WO2021056858A1 - 一种丙烯共聚物及其制备方法与应用 - Google Patents

一种丙烯共聚物及其制备方法与应用 Download PDF

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WO2021056858A1
WO2021056858A1 PCT/CN2019/125861 CN2019125861W WO2021056858A1 WO 2021056858 A1 WO2021056858 A1 WO 2021056858A1 CN 2019125861 W CN2019125861 W CN 2019125861W WO 2021056858 A1 WO2021056858 A1 WO 2021056858A1
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propylene
aluminum
added
reaction
ethylene
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French (fr)
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牛慧
华哲
何宗科
刘姝慧
包卓
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Dalian University of Technology
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Dalian University of Technology
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst

Definitions

  • the invention relates to a propylene copolymer and a preparation method and application thereof, in particular to a preparation method of a propylene copolymer with a thermally reversible crosslinked structure and its application as an impact resin.
  • Polypropylene heterophasic copolymer is one of the main varieties of polypropylene resin. By dispersing the elastomeric ethylene/ ⁇ -olefin copolymer in the polypropylene matrix, it can overcome the toughness of homopolypropylene resin (especially the low temperature toughness). ), which greatly broadens the scope of application of polypropylene resin.
  • the continuous multi-stage propylene polymerization and ethylene/ ⁇ -olefin copolymerization in the reactor has become the current trend for the preparation of polypropylene heterophasic copolymers: firstly, the isotactic polypropylene resin matrix is synthesized in the first-stage reactor, and then Transfer the produced polypropylene to the second-stage reactor to continue the copolymerization of ethylene and propylene (or ethylene and other ⁇ -olefins) to synthesize a copolymer with rubber properties and realize its originality in the polypropylene resin matrix. Dispersion, providing toughness for polypropylene resin.
  • the toughening mechanism is: the rubber phase in this propylene copolymer can absorb or partially absorb the impact energy at the fracture, thereby increasing the overall impact strength of the material.
  • the main factors that affect its toughening effect include three aspects: (1) Rubber phase content: Patent US3,627,852 mentions that only a certain content of this rubber phase can achieve an obvious toughening effect. (2)
  • the dispersion size and uniformity of the rubber phase The rubber phase is generally distributed in the polypropylene resin matrix as the dispersed phase. When the scale of the dispersed phase is about 1 ⁇ m, the rubber phase can play a good role in toughening polypropylene.
  • the Diels-Alder (DA) reaction [4+2] cyclization reaction
  • DA Diels-Alder
  • rD-A reverse DA reaction
  • the DA reaction between furan/maleimide at low temperature (around 60°C) and the rD-A reaction at around 120°C are an effective way to prepare high-performance materials.
  • the present invention provides a novel propylene copolymer, in which the mass content of propylene is 49-95%, the mass content of ethylene is 3 to 49%, the mass content of furan-substituted olefin monomer is 1-30%, and the mass content of coupling agent The content is 0.1-30%.
  • the furan-substituted olefin monomer has the following structure:
  • R 1 , R 2 and R 3 may be the same or different, and are each independently selected from hydrogen, methyl, ethyl, and isopropyl; m is an integer between 1-12.
  • the coupling agent is an aliphatic or aromatic hydrocarbon containing maleimide substituents at both ends, and has the following structure:
  • R 4 is selected from alkyl groups containing 1-20 carbons.
