchanged.
  • the suitable amount of KY-616 in BR is 1 phr; the rational use of the antioxidant KY-616 has an unexpected technical effect on improving the performance of the butadiene rubber composition.

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Abstract

本发明提供一种KY-616作为顺丁橡胶组合物改性添加剂的应用。本发明中KY-616能够应用于顺丁橡胶组合物，起到改性并提升橡胶性能的意想不到的技术效果；本发明的顺丁橡胶组合物加工性能显著提升，防焦烧能力增强，硫化时间延长，硫化速度降低，硫化胶力学性能和抗热氧老化性能提升。抗氧剂KY-616在BR中具有良好的抗热氧老化效果。随着KY-616用量的增加，硫化胶的力学性能和耐热氧老化性能提高，氧化诱导时间先增大后趋于稳定值；KY-616在BR中的适宜用量为1phr。

Description

KY-616作为顺丁橡胶组合物改性添加剂的应用 技术领域
本发明涉及橡胶制备技术领域，特别涉及一种KY-616作为顺丁橡胶组合物改性添加剂的应用。
背景技术
高分子材料在贮存、加工、使用过程中，容易受到热、氧、臭氧、机械力等的作用，使其结构与性能发生变化，逐渐失去使用价值，这种现象称为高分子材料的老化。而在橡胶中，由于其分子链上含有大量的双键，热氧老化问题更加突出。为了抑制或延缓氧化反应的发生，通常在橡胶中加入抗氧剂。目前最常用的主抗氧剂有受阻酚类和芳胺类，其中受阻酚具有不变色、无毒无污染等优点，在高分子材料中广泛应用。
一般来说，抗氧剂除了应具有较好的抗氧化性能外，还应具备良好的热稳定性、耐迁移性和耐抽提性。然而，目前大多数使用的抗氧剂为小分子物质，其存在着受热易挥发、不耐迁移及抽提等缺点，不利于其在聚合物中长期稳定的存在，因而难以满足材料与日俱增的防老化要求。近年来，为了克服传统低分子量抗氧剂不耐抽提等缺点，国内外学者对大分子抗氧剂的制备及其在高分子材料中的应用进行了大量研究，大分子抗氧剂已成为抗氧剂发展的一个重要方向。顺丁橡胶(BR)是目前仅次于丁苯橡胶(SBR)的世界上第二大通用合成胶，有关顺丁橡胶的抗氧剂的研究较少。
中国发明专利201310711836.8(公开日2014年4月23日)披露了一种新型顺丁橡胶，包括：丁二烯、聚异戊二烯、填充油、炭黑粉末和添加剂，所述丁二烯在新型顺丁橡胶中所占的重量百分比为43％，所述聚异戊二烯在新型顺丁橡胶中所占的重量百分比为9％，所述填充油在新型顺丁橡胶中所占的重量百分比为26％，所述炭黑粉末在新型顺丁橡胶中所占的重量百分比为6％，所述添加剂在新型顺丁橡胶中所占的重量百分比为16％，所述添加剂包括催化剂、终止剂和抗老化剂。该发明披露的新型顺丁橡胶，采用了多种优质原料，得到的新型顺丁橡胶提高了抗湿滑性能和 加工性能，抗撕裂强度高，粘着性好，应用范围广泛；但该发明并未记载有关顺丁橡胶的抗氧剂的相关技术内容。
