WO2021134854A1 - 一类硫化剂及其应用 - Google Patents

一类硫化剂及其应用 Download PDF

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Publication number
WO2021134854A1
WO2021134854A1 PCT/CN2020/073464 CN2020073464W WO2021134854A1 WO 2021134854 A1 WO2021134854 A1 WO 2021134854A1 CN 2020073464 W CN2020073464 W CN 2020073464W WO 2021134854 A1 WO2021134854 A1 WO 2021134854A1
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vulcanizing agent
polymer
temperature
initiator
cross
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English (en)
French (fr)
Inventor
牛慧
谢诗琪
刘姝慧
何宗科
包卓
刘丽英
华哲
王爱慧
尹文静
王晶
李旭
孙爽
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Dalian University of Technology
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Dalian University of Technology
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Priority to JP2022540397A priority Critical patent/JP7424682B2/ja
Priority to US17/758,285 priority patent/US12359040B2/en
Publication of WO2021134854A1 publication Critical patent/WO2021134854A1/zh
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Definitions

  • the invention relates to the technical field of polymer vulcanizing agents, in particular to a type of vulcanizing agent and its application, and in particular to a type of vulcanizing agent with reversible crosslinking function and its application in polymers.
  • Vulcanization is an important means of cross-linking polymers.
  • the three-dimensional network structure formed by polymers after vulcanization can give polymer materials higher strength, temperature stability and chemical stress cracking resistance, especially for rubber Polymer materials, only through cross-linking modification, can make them have the required elasticity, resilience, strength and dimensional stability in the application process.
  • Sulfur vulcanization is the earliest rubber cross-linking process discovered by centuries.
  • the vulcanization process greatly improves the physical and chemical properties of rubber products.
  • the vulcanization process has developed peroxide vulcanization, radiation vulcanization, functional group vulcanization and other methods, but sulfur vulcanization is still the most economical method with cheap raw materials.
  • vulcanization accelerators and activators added to the sulfur vulcanization system, the amount of sulfur can be further reduced, the vulcanization time, and the vulcanization temperature can be reduced.
  • Organic peroxide vulcanization is the use of compounds containing one or more peroxy bonds (-OO-) in the structure to generate free radicals through homolytic cracking, which initiates free radical reactions between polymer molecules to produce a cross-linked network structure .
  • Peroxide crosslinking can be implemented in saturated polymers (usually it is necessary to add more than 2wt% peroxide in the polymer), which overcomes the problem that saturated polymers (such as ethylene propylene rubber) are difficult to vulcanize with sulfur.
  • Radiation vulcanization is a technology that uses high-energy rays to crosslink polymer molecules, which can eliminate the need to add peroxides or sulfur and other sulfides.
  • the basic principle is that high-energy rays activate polymer molecules when they pass through the polymer substrate. Generate free radicals, and then combine these free radicals to form a cross-linked network.
  • people also use the introduction of reactive groups in the polymer side groups to implement crosslinking.
  • Vinylsiloxane is a kind of mild and efficient functional monomer commonly used in crosslinking polyolefins. It can be used in the presence of water.
  • the crosslinking reaction is realized under the following conditions, and a highly crosslinked material is obtained.
  • Direct crosslinking of polymers with diolefin vulcanizing agents such as divinylbenzene
  • Vulcanization cross-linking is currently the main cross-linking technology for polymer materials.
  • the cross-linked covalent bonds formed by it are irreversible, making the cross-linked polymer unable to be reprocessed. Therefore, while giving the material excellent performance, it also brings about polymerization.
  • rubber desulfurization and recycling technology emerged as the times require, and has been applied in the recycling of polymer rubber species represented by natural rubber and butyl rubber.
  • the purpose of the present invention is to provide a new type of vulcanizing agent which has at least two ⁇ -olefin structures and is the product of [4+2] cycloaddition reaction.
  • the vulcanizing agent has the following formula (I) ⁇ Any structure in (VI):
  • the structure of formula (I) in the present invention is directly prepared from bismaleimide and substituted furan or substituted pyrrole through Diels-Alder reaction ([4+2] cycloaddition reaction); or from bismaleimide After the imine is reacted with substituted furan or substituted pyrrole through Diels-Alder, it is prepared by modifying the substituent;
  • the structure of the formula (II) of the present invention is directly prepared by the Diels-Alder reaction of diene and substituted furan or substituted pyrrole; or is obtained by Diels-Alder reaction of diene and substituted furan or substituted pyrrole, and then substituted
  • the base is modified and prepared;
  • the structure of the formula (III) of the present invention is obtained by dimerization of the cyclopentadiene compound substituted by the alkenyl group itself through the Diels-Alder reaction; or the cyclopentadiene compound substituted by the alkenyl group is dimerized through the Diels-Alder reaction , And then modify the substituents to prepare and obtain;
  • the structure of the formula (IV) of the present invention is prepared from trimaleimide or tetramaleimide, and alkenyl substituted furan or alkenyl substituted pyrrole through Diels-Alder reaction; or from trimaleimide After Diels-Alder reaction of imine or tetramaleimide with substituted furan or substituted pyrrole, the substituent is modified to obtain it;
  • the structure of formula (V) of the present invention is prepared by Diels-Alder reaction with triene or tetraene, and alkenyl substituted furan or alkenyl substituted pyrrole; or from triene or tetraene, substituted with furan or substituted with alkenyl
  • the pyrrole is prepared by the Diels-Alder reaction and then modified by the substituents;
  • the structure of formula (VI) in the present invention is directly prepared by Diels-Alder reaction between substituted maleimide and substituted furan or substituted pyrrole; or directly prepared by Diels-Alder reaction from substituted maleimide and substituted furan or substituted pyrrole through Diels After the Alder reaction, the substituent is modified to obtain it.
  • Another object of the present invention is to provide the application of the above-mentioned novel vulcanizing agent in polymer vulcanization and cross-linking, using polymer, vulcanizing agent, and initiator as raw materials, and adopting a melting method.
  • the mass ratio of the polymer to the vulcanizing agent is 100:0.01 to 100:10; the mass ratio of the polymer to the initiator is 100:0.01 to 100:1; a heat stabilizer can also be added, and the polymer and the The mass ratio of the heat stabilizer is 100:0 ⁇ 100:1, and the addition amount of the heat stabilizer can be 0.