  • Another object of the present invention is to provide a method for preparing the above-mentioned propylene copolymer. The specific steps are as follows:
  • step 2) Preparation of ethylene-propylene copolymer elastomer: After the reaction in step 1) is completed, the remaining propylene is vented, and a mixture of ethylene, propylene and furan substituted olefin monomers is introduced into the reaction system of step 1). Polymerization;
  • step 2) After the reaction in step 2) is completed, the polymer product and the coupling agent are mixed to obtain the pre-mixed raw material, which is added to the extrusion equipment, and the propylene copolymer is obtained by melt extrusion;
  • the amount of the Ziegler-Natta catalyst in step 1) is 0.0005 to 0.1%, preferably 0.001 to 0.01% of the mass of the propylene; the amount of the furan-substituted olefin monomer is the amount of the propylene 0.1 to 5% of the mass, preferably 0.5 to 2%;
  • the reaction temperature in step 1) is -20 to 120°C, preferably 50 to 90°C; the reaction time is 0.1 to 10 hours, preferably 0.5 to 3 hours; the reaction pressure is 0.01 to 6 MPa, Preferably 0.1 ⁇ 4MPa;
  • step 1) hydrogen is added to the reaction system; the added amount of hydrogen is 0.01 to 0.5% by weight of the propylene, preferably 0.01 to 0.2%;
  • the Ziegler-Natta catalyst in step 1) includes the following components I to III;
  • Component I Ti chloride, wherein the weight percentage of Ti element in the Ziegler-Natta catalyst is 0.5-10%; wherein, the Ti chloride is selected from TiCl 3 , TiCl 4 , and TiOCl 3 At least one of
  • Component II magnesium chloride, wherein the weight percentage of the metal element Mg in the Ziegler-Natta catalyst is 5-25%;
  • Component III internal electron donor, the weight percentage of the internal electron donor in the Ziegler-Natta catalyst is 1-30%; wherein, the internal electron donor includes diethyl succinate, Dibutyl adipate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, succinate, 2,2-diisobutyl-1,3- Dimethoxypropane or 9,9-bis(methoxymethyl)fluorene.
  • the internal electron donor includes diethyl succinate, Dibutyl adipate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, succinate, 2,2-diisobutyl-1,3- Dimethoxypropane or 9,9-bis(methoxymethyl)fluorene.
  • a co-catalyst is added to the reaction system;
  • the co-catalyst is one of alkyl aluminum or alkyl aluminoxane;
  • the aluminum alkyl is trialkyl aluminum or a mixture composed of trialkyl aluminum and halogenated alkyl aluminum or polyhalogenated aluminum alkyl, wherein the trialkyl aluminum is preferably triethyl aluminum, triisobutyl aluminum , At least one of tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum and trialkyl aluminum, the halogenated alkyl aluminum is preferably AlEt 2 Cl; the polyhalogenated aluminum alkyl is preferably Al 2 Et 3 Cl 3 ;
  • the alkyl aluminoxane is preferably at least one of methyl aluminoxane and isobutyl aluminoxane;
  • the external electron donor and the internal electron donor are the same or different; when the external electron donor is different from the internal electron donor, the external electron donor has a structure such as R 1 R 2 Si(OR) The compound shown in 2 , wherein R 1 and R 2 are both an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and R Is an alkyl group having 1 to 5 carbon atoms;
  • the external electron donor is preferably tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, dicyclopentoxydi At least one of ethylsilane, diphenyldimethoxysilane and diphenyldiethoxysilane;
  • the amount of the external electron donor is 0.01-100 times, preferably 1-50 times, of the molar amount of the metal Ti element in the Ziegler-Natta catalyst.
  • the added amount of ethylene in step 2) is 1-100%, preferably 10-40% of the added mass of propylene in step 1); the added amount of propylene in step 2) Is 1-100% of the added mass of propylene in step 1), preferably 10-40%; the added amount of furan-substituted olefin in step 2) is 1 ⁇ 100% of the total mass of ethylene and propylene added in step 2) 40%, preferably 5-20%;
  • the reaction temperature in step 2) is -20 to 120°C, preferably 45 to 95°C; the reaction time is 0.1 to 10 hours, preferably 0.5 to 4 hours; the reaction pressure is 0.01 to 6 MPa , Preferably 0.1 ⁇ 4MPa;
  • the amount of hydrogen added is 0.001 to 5% of the total weight of the ethylene and ⁇ -olefin monomers, preferably 0.005% to 1%, more preferably 0.02% to 0.15%.
  • the coupling agent in step 3) is added in an amount of 0.1-40%, preferably 1-10%, of the mass of the product in step 2);
  • the temperature at which the mixture of the polymer product and the coupling agent in step 3) is melt-extruded is 160-250°C, preferably 180-230°C.
  • the propylene copolymer of the present invention is a material with a reversible cross-linked network structure: the coupling agent functions between the polypropylene resin prepared in step 1) and the ethylene-propylene copolymer elastomer prepared in step 2). Realize chemical bond connection, form a cross-linked network structure, fundamentally enhance the force between the two phases; use the thermal reversibility of the DA reaction, when the copolymer is heated to 120 °C or higher, the material can be de-cross-linked, so that the material has Thermoplastic; when the temperature is lowered to 60°C, it can be cross-linked again to produce a network structure, which enhances the mechanical properties of the material.