中国发明专利201410516405.0(公开日2015年2月4日)披露了一种顺丁橡胶，包含如下组成成分：顺式聚丁二烯混合物30-50份，环己烷5-9份，氧化钴1-3份，氧化锌2-5份，硫磺3-7份，硬脂酸1-3份，环烷酸镍1-5份，三异丁基铝5-9份，三氟化硼乙醚2-4份，庚烷2-6份，氢汽油3-8份，促进剂NS15-19份，HAF10-13份，ASTM型103油11-15份，铝氧熟料2-8份，对氯间二甲酚2-5份。所述顺式聚丁二烯混合物由顺式1，4-聚丁二烯和顺式1，3-聚丁二烯混合而成。所述顺式1，4-聚丁二烯和顺式1，3-聚丁二烯占混合物总重量比为2：5。该发明所提供的顺丁橡胶含有顺式聚丁二烯混合物，能够有效的降低撕裂强度，提高抗湿滑性能及粘着性，具备较低的生热性。同样，该发明并未记载有关顺丁橡胶的抗氧剂的相关技术内容。
抗氧剂KY-616(或称Wingstay L，Lowinox CPL，Vanox L等)是一种聚合多酚类抗氧剂，其化学结构式如图1所示。该抗氧剂分子量较大、与聚合物相容性较好，具有耐热、耐抽出等特点，是近年来开发的一种新型大分子抗氧剂，其在高分子材料中的应用研究受到了研究者的关注。李志弘研究了抗氧剂KY-616在天然橡胶中的抗热氧老化性能，发现其在天然橡胶中表现出较好的稳定化效果，而且其耐水抽提性能优于胺类抗氧剂-MB。骆静研究了抗氧剂KY-616在避孕套生产中应用，发现在天然胶乳制备的避孕套制品中，抗氧剂KY-616的抗老化性能优于抗氧剂264及抗氧剂甲叉4426-S。但是抗氧剂KY-616在BR中的应用研究则鲜见报道。本申请研究了抗氧剂KY-616对顺丁橡胶(BR)硫化特性、力学性能和耐热氧老化性能的影响，以评价KY-616在丁二烯类橡胶中的抗氧化效果，并确定抗氧剂KY-616的适宜用量，为提升顺丁橡胶(BR)的性能提供了技术支撑。
发明内容
在下文中给出关于本发明的简要概述，以便提供关于本发明的某些方面的基本理解。应当理解，这个概述并不是关于本发明的穷举性概述。它并不是意图确定本发明的关键或重要部分，也不是意图限定本发明的范围。其目的仅仅是以简化的形式给出某些概念，以此作为稍后论述的更详 细描述的前序。
本发明的目的在于克服现有技术的不足，提供一种KY-616作为顺丁橡胶组合物改性添加剂的应用。
本发明是通过以下的技术方案实现的，本发明涉及一种KY-616作为顺丁橡胶组合物改性添加剂的应用。
与现有技术相比，本发明具有如下的有益效果：添加KY-616，可使得制备的顺丁橡胶组合物加工性能显著提升，防焦烧能力增强，硫化时间延长，硫化速度降低，硫化胶力学性能和抗热氧老化性能提升。抗氧剂KY-616实现了良好的抗热氧老化效果；随着KY-616用量的增加，硫化胶的力学性能和耐热氧老化性能提高，氧化诱导时间先增大后趋于稳定值；KY-616在BR中的适宜用量为1phr；添加抗氧剂KY-616，制备的顺丁橡胶组合物加工性能显著提升，防焦烧能力增强，硫化时间延长，硫化速度降低，硫化胶力学性能和抗热氧老化性能提升。
附图说明
参照下面结合附图对本发明实施例的说明，会更加容易地理解本发明的以上和其它目的、特点和优点。附图中的部件只是为了示出本发明的原理。在附图中，相同的或类似的技术特征或部件将采用相同或类似的附图标记来表示。
图1为抗氧剂KY-616的化学结构式；
图2为抗氧剂KY-616的红外光谱；
图3为添加不同用量抗氧剂KY-616的BR混炼胶的硫化曲线图；
图4为抗氧剂KY-616用量和老化时间对BR硫化胶拉伸强度的影响；
图5为抗氧剂KY-616用量与老化时间对BR硫化胶断裂伸长率影响。