  • the polymer is selected from at least one of polyolefin resin or polyolefin rubber.
  • the mass ratio of the polymer to the vulcanizing agent is 100:0.1-100:5; the mass ratio of the polymer to the initiator is 100:0.05-100:0.5; the polymer and the heat stabilizer The mass ratio is 100:0.1 ⁇ 100:0.5.
  • the initiator is selected from organic peroxides or azo initiators.
  • the organic peroxide is cyclohexanone peroxide, dicumyl peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, or 2,5-dimethyl-2,5 -Di(tert-butylperoxy)hexane.
  • the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile.
  • the heat stabilizer is selected from at least one of hindered phenolic macromolecular antioxidants, phosphorous acid antioxidants or alkyl ester antioxidants.
  • the heat stabilizer is a combination of the hindered phenolic macromolecular antioxidant and the phosphorous acid antioxidant.
  • the heat stabilizer is antioxidant 1010 (tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester) and antioxidant 168 (three [2.4 -Di-tert-butylphenyl] phosphite).
  • the mass ratio of the antioxidant 1010 and the antioxidant 168 is 1:0.5 to 1:2.
  • the polymer is selected from at least one of saturated polyolefin resin or saturated polyolefin rubber.
  • the polyolefin resin is selected from homopolymers or copolymer resins such as polyethylene, polypropylene, poly-1-butene, and the like.
  • the polyolefin rubber is selected from ethylene propylene rubber, ethylene/higher ⁇ -olefin copolymer elastomer, butyl rubber, styrene/isobutylene copolymer rubber, and the like.
  • the polymer vulcanization crosslinking method includes the following steps:
  • the reactive processing equipment used in the method is any one of a single-screw extruder, a twin-screw extruder, an open mixer, and an internal mixer.
  • the vulcanizing agent When the vulcanizing agent is solid, it can be uniformly mixed by dissolving the vulcanizing agent in a solvent and then mixing the polymer.
  • the solvent is generally acetone, ethanol, etc., which is volatile and does not react with the vulcanizing agent or polymer, and then evaporates naturally. Solvent.
  • the novel vulcanizing agent of the present invention is a compound with a reversible covalent bond: the functional group in the molecule undergoes a reverse Diels-Alder reaction at high temperature (100-200°C, depending on the structure). (Reverse [4+2] cycloaddition reaction) can be decomposed into two parts; then at low temperature (0 ⁇ 120°C, depending on the structure, the temperature is different), through the Diels-Alder reaction ([4+2] ring Addition reaction) can recombine into the original functional group, that is, it has thermally reversible reaction characteristics.
  • the two or more double bonds of the molecular end group can chemically crosslink the polymer under the action of the initiator to form a network structure and realize the enhancement of the polymer.
  • the material can be de-crosslinked, so that the material has thermoplasticity; it can be cross-linked again after cooling to produce a network structure, thereby giving the material repetitive processability and Recyclability.
  • the present invention provides the application of the above-mentioned vulcanizing agent in a recyclable cross-linked polymer material.
  • Figure 1 is the cross-linked rubber product prepared in Example 4 after being cut into pieces and then hot-pressed again;
  • A is the cross-linked rubber spline added with the vulcanizing agent of the present invention;
  • B is the rubber spline being cut into fragments;
  • C is the fragments again Its performance can be restored after processing and forming.
  • vulcanizing agent A The structural formula of vulcanizing agent A is:
  • reaction formula 1 The synthesis method is shown in reaction formula 1.
  • the reactant 2N,N'-(4,4'-methylenediphenyl)bismaleimide is a commercial product (CAS13676-54-5), which was purchased from Anaiji Chemical Co., Ltd. in this experiment.
  • Synthesis of vulcanizing agent A Dissolve reactant 1 (8.00g, 0.04mol) and reactant 2 (7.14g, 0.02mol) in 50ml tetrahydrofuran, and react at 60°C for 24h under nitrogen protection. After the reaction is completed, cool to room temperature, pour the reaction solution into excess ether, extract the organic phase, and distill the organic phase product under reduced pressure to remove the solvent. The viscous liquid obtained is the vulcanizing agent A.
  • vulcanizing agent B The structural formula of vulcanizing agent B is:
  • reaction formula 2 The synthesis method is shown in reaction formula 2.
  • the reactant 1 Furfuryl alcohol is a commercial product (CAS 98-00-0), which was purchased from Anaiji Chemical Co., Ltd. in this experiment.
  • the reactant 2 1,4-butanediol diacrylate is a commercial product (CAS 1070-70-8), which was purchased from Anaiji Chemical Co., Ltd. in this experiment.
  • Synthesis of vulcanizing agent B Dissolve reactant 1 (3.92g, 0.04mol) and reactant 2 (3.96g, 0.02mol) in 50ml tetrahydrofuran, and react at room temperature for 72h under nitrogen protection. After the reaction is completed, the low boiling point liquid is removed under reduced pressure to obtain the intermediate product M. Dissolve the intermediate product M in dichloromethane, and add 3 mL of triethylamine, add 0.04 mol of methacryloyl chloride under a nitrogen atmosphere, stir and react at room temperature for 4 hours.
  • vulcanizing agent C The structural formula of vulcanizing agent C is:
  • reaction formula 3 The synthesis method is shown in reaction formula 3.
  • Synthesis of vulcanizing agent C The reactant (12.0g, 0.08mol) was dissolved in 50ml of tetrahydrofuran and reacted at room temperature for 48h. After the reaction is completed, it is cooled to room temperature and distilled under reduced pressure to obtain the vulcanizing agent C.
  • vulcanizing agent D The structural formula of vulcanizing agent D is:
  • reaction formula 4 The synthesis method is shown in reaction formula 4.
  • vulcanizing agent D Synthesis of vulcanizing agent D: reactant 1 (4.96g, 0.03mol) and reactant 2 (3.86g, 0.01mol) were dissolved in 50ml of tetrahydrofuran, and reacted at 60°C for 48h under nitrogen protection. After the reaction is completed, it is cooled to room temperature, and the low-boiling liquid is removed by distillation under reduced pressure to obtain the sulfurizing agent D.