  • the invention also provides an application of the propylene copolymer as an impact polymer resin material.
  • Figure 1 is a comparison of the proton NMR spectra of the products of Comparative Example 3 and Example 7.
  • Figure 2 is a comparison of the infrared spectra of the products of Comparative Example 3 and Example 7.
  • Example 3 is a comparison of scanning electron micrographs of the cross-sections of the products of Comparative Example 4 and Example 3 before and after hexane etching.
  • the present invention proposes the following embodiments as further explanation, but they do not limit the scope of protection of the claims of the present invention.
  • the olefin monomer A containing furan substituent, the olefin monomer B containing furan substituent, the coupling agent C and the coupling agent D used in the comparative examples and examples of the present invention are obtained through the following ways or methods.
  • Olefin monomers containing furan substituents can be purchased from commercial products or can be directly synthesized.
  • this application provides a conventional synthesis method, which is not a limitation on olefin monomers containing furan substituents.
  • the n-butyllithium solution (90mmol) was added to 50mL of anhydrous tetrahydrofuran in which 147mmol of furan was dissolved at -78°C. The temperature was raised to room temperature to react for 4 hours, and then the temperature was lowered to -78°C, and 126mmol of 5-bromo-1-pentan was added. The alkene was dissolved in 20 mL of anhydrous tetrahydrofuran, added dropwise to the reaction system, and stirred overnight at room temperature.
  • n-butyllithium solution (44mmol) was added to 20mL of anhydrous tetrahydrofuran in which 73.5mmol of furan was dissolved at -78°C, the temperature was raised to room temperature and reacted for 4 hours, and then the temperature was reduced to -78°C, and 68mmol of 8-bromo-1-
  • the octene was dissolved in 10 mL of anhydrous tetrahydrofuran, added dropwise to the reaction system, and stirred overnight at room temperature.
  • reaction solution was poured into ice-water, extracted with ethyl acetate, dried over anhydrous MgSO 4, evaporated under reduced pressure to remove the solvent and unreacted bromo-1-octene, furan-octene to give product B.
  • the structural formula is:
  • Coupling agents can be purchased from commercial products or directly synthesized.
  • this application provides a conventional synthesis method, which is not a limitation on the structure of the coupling agent.
  • Coupling agent C (1) Coupling agent C:
  • the remaining propylene in the reactor is vented, and then a mixed gas of 300 g of ethylene and 300 g of propylene, 0.1 MPa of hydrogen, and the temperature is raised to 80° C., reacted for 40 minutes, and finally 1040 g of the product is obtained.
  • the mass content of ethylene was 18.0%, and the mass content of propylene was 82.0%.
  • the product structure and properties are shown in Table 1.
  • the product structure and properties are shown in Table 1.
  • the remaining propylene in the reactor is vented, 20g of olefin monomer A containing furan substituents is added, and then a mixed gas of 300g of ethylene and 300g of propylene, hydrogen 0.1MPa, heated to 80°C, reacted for 40min, and finally 950g of product is obtained.
  • the mass content of ethylene was 11.2%
  • the mass content of propylene was 81.8%
  • the mass content of monomer A was 2.0%
  • the mass content of coupling agent C was 5.0%.
  • the product structure and properties are shown in Table 1.
  • the mass content of ethylene was 10.4%
  • the mass content of propylene was 80.3%
  • the mass content of monomer A was 2.0%
  • the mass content of coupling agent D was 7.3%.
  • the extruded product After mixing 1250g of the polymer product with 40g of coupling agent C, it 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 melt conveying section is 200°C
  • the temperature of the discharge port is At 180°C
  • the extruded product is cooled in a circulating water bath and pelletized to obtain the target product.
  • the mass content of ethylene is 6.7%
  • the mass content of propylene is 88.8%
  • the mass content of monomer A is 1.4%
  • the mass content of coupling agent C is 3.1%.
  • the mass content of ethylene was 21.0%
  • the mass content of propylene was 65.6%
  • the mass content of monomer A was 0.5%
  • the mass content of monomer B was 3.9%
  • the mass content of coupling agent D was 9.0%.