具体实施方式
下面参照附图来说明本发明的实施例。在本发明的一个附图或一种实施方式中描述的元素和特征可以与一个或更多个其它附图或实施方式中示出的元素和特征相结合。应当注意，为了清楚的目的，附图和说明中省略了与本发明无关的、本领域普通技术人员已知的部件和处理的表示和描 述。
实施例1
本发明涉及的顺丁橡胶组合物，由如下重量份数的各组分组成，顺丁橡胶100，炭黑56-64，硬脂酸1-4，氧化锌2-7，促进剂1.1-4.2，硫磺1-4，橡胶油3-7，抗氧剂KY-616 0.1-5。
优选地，所述促进剂为促进剂CZ、或促进剂DM，或为促进剂CZ和促进剂DM的混合。优选地，所述促进剂为促进剂CZ和促进剂DM的混合，其中促进剂CZ 1-3，促进剂DM 0.1-1.2。
优选地，所述组合物由如下重量份数的各组分组成：顺丁橡胶100，炭黑60，硬脂酸2，氧化锌5，促进剂CZ 1.5，促进剂DM 0.5，硫磺2，橡胶油6，抗氧剂KY-616 0.8-4。
优选地，所述组合物由如下重量份数的各组分组成：顺丁橡胶100，炭黑60，硬脂酸2，氧化锌5，促进剂CZ 1.5，促进剂DM 0.5，硫磺2，橡胶油6，抗氧剂KY-616 1。
优选地，所述橡胶油为环保橡胶油。
本实施例中涉及的顺丁橡胶组合物组分如下：BR 100，炭黑60，硬脂酸2，氧化锌5，促进剂CZ 1.5，促进剂DM 0.5，硫磺2,环保橡胶油6，抗氧剂KY-616 1。
一、实验过程：
1.1原材料
顺丁橡胶(BR)：BR 9000，北京燕山石化橡塑化工有限责任公司；
对甲基苯酚-双环戊二烯-异丁基化树脂(抗氧剂KY-616)：江苏飞亚化学工业有限责任公司；
高耐磨炭黑(HAF)：N330，上海卡博特化工有限公司；
环保橡胶油：中海油沥青股份有限公司；
氧化锌(ZnO)、硬酯酸(SA)、硫黄(S)、N-环已基-2-苯并噻唑次磺酰胺(促进剂CZ)和2,2'-二硫代二苯并噻唑(促进剂DM)：广州金昌盛科技有限公司。
1.2基本配方
BR 100，炭黑60，硬脂酸2，氧化锌5，促进剂CZ 1.5，促进剂DM 0.5，硫磺2,环保橡胶油6，抗氧剂KY-616 1。
1.3仪器与设备
密炼机(LN-1，利拿机械(东莞)实业有限公司)，
橡胶开炼机(XK-168,利拿机械(东莞)实业有限公司)，
平板硫化机(KSHR 100，广东深圳科盛机械有限公司)，
拉力试验机(UT-2080，优肯科技股份有限公司)，
无转子硫化仪(UR-2010SD-A，优肯科技股份有限公司)，
DSC(Q20，美国TA仪器公司)，
老化试验箱(GT-717，高铁检测仪器(东莞)有限公司)，
傅里叶变换红外光谱仪(Tensor 27，德国Bruker)。
1.4顺丁橡胶硫化胶的制备
将顺丁橡胶在密炼机中塑炼2min，然后加入炭黑、氧化锌、硬脂酸、橡胶油混炼8min，其中每隔2min停机清理边角料，混炼均匀后，排胶备用。然后按照配方，将抗氧剂、促进剂、硫磺在开炼机上按照常规方法加入到上述得到的胶料中，出片后得到混炼胶。混炼胶在室温停放24h后在平板硫化胶上硫化，硫化温度为160℃，硫化时间为无转子硫化仪测定的正硫化时间(T90)。
1.5测试与表征