  • Vulcanizing agent having the structure shown in formula (V)
  • vulcanizing agent E The structural formula of vulcanizing agent E is:
  • reaction formula 5 The synthesis method is shown in reaction formula 5.
  • vulcanizing agent E Dissolve pentaerythritol tetraacrylate (3.52g, 0.01mol) and furfuryl alcohol (3.92g, 0.04mol) in 50ml tetrahydrofuran, and react at room temperature for 72h under nitrogen protection. After the reaction is completed, the low boiling point liquid is removed under reduced pressure to obtain the intermediate product M. Dissolve the intermediate product M in dichloromethane, and add 3 mL of triethylamine, add 0.04 mol of methacryloyl chloride under a nitrogen atmosphere, stir and react at room temperature for 4 hours.
  • vulcanizing agent F The structural formula of vulcanizing agent F is:
  • vulcanizing agent F The reactant 1 (8.00 g, 0.04 mol) and reactant 2 (7.95 g, 0.04 mol) were dissolved in 50 ml of tetrahydrofuran, and reacted at 60° C. for 24 hours under nitrogen protection. After the reaction is completed, it is cooled to room temperature, the reaction liquid is poured into excess ether, the organic phase is extracted, and the organic phase product is distilled under reduced pressure to remove the solvent, and the viscous liquid obtained is the vulcanizing agent F.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw setting speed is 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • vulcanizing agent A of the present invention 100 parts of polypropylene, 0.1 part of 1010 (antioxidant), 0.1 part of 168 (antioxidant), 0.2 part of 2,5-dimethyl-2,5-bis(tert-butylperoxy) Base) hexane (initiator) and 5 parts of the vulcanizing agent A of the present invention are mixed, and then the mixture is added to a 35-type twin-screw extruder for melting.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • 0.1 part of 1010 antioxidant
  • 0.1 part of 168 antioxidant
  • 0.2 part of excess Dicumyl oxide initiator
  • 5 parts of the vulcanizing agent B of the present invention are mixed, and then the mixture is added to the open mill (X(S)K-160, Shanghai Shuangyi Rubber Machinery Co., Ltd.) with a roller pitch of 0.7mm , The temperature of the roller is 60°C, and the triangle bag is thinned and punched for 5 times, and then left for 2 hours to obtain the final product.
  • vulcanizing agent of the present invention C 100 parts of ethylene propylene rubber, 0.1 part of 1010 (antioxidant), 0.1 part of 168 (antioxidant), 0.2 part of dicumyl peroxide (initiator), 8 parts of vulcanizing agent of the present invention C is mixed, and then the mixture is added to an open mill (X(S)K-160) with a roller pitch of 0.7mm, a roller temperature of 60°C, thin-opening and triangulation for 5 times, and it is left for 2h to obtain the final product.
  • X(S)K-160 open mill with a roller pitch of 0.7mm, a roller temperature of 60°C, thin-opening and triangulation for 5 times, and it is left for 2h to obtain the final product.
  • vulcanizing agent of the present invention E 100 parts of ethylene propylene rubber, 0.1 part of 1010 (antioxidant), 0.1 part of 168 (antioxidant), 0.2 part of dicumyl peroxide (initiator), 5 parts of vulcanizing agent of the present invention E is mixed, and then the mixture is added to the open mill (X(S)K-160) with a roller distance of 0.7mm, a roller temperature of 60°C, thin-opening and triangulation for 5 times, and it is left for 2h to obtain the final product.
  • open mill X(S)K-160
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw setting speed is 150 rpm
  • the extruded product is cooled by a circulating water bath. And diced to get the final product.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • vulcanizing agent D of the present invention In parts by mass, 80 parts of polypropylene, 20 parts of ethylene-propylene rubber, 0.1 part of 1010 (antioxidant), 0.1 part of 168 (antioxidant), 0.15 part of 2,5-dimethyl-2,5-di (Tert-butylperoxy)hexane (initiator) and 3 parts of vulcanizing agent D of the present invention are mixed, and then the mixture is added to a 35-type twin-screw extruder for melting.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 170°C
  • the screw setting speed is 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • vulcanizing agent A of the present invention In parts by mass, 40 parts of polypropylene, 40 parts of polyethylene, 20 parts of ethylene-propylene rubber, 0.1 part of 1010 (antioxidant), 0.1 part of 168 (antioxidant), 0.2 part of 2,5-dimethyl- 2,5-Di(tert-butylperoxy)hexane (initiator) and 5 parts of vulcanizing agent A of the present invention are mixed, and then the mixture is added to a 35-type twin-screw extruder for melting.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • Example 9 The product obtained in Example 9 was added to a 35-type twin-screw extruder again for melting.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • Example 13 The product obtained in Example 13 was added to a 35-type twin-screw extruder again for melting.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • vulcanizing agent F of the present invention In parts by mass, 80 parts of polypropylene, 20 parts of ethylene-propylene rubber, 0.1 part of 1010 (antioxidant), 0.1 part of 168 (antioxidant), 0.15 part of 2,5-dimethyl-2,5-di (Tert-butylperoxy)hexane (initiator) and 8 parts of the vulcanizing agent F of the present invention are mixed, and then the mixture is added to a 35-type twin-screw extruder for melting.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • the product obtained in Comparative Example 4 was added to a 35-type twin-screw extruder again for melting.
  • the temperature of the melting section of the extruder is 160°C
  • the temperature of the reaction section is 190°C
  • the temperature of the melt conveying section is 200°C
  • the temperature of the discharge port is 180°C
  • the screw speed is set to 150rpm
  • the extruded product is cooled and cooled by a circulating water bath. Cut into pellets to obtain the final product.
  • Table 1 lists the performance data of the modified polypropylene resin.
  • the vulcanizing agent of the present invention is a new type of vulcanizing agent with reversible cross-linking function.
  • the cross-linked polymer prepared by it has a thermally reversible cross-linked structure, that is, the cross-linked network can be de-cross-linked under the state of melt processing ( Through the reverse Diels-Alder reaction mechanism), the material has thermoplasticity.
  • the cross-linked polymer samples of all the examples can be measured for melt index, indicating that the material has thermoplasticity. For example, comparing the results of Comparative Example 4 and Example 9, it can be seen that Example 9 has remarkable performance due to its cross-linked structure.