  • the mass content of ethylene is 17.6%
  • the mass content of propylene is 69.5%
  • the mass content of monomer B is 5.5%
  • the mass content of coupling agent C is 7.4%.
  • Vent the remaining propylene in the reactor add 40g of olefin monomer A containing furan substituents, and then pass in a mixed gas of 300g of ethylene and 300g of propylene, hydrogen 0.075MPa, raise the temperature to 80°C, react for 40min, and finally obtain 1220g of polymer product .
  • the mass content of ethylene was 16.1%
  • the mass content of propylene was 77.4%
  • the mass content of monomer A was 2.6%
  • the mass content of coupling agent C was 3.9%.
  • Vent the remaining propylene in the reactor add 200g of olefin monomer A containing furan substituents, and then pass in a mixed gas of 400g of ethylene and 400g of propylene, hydrogen 0.15MPa, heat up to 80°C, react for 40min, and finally obtain 1220g of polymer product .
  • 1070g of the polymerized product was mixed with 75g of coupling agent D and then 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 melt conveying section is 200°C
  • the temperature of the discharge port is At 180°C, the extruded product is cooled in a circulating water bath and pelletized to obtain the target product.
  • the mass content of ethylene is 19.8%
  • the mass content of propylene is 71.9%
  • the mass content of monomer A is 1.7%
  • the mass content of coupling agent D is 6.6%.
  • Unbroken means that the sample is not completely broken under the impact test conditions.
  • Table 1 lists the performance data of the propylene copolymer.
  • the xylene solubles represent the true content of the ethylene-propylene copolymer elastomer in the copolymer, and the hexane solubles represent the content of the ethylene-propylene copolymer elastomer without a chemical bond with the polypropylene resin.
  • the prepared polypropylene resin and the prepared ethylene-propylene copolymer elastomer are connected by chemical bonds to form a cross-linked network structure.
  • the propylene copolymer prepared by the present invention is a new type of propylene copolymer with a cross-linked network structure, and due to the chemical link between the two phases (the formation of cross-linked bonds can be observed from the infrared spectrum of Figure 2) , Fundamentally enhance the force between the two phases, and finally make the performance of the material significantly improved.
  • the copolymer of the present invention has a thermally reversible cross-linked structure, that is, the cross-linked network can be de-cross-linked in the melt processing state (using the thermally reversible Diels-Alder reaction between furan and maleimide groups) , Make the material have thermoplasticity, can realize repeated processing.
  • the melt index of all the samples in the examples can be measured, and the material on the surface has thermoplasticity; at the same time, comparing the results of Comparative Example 3 and Example 8, it can be seen that the melt index of the two copolymers is similar (that is, the processability is similar), but the implementation
  • the performance of Example 8 is significantly better than that of Comparative Example 3, which indicates that the propylene copolymer prepared by the present invention is cooled to normal use conditions after being processed and formed, and the crosslinked network structure can be produced again, which greatly improves the performance of the material.
  • the propylene copolymer of the present invention is a new type of material with a reversible cross-linked network structure. It has the remarkable characteristics of de-cross-linking during processing and easy processing, and cross-linking formation after molding and high performance.