红外光谱通过KBr压片法进行测试，测试范围为4000-400cm-1，分辨率为4cm-1，扫描次数为16次。硫化特性测试按照GB/T16584-1996测定，温度为160℃。拉伸性能按照GB/T 528-2009测定，拉伸速率为500mm/min。耐热老化性能按GB/T 3512-2001测定，老化条件100℃×(24,48,72,96,120)h。氧化诱导时间利用DSC按照GB/T 19466.6-2009进行，首先，样品在60℃，50mL/min的氮气流速下保持5min，之后以20℃/min的升温速度升至170℃，保持5min后，改为流量为50mL/min的氧气氛围，从开始通氧气至出现氧化放热峰所需要的时间为氧化诱导时间(OIT)。
二、实施效果；
2.1 FT-IR分析
抗氧剂KY-616的红外光谱如图2所示。在图2中，3611cm-1为酚羟基的伸缩振动吸收峰，3485cm-1为部分酚羟基产生了缔合作用后的伸缩振动吸收峰。2950cm-1和2870cm-1分别为甲基的非对称伸缩振动与对称伸 缩振动吸收峰。1465cm-1和1447cm-1分别为亚甲基与甲基的弯曲振动吸收峰，由于甲基吸收峰较强，吸收峰位置比较相近，从而使两者的吸收峰发生了部分重叠。1395cm-1和1361cm-1为叔丁基的弯曲振动吸收峰，1170cm-1为酚羟基的C-O伸缩振动吸收峰，858cm-1与766cm-1为苯环的面外弯曲振动吸收峰。
2.2抗氧剂KY-616对BR混炼胶硫化特性的影响
添加不同用量抗氧剂KY-616混炼胶的硫化特性曲线及硫化参数分别如图3和表1所示。可以看出，随着抗氧剂KY-616用量的增大，一方面，混炼胶在硫化过程中的最低转矩与最高转矩均成下降的趋势，表明抗氧剂KY-616对混炼胶具有一定的软化能力，能够改善混炼胶的加工性能[8]；另一方面，焦烧时间和正硫化时间缓慢增加，硫化速率下降，表明抗氧剂KY-616能够防止焦烧、延缓橡胶的硫化，其原因可能是由于抗氧剂捕捉了橡胶在硫化过程中产生的自由基。
表1添加不同用量抗氧剂KY-616的BR混炼胶的硫化参数
Figure PCTCN2015091549-appb-000001
2.3抗氧剂KY-616对BR硫化胶氧化诱导时间的影响
通过DSC曲线测试硫化胶的氧化诱导时间(OIT)，是评价抗氧剂对聚合物抗氧化效果最为简单的方法之一。从表2中可以看出，与没有添加任何抗氧剂的BR硫化胶相比，添加抗氧剂KY-616的BR的OIT值明显增加，说明了抗氧剂KY-616对BR具有良好的抗氧化效果。当抗氧剂KY-616用量从0增加至1和2phr时，OIT值增加较明显，从45min分别增加到96.7min和107.4min，而随着抗氧剂KY-616用量继续增加，BR硫化胶的OIT值反而出现了小幅下降。因此，抗氧剂KY-616在顺丁橡胶中的适 宜用量为1-2phr左右。
表2 KY-616用量对BR硫化胶的氧化诱导时间的影响
用量(phr) 氧化诱导时间(OIT)/(min)
0 45
0.5 66
1 96.7
2 107.4
3 103.4
4 101.2
2.4抗氧剂KY-616对BR硫化胶力学性能和抗热氧老化性能的影响
添加不同用量抗氧剂KY-616的顺丁橡胶硫化胶的拉伸强度和断裂伸长率与老化时间的关系分别如图4和图5所示。从图中可以看出，在没有老化的情况下，随着抗氧剂KY-616用量的增大，硫化胶的拉伸强度、断裂伸长率升高。这说明抗氧剂KY-616有利于提高BR硫化胶的力学性能。其原因可能是BR在混炼及硫化成型的过程中，抗氧剂KY-616有效抑制了BR老化的发生，抗氧剂KY-616用量越多，在硫化胶制备过程中老化的几率越小。