  • the performance of the crosslinked polymer prepared by the present invention can still be better maintained after repeated processing: the sample of Comparative Example 5 was processed again from Comparative Example 4, and its performance has been significantly weakened and its strength reduced ( The reason is that the polymer is reprocessed to cause partial degradation, and the second is that the performance of the two-phase separation is weakened); and the embodiment 13 of the present invention is obtained from the secondary processing of the embodiment 12, and the embodiment 14 is obtained from the embodiment 13 It is obtained by further processing. After several consecutive processing treatments, the material properties remain basically unchanged. This is due to the thermally reversible cross-linking function of the vulcanizing agent of the present invention.
  • the cross-linked structure can still be stably recovered after repeated processing.
  • the cross-linked structure between the phases can also make up for the problems caused by the separation of the two phases, so that the performance can be maintained.
  • the vulcanizing agent of the present invention is a new type of vulcanizing agent with reversible cross-linking function. When used in polymer processing, it has high temperature (during processing) de-crosslinking, easy processing, and low temperature (after molding) ) Remarkable characteristics of cross-linking formation and high performance.
  • the crosslinking agent can also be used to strengthen the performance of waste plastics and rubber during recycling.

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Abstract

涉及一类新型硫化剂及其在聚合物中的应用，该硫化剂在聚合物加工时加入，可在聚合物中形成交联网络，提高材料力学性能；同时该交联剂在高温时又可使聚合物材料解交联，其降温后可再次交联产生网络结构，赋予聚合物材料反复加工的热塑性。所述硫化剂可解决高分子材料交联增强和回收利用的矛盾。

Description

一类硫化剂及其应用 技术领域
本发明涉及聚合物硫化剂技术领域，具体涉及一类硫化剂及其应用，特别涉及一类具有可逆交联功能的硫化剂及其在聚合物中的应用。
背景技术
硫化是对聚合物进行交联的重要手段，聚合物经过硫化后形成的三维网络结构，能够赋予聚合物材料更高的强度、温度稳定性及耐化学应力开裂性能等，特别是对于橡胶类的聚合物材料，只有通过交联改性，才能使其具有应用过程中所需的弹性、回弹性、强度和尺寸稳定性。
硫磺硫化是人类最早发现的橡胶交联工艺，硫化过程极大地改善了橡胶制品的物化性能。经过近两百年的发展，硫化工艺已经发展出了过氧化物硫化、射线辐照硫化、功能性基团硫化等方法，但硫磺硫化仍以原料廉价成为最经济的方法。通过在硫磺硫化体系中加入硫化促进剂和活性剂，可以进一步减少硫磺用量、缩短硫化时间、降低硫化温度。有机过氧化物硫化，是利用结构中含有一个或多个过氧键(-O-O-)的化合物，通过其均裂生成自由基，引发聚合物分子之间的自由基反应，产生交联网络结构，过氧化物交联可以在饱和聚合物中实施(通常需要在聚合物中添加2wt％以上的过氧化物)，克服了饱和聚合物(如乙丙橡胶)难以用硫磺硫化的问题。辐照硫化是一种利用高能射线使聚合物分子发生交联的技术，可以免去添加过氧化物或硫磺等硫化物，其基本原理是高能射线穿过聚合物基材时，激活聚合物分子产生自由基，再通过这些自由基之间的相互结合，形成交联网络。除此以外，人们还利用在聚合物侧基引入反应性基团实施交联，乙烯基硅氧烷是交联聚烯烃常用的一类温和而高效的功能性单体，可以在水存在的条件下实现交联反应，获得高度交联的材料。用双烯烃硫化剂(如二乙烯基苯)直接对聚合物进行交联也是硫化方法之一，更多用于聚烯烃树脂的交联改性。
硫化交联作为目前聚合物材料的主要交联技术，其形成的交联共价键具有不可逆性，使交联聚合物无法进行再次加工，因而在赋予材料优异性能的同时，也带来了聚合物材料回收和再利用的难题。在此背景下，橡胶脱硫回收技术应运而生，并在以天然橡胶和丁基橡胶等为代表的聚合物胶种回收处理中获得应用。章明秋等在硫化天然橡胶的回收方面做了大量工作，发现利用交联橡胶中二硫键的动态交换可逆反应，能够实现硫化天然橡胶的固相回收(高分子学报，2017，7， 1130-1140)，他们通过在橡胶中添加甲基丙烯酸铜(MA-Cu)或氯化铜(CuCl 2)作为二硫键交换反应催化剂，使交联网络具有动态特性，从而使硫化天然橡胶在高于120℃的温度下实现了回收和再加工，为现存的大量硫化天然橡胶制品提供了再利用方案，具有长远的社会意义。然而，以过氧化物交联、辐照交联、硅烷交联、二乙烯基苯交联等方法产生的是更稳定的C-C键，使此类聚合物的脱硫(解交联)更加困难。人们通常利用热处理和机械处理相结合的方法来破坏硫化交联键，但是这一过程会引起聚合物主链断裂，脱硫后所得产物仅有25％能够实现再利用。