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Abstract

本发明公开了一种丙烯共聚物及其制备方法与应用，该共聚物由含呋喃的丙烯共聚物与偶联剂小分子之间反应形成交联网络，从而在聚丙烯树脂相和乙丙共聚物弹性体相之间实现化学键连接，从根本上增强两相之间的作用力，提高材料力学性能。同时该共聚物熔融加工时可实现材料的解交联，使材料具有热塑性；其降温后可以再次交联产生网络结构。

Description

一种丙烯共聚物及其制备方法与应用 技术领域
本发明涉及一种丙烯共聚物及其制备方法与应用，特别是一种具有热可逆交联结构的丙烯共聚物的制备方法及其作为抗冲树脂的应用。
背景技术
聚丙烯多相共聚物作为聚丙烯树脂的主要品种之一，通过在聚丙烯基体中分散具有弹性体性质的乙烯/α-烯烃共聚物，从而克服均聚聚丙烯树脂在韧性(尤其是低温韧性)的不足，大大拓宽了聚丙烯树脂的应用范围。在反应釜内连续进行多级的丙烯聚合和乙烯/α-烯烃共聚合，已经成为目前制备聚丙烯多相共聚物的趋势：首先在第一级反应釜中合成等规聚丙烯树脂基体，然后将生成的聚丙烯转移到第二级反应釜中继续进行乙烯与丙烯(或者乙烯与其它α-烯烃)的共聚合反应，合成具有橡胶性质的共聚物并实现其在聚丙烯树脂基体中的原位分散，为聚丙烯树脂提供韧性。其增韧机理是：这种丙烯共聚物中的橡胶相可以吸收或部分吸收断裂处的冲击能量，进而提高材料的整体冲击强度。影响其增韧效果的主要因素包括三方面：(1)橡胶相含量：专利US3,627,852中提到，这种橡胶相只有达到一定含量，才能起到明显的增韧效果。(2)橡胶相的分散尺寸和均匀性：橡胶相一般是作为分散相分布于聚丙烯树脂的基体中，当分散相的尺度在1μm左右时，橡胶相能够起到良好的增韧聚丙烯的作用(Journal of Applied Polymer Science,1996,60,1391-1403)，太大或太小尺度的分散相都将不利于材料性能的提高。然而，聚烯烃本身的非极性特点，使得两相之间的作用力很弱，加之两相之间又无化学键接，随着热处理时间或次数的增加，相分离将逐渐发展，分散相(弹性体共聚物)容易出现大尺度的聚集。中科院化学所董金勇等人通过将橡胶相在聚合时交联(Polymer,2016,85,10-18)，获得橡胶相尺度稳定的抗冲聚丙烯共聚物， 解决了加工过程中相分离逐渐发展、橡胶相发生聚集的问题。(3)橡胶相与树脂基体相的相互作用力大小(即相容性)：增强两相之间的相互作用对抑制相分离、提高材料性能十分关键，目前人们通过在聚合过程中引入具有嵌段结构的乙烯/丙烯共聚物，从而改善两相之间的相容性，但是由于两相之间没有化学键作用，改善效果十分有限。
呋喃/马来酰亚胺之间的Diels-Alder(D-A)反应([4+2]环化反应)具有原料易得、易发生逆向D-A反应(rD-A)的特点，在常温或者加热条件下(60℃左右)呋喃/马来酰亚胺之间发生D-A反应，在120℃左右发生rD-A反应，是制备高性能材料的一种有效途径。如果利用该反应实现树脂相和橡胶相的化学键接，就能够从根本上解决两相之间相容性差的问题，获得性能优异的抗冲聚合物材料；同时，由于该化学键可在120℃断裂，从而满足材料熔融加工的需求，加工成型后冷却时又可实现化学键接，从而获得功能性新材料。
发明内容
本发明提供一种新型丙烯共聚物，该共聚物中：丙烯质量含量为49～95％，乙烯质量含量为3～49％，呋喃取代烯烃单体质量含量为1～30％，偶联剂质量含量0.1～30％。
其中，所述呋喃取代烯烃单体具有如下结构：
Figure PCTCN2019125861-appb-000001
其中，R 1、R 2和R 3可以相同或者不同，且各自独立的选自氢、甲基、乙基、异丙基；m为1～12之间的整数。
所述偶联剂为两端含有马来酰亚胺取代基的脂肪族或芳香族烃类，具有如下结构：
Figure PCTCN2019125861-appb-000002
其中，R 4选自含1～20个碳的烷基。
本发明的另一目的在于提供上述丙烯共聚物的制备方法，具体步骤如下：
1)聚丙烯树脂的制备：将Ziegler-Natta催化剂、助催化剂、丙烯与呋喃取代烯烃单体混合进行聚合反应；