从图4和图5中可以看出，随着老化时间的增加，硫化胶拉伸强度和断裂伸长率下降，其中没有添加抗氧剂的硫化胶下降幅度最大，下降速度最快。而添加了抗氧剂的硫化胶下降幅度较小、速度较慢。这也说明了KY-616对抑制BR硫化胶的热氧老化具有较好的效果。另外从图4和图5中也可以看出，在对硫化胶老化相同的时间后，随着KY-616用量的增加，硫化胶的拉伸强度和断裂伸长率相应地变大，即抗热氧老化效果提高，但当KY-616用量超过1phr，则其提高幅度不大。因此，当抗氧剂KY-616用量大于1phr时，硫化胶能够达到较好的抗热氧老化效果。但考虑到成本因素，KY-616的适宜用量为1phr。
实施例2
本实施例中涉及的顺丁橡胶组合物组分如下：BR 100，炭黑56，硬脂酸1，氧化锌2，促进剂CZ 1，促进剂DM 0.1，硫磺1,环保橡胶油3，抗氧剂KY-616 0.1。制备方法参照实施例1。
实施效果：本实施例制备的顺丁橡胶组合物加工性能显著提升，防焦烧能力增强，硫化时间延长，硫化速度降低，硫化胶力学性能和抗热氧老 化性能提升。
实施例3
本实施例中涉及的顺丁橡胶组合物组分如下：BR 100，炭黑64，硬脂酸4，氧化锌7，促进剂CZ 3，促进剂DM 1.2，硫磺4,环保橡胶油7，抗氧剂KY-616 5。制备方法参照实施例1。
实施效果：本实施例制备的顺丁橡胶组合物加工性能显著提升，防焦烧能力增强，硫化时间延长，硫化速度降低，硫化胶力学性能和抗热氧老化性能提升。
综上可见，本发明的顺丁橡胶组合物添加了KY-616，抗氧剂KY-616实现了良好的抗热氧老化效果；随着KY-616用量的增加，硫化胶的力学性能和耐热氧老化性能提高，氧化诱导时间先增大后趋于稳定值；KY-616在BR中的适宜用量为1phr，本发明的顺丁橡胶组合物加工性能显著提升，防焦烧能力增强，硫化时间延长，硫化速度降低，硫化胶力学性能和抗热氧老化性能提升。
同时，本发明亦对顺丁橡胶组合物的制备方法进行研究，顺丁橡胶组合物的制备方法由如下步骤组成：
步骤一，取顺丁橡胶，放入密炼机中塑炼；步骤二，之后加入炭黑、氧化锌、硬脂酸、橡胶油，混炼，得混合胶料；步骤三，取抗氧剂、促进剂和硫磺，加入混合胶料中，得混炼胶；步骤四，之后静置，硫化，即得所述顺丁橡胶组合物。
优选地，步骤一中，所述塑炼的时间为1-3min。进一步优选地，步骤一中，所述塑炼的时间为2min。
优选地，步骤二中，所述混炼的时间为5-9min。进一步优选地，步骤二中，所述混炼的时间为8min。
优选地，步骤四中，所述静置具体为室温停放20-30小时。进一步优选地，步骤四中，所述静置具体为室温停放24小时。
优选地，步骤四中，所述硫化的温度为150-165℃。进一步优选地，步骤四中，所述硫化的温度为160℃。优选地，步骤四中，所述硫化的时间为无转子硫化仪测定的正硫化时间。
同时，本发明还涉及KY-616作为顺丁橡胶组合物改性添加剂的应用。
优选地，所述应用具体为，在顺丁橡胶组合物中添加KY-616，进而 提升顺丁橡胶组合物的加工性能。
优选地，所述应用具体为，在顺丁橡胶组合物中添加KY-616，进而提升防焦烧能力。
优选地，所述应用具体为，在顺丁橡胶组合物中添加KY-616，进而延长硫化时间和降低硫化速度。
优选地，所述应用具体为，在顺丁橡胶组合物中添加KY-616，进而提升抗热氧老化。