实现交联聚合物的循环再利用，是科研人员和工业界共同追求的目标，不仅具有重要的经济效益，更具有长远的社会效益。然而总体来看，目前的技术还集中在脱硫阶段，尚未从硫化交联的源头上对交联方法进行可逆化设计。如能设计新型硫化剂，使其制备的交联聚合物具有高温解交联、降温再次交联的特性，将使材料具有反复加工的功能，从根本上解决交联聚合物无法回收的难题。
发明内容
本发明的目的是提供一类新型硫化剂，所述硫化剂具有至少两个α-烯烃结构，是[4+2]环加成反应的产物，所述硫化剂具有如下式(I)～式(VI)中的任一结构：
Figure PCTCN2020073464-appb-000001
Figure PCTCN2020073464-appb-000002
式中，R 1、R 2可以相同或不同，为丙烯酸酯基、苯乙烯基或乙烯基硅烷基，或丙烯酸酯基、苯乙烯基、乙烯基硅烷基的含有1～12个碳原子的取代物；R 3、R 4可以相同或不同，为-O-，或-NH-，或-N(CH 3)-，或-N(C 2H 5)-；R 5为脂肪类基团、芳香类基团、酯类基团或醚类基团：当R 5为脂肪类基团时，结构I或II可表示为-C mH 2m-，结构IV或V可表示为
Figure PCTCN2020073464-appb-000003
(n＝3时)，或
Figure PCTCN2020073464-appb-000004
(n＝4时)；当R 5为芳香类基团时，结构I或II可表示为-(C 6H 4) xC mH 2m-，结构IV或V可表示为
Figure PCTCN2020073464-appb-000005
(n＝3时)，或
Figure PCTCN2020073464-appb-000006
(n＝4时)；当R 5为酯类基团时，结构I或II可表示为-(C 6H 4) y(C mH 2m)(COO) x-，结构IV或V可表示为
Figure PCTCN2020073464-appb-000007
(n＝3时)，或
Figure PCTCN2020073464-appb-000008
(n＝4时)；当R 5为醚类基团时，结构I或II可表示为-(C 6H 4) yC mH 2mO x-，结构IV或V可表示为
Figure PCTCN2020073464-appb-000009
(n＝3时)，或
Figure PCTCN2020073464-appb-000010
(n＝4时)；其中，m为1～18的整数，x为1～8的整数，y为0～8的整数；R 6、R 7可以相同或不同，为-H或-CH 3；n＝3或4。
本发明所述式(I)结构是由双马来酰亚胺与取代呋喃或与取代吡咯通过Diels-Alder反应([4+2]环加成反应)直接制备获得；或由双马来酰亚胺与取代呋喃或与取代吡咯通过Diels-Alder反应后，再将取代基进行修饰而制备获得；
本发明所述式(II)结构是由双烯与取代呋喃或与取代吡咯通过Diels-Alder反应直接制备获得；或由双烯与取代呋喃或与取代吡咯通过Diels-Alder反应后，再将取代基进行修饰而制备获得；
本发明所述式(III)结构是由烯基取代的环戊二烯化合物自身通过Diels-Alder反应进行二聚获得；或由烯基取代的环戊二烯化合物通过Diels-Alder反应二聚后，再将取代基进行修饰而制备获得；
本发明所述式(IV)结构是由三马来酰亚胺或四马来酰亚胺，与烯基取代呋喃或与烯基取代吡咯通过Diels-Alder反应制备获得；或由三马来酰亚胺或四马来酰亚胺与取代呋喃或与取代吡咯通过Diels-Alder反应后，再将取代基进行修饰而制备获得；
本发明所述式(V)结构是由三烯或四烯，与烯基取代呋喃或与烯基取代吡咯通过Diels-Alder反应制备获得；或由三烯或四烯，与取代呋喃或与取代吡咯通过Diels-Alder反应后，再将取代基进行修饰而制备获得；
本发明所述式(VI)结构是由取代马来酰亚胺与取代呋喃或与取代吡咯通过Diels-Alder反应直接制备获得；或由取代马来酰亚胺与取代呋喃或与取代吡咯通过Diels-Alder反应后，再将取代基进行修饰而制备获得。
本发明的另一目的是提供上述新型硫化剂在聚合物硫化交联中的应用，以聚合物、硫化剂、引发剂为原料，采用熔融法实施。所述聚合物与硫化剂的质量比为100：0.01～100：10；所述聚合物与引发剂的质量比为100:0.01～100:1；还可加入热稳定剂，所述聚合物与热稳定剂的质量比为100:0～100:1，热稳定剂加入量可以为0。
所述聚合物选自聚烯烃树脂或聚烯烃橡胶中的至少一种。
作为优选地，所述聚合物与硫化剂的质量比为100：0.1～100：5；所述聚合物与引发剂的质量比为100:0.05～100:0.5；所述聚合物与热稳定剂的质量比为100:0.1～100:0.5。
作为优选地，所述引发剂选自有机过氧化物或偶氮类引发剂。
进一步优选地，所述有机过氧化物为过氧化环己酮、过氧化二异丙苯、过氧化二苯甲酰、叔丁基过氧化氢，或2,5-二甲基-2,5-二(叔丁基过氧基)己烷。
进一步优选地，所述偶氮类引发剂为偶氮二异丁腈或偶氮二异庚腈。
作为优选地，所述热稳定剂选自受阻酚类大分子型抗氧剂、亚磷酸类抗氧剂或烷酯类抗氧剂中的至少一种。
进一步优选地，所述热稳定剂为所述受阻酚类大分子型抗氧剂和亚磷酸类抗氧剂的联用。
最优选地，所述热稳定剂为抗氧剂1010(四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)和抗氧剂168(三[2.4-二叔丁基苯基]亚磷酸酯)。优选地，所述抗氧剂1010和抗氧剂168的质量比例为1:0.5～1:2。
作为优选地，所述聚合物选自饱和聚烯烃树脂或饱和聚烯烃橡胶中的至少一种。
进一步优选地，所述聚烯烃树脂选自聚乙烯、聚丙烯、聚1-丁烯等均聚物或其共聚物树脂等。
进一步优选地，所述聚烯烃橡胶选自乙丙橡胶、乙烯/高级α-烯烃共聚物弹性体、丁基橡胶、苯乙烯/异丁烯共聚物橡胶等。
作为优选地，所述聚合物硫化交联方法包括以下步骤：
1)将聚合物、硫化剂、引发剂、热稳定剂进行混合，得到预混合原料；
2)将所述的预混合原料加入到反应性加工设备中，在120℃以上进行反应；
3)挤出产物经冷却后交联。
作为优选地，所述方法采用的反应性加工设备为单螺杆挤出机、双螺杆挤出 机、开炼机、密炼机中的任意一种。
当硫化剂为固态时，可通过溶剂溶解硫化剂后再混合聚合物的办法使其混合均匀，使用溶剂一般是易挥发且不与硫化剂或者聚合物反应的丙酮、乙醇等，然后自然挥发除去溶剂。
本发明所述的新型硫化剂，是一种具有可逆共价键的化合物：该分子中的官能团在高温时(100～200℃，根据结构不同，温度有所差异)，通过逆向Diels-Alder反应(逆向[4+2]环加成反应)能够分解为两部分；随后在低温时(0～120℃，根据结构不同，温度有所差异)，通过Diels-Alder反应([4+2]环加成反应)能够再次结合成原官能团，即具有热可逆的反应特性。
与此同时，本发明所述的新型硫化剂，其分子端基的两个或多个双键，可以在引发剂作用下对聚合物实施化学交联，形成网络结构，实现对聚合物的增强；同时利用Diels-Alder反应的热可逆性，将聚合物加热时可实现材料的解交联，使材料具有热塑性；其降温后又可再次交联产生网络结构，从而赋予材料重复加工性和可回收性。