2)乙丙共聚物弹性体的制备：在所述步骤1)反应完毕后，将残留的丙烯放空，向步骤1)的反应体系中通入乙烯、丙烯和呋喃取代烯烃单体组成的混合物进行聚合反应；
3)聚合物的偶联反应：在所述步骤2)反应完毕后，将聚合产物与偶联剂混合得到预混合原料，加入到挤出设备中，进行熔融挤出得到所述丙烯共聚物；
进一步地，上述技术方案中，步骤1)中所述Ziegler-Natta催化剂的用量为所述丙烯质量的0.0005～0.1％，优选0.001～0.01％；所述呋喃取代烯烃单体的用量为所述丙烯质量的0.1～5％，优选0.5～2％；
进一步地，上述技术方案中，步骤1)中所述反应温度为-20～120℃，优选50～90℃；反应时间为0.1～10小时，优选0.5～3小时；反应压力为0.01～6MPa，优选0.1～4MPa；
进一步地，上述技术方案中，在所述步骤1)所述聚合反应之前，向反应体系中加入氢气；所述氢气的加入量为所述丙烯重量的0.01～0.5％，优选0.01～0.2％；
进一步地，上述技术方案中，步骤1)中所述Ziegler-Natta催化剂包括如下组分I至组分Ⅲ；
组分I：Ti的氯化物，其中，Ti元素在所述Ziegler-Natta催化剂中的重量百分含量为0.5～10％；其中，所述Ti的氯化物选自TiCl 3、TiCl 4、TiOCl 3中的至少一种；
组分II：氯化镁，其中，金属元素Mg在所述Ziegler-Natta催化剂中的重量百分含量为5-25％；
组分Ⅲ：内给电子体，所述内给电子体在所述Ziegler-Natta催化剂中的重量百分 含量为1-30％；其中，所述内给电子体包括丁二酸二乙酯、己二酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二正丁酯、邻苯二甲酸二异丁酯、琥珀酸酯、2,2-二异丁基-1,3-二甲氧基丙烷或9,9-二(甲氧基甲基)芴。
进一步地，上述技术方案中，在步骤1)所述聚合反应之前，向反应体系中加入助催化剂；所述助催化剂为烷基铝或烷基铝氧烷中的一种；
其中，所述烷基铝为三烷基铝或由三烷基铝与卤代烷基铝或多卤代烷基铝组成的混合物，其中，所述三烷基铝优选三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝和三烷基铝中的至少一种，所述卤代烷基铝优选AlEt 2Cl；所述多卤代烷基铝优选Al 2Et 3Cl 3；所述烷基铝氧烷优选甲基铝氧烷和异丁基铝氧烷中的至少一种；
所述助催化剂的添加量以Al与所述Ziegler-Natta催化剂中的Ti的摩尔比计，分别为Al：Ti＝10～20000，优选100～10000。
进一步地，上述技术方案中，在步骤1)所述聚合反应之前，向反应体系中加入外给电子体；
所述外给电子体与所述内给电子体相同或不同；所述外给电子体与所述内给电子体不同时，所述外给电子体为结构如R 1R 2Si(OR) 2所示的化合物，其中，R 1和R 2均为碳原子数为1～18的烷基、碳原子数为3～18的环烷基或碳原子数为6～18的芳基，R为碳原子数为1～5的烷基；
进一步地，上述技术方案中，所述外给电子体优选四甲氧基硅烷、二甲基二甲氧基硅烷、四乙氧基硅烷、三乙氧基乙基硅烷、二环戊氧基二乙基硅烷、二苯基二甲氧基硅烷和二苯基二乙氧基硅烷中的至少一种；
进一步地，上述技术方案中，所述外给电子体的用量为所述Ziegler-Natta催化剂中金属Ti元素摩尔用量的0.01～100倍，优选1～50倍。
进一步地，上述技术方案中，步骤2)中所述乙烯的加入量为步骤1)中所述丙烯 加入质量的1～100％，优选10～40％；步骤2)中所述丙烯的加入量为步骤1)中所述丙烯加入质量的1～100％，优选10～40％；步骤2)中所述呋喃取代烯烃的加入量为步骤2)中所述乙烯和丙烯加入总质量的1～40％，优选5～20％；
进一步地，上述技术方案中，步骤2)中所述反应温度为-20～120℃，优选为45～95℃；反应时间为0.1～10小时，优选0.5～4小时；反应压力为0.01～6MPa，优选0.1～4MPa；
进一步地，上述技术方案中，所述步骤2)的聚合反应之前，向反应体系中加入氢气；所述氢气的加入量为所述乙烯和α-烯烃单体总重的0.001～5％，优选0.005％～1％，更优选0.02％～0.15％。