综上所述，本发明提出了一种性能优异的顺丁橡胶组合物，同时系统研究了所述顺丁橡胶组合物的制备方法，同时也提出了KY-616的全新应用，发现KY-616能够应用于顺丁橡胶组合物，起到改性并提升橡胶性能的意想不到的技术效果。本发明的顺丁橡胶组合物加工性能显著提升，防焦烧能力增强，硫化时间延长，硫化速度降低。抗氧剂KY-616在BR中具有良好的抗热氧老化效果。随着KY-616用量的增加，硫化胶的力学性能和耐热氧老化性能提高，氧化诱导时间先增大后趋于稳定值。KY-616在BR中的适宜用量为1phr。
本发明中，发明人经过大量实验，意外地发现甲基苯酚-双环戊二烯-异丁基化树脂(KY-616)在制备顺丁橡胶组合物中能够产生令人意想不到的技术效果。对甲基苯酚-双环戊二烯-异丁基化树脂(KY-616)是一种新型大分子多酚抗氧剂，具有高活性、低挥发性和优良的耐迁移性等特点；本发明中，申请人采用红外光谱(FT-IR)对KY-616的结构进行了表征，研究了其对顺丁橡胶(BR)的硫化特性、力学性能和耐热氧老化性能的影响。本发明人发现抗氧剂KY-616具有防止焦烧和改善胶料加工性能的作用；随着抗氧剂KY-616用量的增加，BR硫化胶的力学性能和耐热氧老化性提高，氧化诱导时间(OIT)先增大后趋于不变。KY-616在BR中的适宜用量为1phr；抗氧剂KY-616的合理使用，对于提升顺丁橡胶组合物的性能起到了意想不到的技术效果。
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (7)

  1. 一种KY-616作为顺丁橡胶组合物改性添加剂的应用。
  2. 根据权利要求1所述的KY-616作为顺丁橡胶组合物改性添加剂的应用，其特征在于，所述应用具体为，在顺丁橡胶组合物中添加KY-616，进而提升顺丁橡胶组合物的加工性能。
  3. 根据权利要求1所述的KY-616作为顺丁橡胶组合物改性添加剂的应用，其特征在于，所述应用具体为，在顺丁橡胶组合物中添加KY-616，进而提升防焦烧能力。
  4. 根据权利要求1所述的KY-616作为顺丁橡胶组合物改性添加剂的应用，其特征在于，所述应用具体为，在顺丁橡胶组合物中添加KY-616，进而延长硫化时间和降低硫化速度。
  5. 根据权利要求1所述的KY-616作为顺丁橡胶组合物改性添加剂的应用，其特征在于，在顺丁橡胶组合物中添加KY-616，进而提升抗热氧老化能力。
  6. 根据权利要求1所述的KY-616作为顺丁橡胶组合物改性添加剂的应用，其特征在于，所述顺丁橡胶组合物由如下重量份数的各组分组成：顺丁橡胶100，炭黑56-64，硬脂酸1-4，氧化锌2-7，促进剂1.1-4.2，硫磺1-4，橡胶油3-7，抗氧剂KY-616 0.1-5。
  7. 根据权利要求6所述的KY-616作为顺丁橡胶组合物改性添加剂的应用，其特征在于，所述顺丁橡胶组合物由如下重量份数的各组分组成：BR 100，炭黑60，硬脂酸2，氧化锌5，促进剂CZ 1.5，促进剂DM0.5，硫磺2,环保橡胶油6，抗氧剂KY-616 1。
PCT/CN2015/091549 2015-03-25 2015-10-09 Ky-616作为顺丁橡胶组合物改性添加剂的应用 WO2016150142A1 (zh)

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