本发明提供上述硫化剂在可回收的交联聚合物材料中的应用。
附图说明
图1为实施例4制备的交联橡胶制品切碎后再次热压成型；A为加入本发明硫化剂的交联橡胶样条；B为将该橡胶样条切割成碎片；C为将碎片再次加工成型后其性能可以恢复。
具体实施方式：
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
实施例1
新型硫化剂的制备：
1、具有(I)式所示的结构的硫化剂
硫化剂A的结构式为：
Figure PCTCN2020073464-appb-000011
合成方法如反应式1所示。
反应物①的合成：将糠醇(6.43g，0.07mol)加入20ml氢氧化钠(40wt％)水溶液中，搅拌反应1h。之后，向上述混合液中加入10ml甲苯，5g 4-氯甲基苯乙烯和4.25g四丁基氢氧化铵水溶液(40wt％)作为催化剂，室温反应48h。反应完成后，反应液加入过量水，用乙醚萃取。有机相用无水硫酸镁干燥，过滤，最后旋蒸除去有机溶剂后即得反应物①，产率为76％。
反应物②N,N’-(4,4’-亚甲基二苯基)双马来酰亚胺为商品(CAS13676-54-5)，本实验购自安耐吉化学有限公司。
硫化剂A的合成：将反应物①(8.00g，0.04mol)和反应物②(7.14g，0.02mol)溶于50ml四氢呋喃中，氮气保护条件下，60℃反应24h。反应完成后，冷却至室温，将反应液倒入过量乙醚中，萃取有机相，将有机相产物减压蒸馏除去溶剂后，所得粘稠液体即为硫化剂A。
Figure PCTCN2020073464-appb-000012
式1：硫化剂A的合成路线
2、具有(II)式所示的结构的硫化剂
硫化剂B的结构式为：
Figure PCTCN2020073464-appb-000013
合成方法如反应式2所示。
反应物①糠醇为商品(CAS 98-00-0)，本实验购自安耐吉化学有限公司。
反应物②1,4-丁二醇二丙烯酸酯为商品(CAS 1070-70-8)，本实验购自安耐吉化学有限公司。
硫化剂B的合成：将反应物①(3.92g，0.04mol)和反应物②(3.96g，0.02mol)溶于50ml四氢呋喃中，氮气保护条件下，室温反应72h。反应完成后，减压除去低沸点液体，得到中间产物M。将中间产物M溶解于二氯甲烷中，并加入3mL三乙胺，在氮气气氛下，加入0.04mol的甲基丙烯酰氯，室温搅拌反应4小时，反应结束后，减压除去低沸点液体，最后用盐酸水溶液中和产物中剩余的三乙胺至溶液pH值呈中性，将洗涤液分液、除水后，得到硫化剂B。
Figure PCTCN2020073464-appb-000014
式2：硫化剂B的合成路线
3、具有(III)式所示的结构的硫化剂
硫化剂C的结构式为：
Figure PCTCN2020073464-appb-000015
合成方法如反应式3所示。
反应物的合成：冰水浴条件下，将2ml新蒸馏的环戊二烯(1.6g，24.3mmol)逐滴加入到正丁基锂(24.2mmol)的正己烷溶液(100ml)中。将混合液室温条件下反应3h。之后，除去溶剂，正戊烷洗涤(3×50mL)后，真空干燥。-78℃条件下，将上述制备的Li(C 5H 5)溶解在四氢呋喃中(75mL)中，逐滴加入到二甲基乙烯基氯硅烷(2.7g，22.0mmol)的四氢呋喃溶液中，0℃条件下，反应半小时后，室温反应过夜。减压蒸馏除去易挥发组分，用正戊烷萃取(3×50mL)，过滤和干燥后，最终得到反应物(产率60％)。
硫化剂C的合成：将反应物(12.0g，0.08mol)溶于50ml四氢呋喃中，室温反应48h。反应完成后，冷却至室温，减压蒸馏得到硫化剂C。
Figure PCTCN2020073464-appb-000016
式3：硫化剂C的合成路线
4、具有(IV)式所示的结构的硫化剂
硫化剂D的结构式为：
Figure PCTCN2020073464-appb-000017
合成方法如反应式4所示。
反应物①的合成：氮气保护条件下，将TMEDA(14.33g，0.123mol)和1-甲基吡咯(10g，0.123mol)溶于80mL的无水四氢呋喃中，逐滴加入77mL正丁基锂的正己烷溶液(1.6M)。搅拌半小时后，加入0.123mol的二甲基乙烯基氯硅烷，室温反应12h。经水洗，乙醚萃取和减压蒸馏后即得反应物①(产率70％)。
反应物②的合成：30g马来酸酐和25g呋喃溶解在300ml甲苯中，室温搅拌36h，过滤后得到呋喃保护马来酸酐白色固体粉末(产率79％)。在带搅拌子、恒漏、回流管的500mL烧瓶中加入150mL甲醇，加入上述呋喃保护马来酸酐(5.66g,34mmol)，将磁转搅拌器打开，待其全部溶解后，0℃条件下，再向其中恒压漏斗逐滴加入50ml甲醇溶解的4,4',4"-三氨基三苯甲烷(1.98g，6.85mmol)，30min滴完。回流3h，混合液变黄。混合液浓缩至75mL，4℃结晶。过滤得浅黄色晶体，50mL乙酸乙酯洗涤，真空干燥后得到中间体M(产率24％)。在带搅拌子、回流管的100mL烧瓶中加入30mL甲苯，中间体M(0.5g,0.85mmol)，将磁转搅拌器打开，待其全部溶解后。混合液冷凝回流7h。旋蒸干燥后即得反应物②(产率84％)。
硫化剂D的合成：反应物①(4.96g，0.03mol)和反应物②(3.86g，0.01mol)溶于50ml四氢呋喃中，氮气保护条件下，60℃反应48h。反应完成后，冷却至室温，减压蒸馏除去低沸点液体，得到硫化剂D。
Figure PCTCN2020073464-appb-000018
式4：硫化剂D的合成路线
5、具有(V)式所示的结构的硫化剂
硫化剂E的结构式为：
Figure PCTCN2020073464-appb-000019
合成方法如反应式5所示。
硫化剂E的合成：将季戊四醇四丙烯酸酯(3.52g，0.01mol)和糠醇(3.92g，0.04mol)溶于50ml四氢呋喃中，氮气保护条件下，室温反应72h。反应完成后，减压除去低沸点液体，得到中间产物M。将中间产物M溶解于二氯甲烷中，并加入3mL三乙胺，在氮气气氛下，加入0.04mol的甲基丙烯酰氯，室温搅拌反应4小时，反应结束后，减压除去低沸点液体，最后用盐酸水溶液中和产物中剩余的三乙胺至溶液pH值呈中性，将洗涤液分液、除水后，得到硫化剂E。
Figure PCTCN2020073464-appb-000020
式5：硫化剂E的合成路线
6、具有(VI)式所示的结构的硫化剂
硫化剂F的结构式为：
Figure PCTCN2020073464-appb-000021
合成方法如下图反应式6所示。
反应物①的合成：将糠醇(6.43g，0.07mol)加入20ml氢氧化钠(40wt％)水溶液中，搅拌反应1h。之后，向上述混合液中加入10ml甲苯，5g 4-氯甲基苯乙烯和4.25g四丁基氢氧化铵水溶液(40wt％)作为催化剂，室温反应48h。反应完成后，反应液加入过量水，用乙醚萃取。有机相用无水硫酸镁干燥，过滤，最后旋蒸除去有机溶剂后即得反应物①，产率为76％。
反应物②的合成：将马来酸酐与对乙烯基苯胺溶于乙酸乙酯中在0℃下搅拌反应1h。之后，将乙酸酐和三乙胺加入上述溶液在55℃下反应一小时，冷却得到反应物②，产率为80％。
硫化剂F的合成：将反应物①(8.00g，0.04mol)和反应物②(7.95g，0.04mol)溶于50ml四氢呋喃中，氮气保护条件下，60℃反应24h。反应完成后，冷却至室温，将反应液倒入过量乙醚中，萃取有机相，将有机相产物减压蒸馏除去溶剂后，所得粘稠液体即为硫化剂F。
Figure PCTCN2020073464-appb-000022
式6：硫化剂F的合成路线
实施例2
以质量份计，将100份聚丙烯(熔指MFR＝2.0g/10min，230℃，下同)、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.1份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)、2份本发明的硫化剂A进行混合，随后将混合物加入到35型双螺杆挤出机(倍隆科亚南京机械有限公司)中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃， 螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例3
以质量份计，将100份聚丙烯、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)、5份本发明的硫化剂A进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例4
以质量份计，将100份乙丙橡胶(门尼粘度ML 1+4＝40，100℃，下同)、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份过氧化二异丙苯(引发剂)、5份本发明的硫化剂B进行混合，随后将混合物加入到开炼机(X(S)K-160，上海双翼橡塑机械有限公司)辊距0.7mm、辊温为60℃，薄通、打三角包5次，停放2h，得到最终产物。
实施例5
以质量份计，将100份乙丙橡胶、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份过氧化二异丙苯(引发剂)、8份本发明的硫化剂C进行混合，随后将混合物加入到开炼机(X(S)K-160)辊距0.7mm、辊温为60℃，薄通、打三角包5次，停放2h，得到最终产物。
实施例6
以质量份计，将100份乙丙橡胶、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份过氧化二异丙苯(引发剂)、5份本发明的硫化剂E进行混合，随后将混合物加入到开炼机(X(S)K-160)辊距0.7mm、辊温为60℃，薄通、打三角包5次，停放2h，得到最终产物。
实施例7
以质量份计，将50份聚丙烯、50份聚乙烯(熔指MFR＝3.0g/10min，230℃，下同)、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)、4份本发明的硫化剂C进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150 rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例8
以质量份计，将50份聚丙烯、50份聚乙烯、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)、5份本发明的硫化剂D进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例9
以质量份计，将80份聚丙烯、20份乙丙橡胶、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.15份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)、3份本发明的硫化剂D进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例10
以质量份计，将100份聚乙烯、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)、2份本发明的硫化剂E进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为170℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例11
以质量份计，将100份丁基橡胶(门尼粘度ML 1+4＝75，100℃)、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.1份过氧化二异丙苯(引发剂)、5份本发明的硫化剂C进行混合，随后将混合物加入到开炼机(X(S)K-160)辊距0.7mm、辊温为60℃，薄通、打三角包5次，停放2h，得到最终产物。
实施例12
以质量份计，将40份聚丙烯、40份聚乙烯、20份乙丙橡胶、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发 剂)、5份本发明的硫化剂A进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例13
将实施例9所得产物，再次加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例14
将实施例13所得产物，再次加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
实施例15
以质量份计，将80份聚丙烯、20份乙丙橡胶、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.15份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)、8份本发明的硫化剂F进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
对比例1
以质量份计，将100份聚丙烯(熔指MFR＝2.0g/10min，230℃，下同)、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.1份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)进行混合，随后将混合物加入到35型双螺杆挤出机(倍隆科亚南京机械有限公司)中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
对比例2
以质量份计，将100份乙丙橡胶(门尼粘度ML 1+4＝40，100℃，下同)、0.1 份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份过氧化二异丙苯(引发剂)进行混合，随后将混合物加入到开炼机(型号X(S)K-160，上海双翼橡塑机械有限公司)辊距0.7mm、辊温为60℃，薄通、打三角包5次，停放2h，得到最终产物。
对比例3
以质量份计，将50份聚丙烯、50份聚乙烯(熔指MFR＝3.0g/10min，230℃，下同)、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.2份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
对比例4
以质量份计，将80份聚丙烯、20份乙丙橡胶、0.1份1010(抗氧剂)、0.1份168(抗氧剂)、0.15份2,5-二甲基-2,5-二(叔丁基过氧基)己烷(引发剂)进行混合，随后将混合物加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
对比例5
将对比例4所得产物，再次加入到35型双螺杆挤出机中进行熔融。挤出机的熔融段温度为160℃，反应段温度为190℃，熔体输送段温度为200℃，出料口温度为180℃，螺杆设定转速为150rpm，挤出产物经过循环水浴冷却和切粒，得到最终产物。
上述实施例所制备的改性聚丙烯树脂的性能测试列于下表1。
表1聚合物性能
Figure PCTCN2020073464-appb-000023
Figure PCTCN2020073464-appb-000024
表1列出了改性聚丙烯树脂的性能数据。
首先，与对比例相比，由于实施例的聚合物中加入了本发明的硫化剂，使制备的聚合物中形成交联网络结构，这可以从实施例聚合物力学性能的显著提高得到证实：通过比较实施例2与对比例1、比较实施例4与对比例2、比较实施例7与对比例3、比较实施例9与对比例4等，可以看出加入硫化剂后材料的强度、模量等性能显著提高，这说明本发明的硫化剂起到了明显的交联效果。
其次，本发明的硫化剂是一种具有可逆交联功能的新型硫化剂，其制备的交联聚合物具有热可逆的交联结构，即在熔融加工状态下交联网络可以发生解交联(通过逆向Diels-Alder反应机理)，使材料具有热塑性。所有实施例的交联聚合物样品均可以进行熔融指数测定，表明该材料具有热塑性，例如：比较对比例4和实施例9的结果可以看出，实施例9由于具有交联结构，其性能显著优于对比例4，但是两种聚合物的熔融指数相近(即加工性能相近)，从这表明本发明的硫化剂具有降温形成网络、高温解除网络的独特性能，完全不同于传统硫化剂所形成的永久性交联网络，从而赋予了交联聚合物热塑性的优异特性。这就实现了交联聚合物的反复加工，附图1展示了实施例4制备的交联橡胶制品，切成碎片后可进行再次热压成型的特点。
第三，利用本发明制备的交联聚合物，反复多次加工后，性能仍可较好保持：对比例5的样品是由对比例4再次加工而得，其性能已明显弱化，强度降低(其原因一是聚合物再次加工而引起部分降解，二是两相分离造成的性能弱化)；而本发明的实施例13是由实施例12二次加工而得，实施例14又是由实施例13进一步再次加工而得，经过连续多次的加工处理，材料性能基本保持不削弱，这是得益于本发明硫化剂的热可逆交联功能，反复加工后交联结构仍可稳定恢复，两相之间的交联结构还能弥补两相分离带来的问题，从而使性能得以保持。
综上，本发明所述的硫化剂，是一种具有可逆交联功能的新型硫化剂，其用于聚合物加工时，具有高温(加工时)解交联、易加工，而低温(成型后)交联形成、高性能的显著特点。该交联剂还可用于废旧塑料、橡胶回收时的性能强化。

Claims (8)

  1. 一类硫化剂，其特征在于，所述硫化剂具有至少两个α-烯烃结构，所述硫化剂具有如下式(I)～式(VI)中的任一结构：
    Figure PCTCN2020073464-appb-100001
    Figure PCTCN2020073464-appb-100002
    其中，
    R 1、R 2可以相同或不同，为丙烯酸酯基、苯乙烯基或乙烯基硅烷基，或丙烯酸酯基、苯乙烯基、乙烯基硅烷基的含有1～12个碳原子的取代物；
    R 3、R 4可以相同或不同，为-O-，或-NH-，或-N(CH 3)-，或-N(C 2H 5)-；
    R 5为脂肪类基团、芳香类基团、酯类基团或醚类基团：
    当R 5为脂肪类基团时，结构I或II为-C mH 2m-，结构IV或V为
    Figure PCTCN2020073464-appb-100003
    (n＝3时)，或
    Figure PCTCN2020073464-appb-100004
    (n＝4时)；
    当R 5为芳香类基团时，结构I或II为-(C 6H 4) xC mH 2m-，结构IV或V为
    Figure PCTCN2020073464-appb-100005
    (n＝3时)，或
    Figure PCTCN2020073464-appb-100006
    (n＝4时)；
    当R 5为酯类基团时，结构I或II为-(C 6H 4) y(C mH 2m)(COO) x-，结构IV或V为
    Figure PCTCN2020073464-appb-100007
    (n＝3时)，或
    Figure PCTCN2020073464-appb-100008
    (n＝4时)；
    当R 5为醚类基团时，结构I或II为-(C 6H 4) yC mH 2mO x-，结构IV或V为
    Figure PCTCN2020073464-appb-100009
    (n＝3时)，或
    Figure PCTCN2020073464-appb-100010
    (n＝4时)；
    其中，m为1～18的整数，x为1～8的整数，y为0～8的整数；
    R 6、R 7可以相同或不同，为-H或-CH 3；
    n＝3或4。
  2. 权利要求1所述的硫化剂在聚合物硫化交联中的应用。
  3. 根据权利要求2所述的应用，其特征在于，聚合物硫化交联反应以聚合物、硫化剂、引发剂、热稳定剂为原料，采用熔融法实施；所述聚合物与硫化剂的质量比为100：0.01～100：10；所述聚合物与引发剂的质量比为100:0.01～100:1；所述聚合物与热稳定剂的质量比为100:0～100:1。
  4. 根据权利要求3所述的应用，其特征在于，所述聚合物选自聚烯烃树脂或聚烯烃橡胶中的至少一种。
  5. 根据权利要求3所述的应用，其特征在于，所述引发剂为有机过氧化物或偶氮类引发剂。
  6. 根据权利要求3所述的应用，其特征在于，所述热稳定剂选自受阻酚类大分子型抗氧剂、亚磷酸类抗氧剂或烷酯类抗氧剂中的至少一种。
  7. 根据权利要求3所述的应用，其特征在于，所述聚合物硫化交联方法包括以下步骤：
    1)将聚合物、硫化剂、引发剂、热稳定剂进行混合，得到预混合原料；
    2)将所述的预混合原料加入到反应性加工设备中，在120℃以上进行反应；
    3)挤出产物经冷却后交联。
  8. 根据权利要求7所述的应用，其特征在于，所述反应性加工设备为单螺杆挤出机、双螺杆挤出机、开炼机、密炼机中的一种。
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