进一步地，上述技术方案中，步骤3)中所述偶联剂加入量为步骤2)产物质量的0.1～40％，优选1～10％；
进一步地，上述技术方案中，步骤3)中所述聚合产物与偶联剂的混合物进行熔融挤出的温度为160～250℃，优选180～230℃。
本发明所述的丙烯共聚物，是一种具有可逆交联网络结构的材料：偶联剂的作用是在步骤1)制备的聚丙烯树脂和步骤2)制备的乙丙共聚物弹性体之间实现化学键连接，形成交联网络结构，从根本上增强两相之间的作用力；利用D-A反应的热可逆性，将共聚物加热至120℃以上时可实现材料的解交联，使材料具有热塑性；其降温至60℃以下时可以再次交联产生网络结构，使材料力学性能增强。
本发明还提供了一种丙烯共聚物在作为抗冲聚合物树脂材料中的应用。
附图说明
图1为对比例3、实施例7的产物的核磁氢谱谱图对比。
图2为对比例3、实施例7的产物的红外光谱谱图对比。
图3为对比例4、实施例3的产物的断面经过己烷刻蚀前后的扫描电镜照片对比。
具体实施方式
本发明提出以下实施例作为进一步的说明，但并非限制本发明权利要求保护的范围。本发明对比例及实施例所用含呋喃取代基的烯烃单体A、含呋喃取代基的烯烃单体B、偶联剂C和偶联剂D通过以下途径或方式获得。
含呋喃取代基的烯烃单体：
含呋喃取代基的烯烃单体可以购自商品，也可以直接合成。对于合成的含呋喃取代基的烯烃单体，本申请提供一种常规合成方法，并非对含呋喃取代基的烯烃单体的限定。
(1)含呋喃取代基的烯烃单体A：
将正丁基锂溶液(90mmol)在-78℃加入到溶解有147mmol呋喃的50mL无水四氢呋喃中，升温至室温反应4小时，再降温至-78℃，将126mmol的5-溴-1-戊烯溶解在20mL无水四氢呋喃中，逐滴加入到反应体系中，室温下搅拌过夜。将反应溶液倒入冰水中，用乙酸乙酯萃取，无水MgSO 4干燥，减压蒸馏除去溶剂和未反应的5-溴-1-戊烯，得到产物呋喃戊烯A。结构式为：
Figure PCTCN2019125861-appb-000003
(2)含呋喃取代基的烯烃单体B：
将正丁基锂溶液(44mmol)在-78℃加入到溶解有73.5mmol呋喃的20mL无水四氢呋喃中，升温至室温反应4小时，再降温至-78℃，将68mmol的8-溴-1-辛烯溶解在10mL无水四氢呋喃中，逐滴加入到反应体系中，室温下搅拌过夜。将反应溶液倒入冰水中，用乙酸乙酯萃取，无水MgSO 4干燥，减压蒸馏除去溶剂和未反应的8-溴-1-辛烯，得到产物呋喃辛烯B。结构式为：
Figure PCTCN2019125861-appb-000004
偶联剂：
偶联剂可以购自商品，也可以直接合成。对于合成两端含有马来酰亚胺的偶联剂，本申请提供一种常规合成方法，并非对偶联剂结构的限定。
(1)偶联剂C：
市售商品：购自安耐吉化学公司，CAS号：13676-54-5。
Figure PCTCN2019125861-appb-000005
(2)偶联剂D：
合成方法：将10g呋喃保护的马来酸酐与7mL三乙胺溶于60mL甲醇，冰水浴滴加入溶于40mL甲醇的己二胺2.92g。氮气保护下70～80℃加热回流48小时。将产物过滤干燥，加入少量甲苯(30～50mL)于120℃加热回流48小时。减压蒸馏除去溶剂，得到产物D。结构如下图所示：
Figure PCTCN2019125861-appb-000006
对比例1
在10L的聚合反应釜中加入2kg液态丙烯，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.076g，三乙基铝0.36g，Ziegler-Natta催化剂60mg，升温至75℃，反应120min，得到聚丙烯产物1524g。产物结构与性能见表1。
对比例2
在10L的聚合反应釜中加入2kg液态丙烯，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.076g，三乙基铝0.36g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯850g。
将反应釜中残留的丙烯放空，再通入300g乙烯和300g丙烯的混合气，氢气0.1 MPa，升温至80℃，反应40min，最终得到产物1040g。
得到的产物中，乙烯质量含量为11.5％，丙烯质量含量为88.5％。产物结构与性能见表1。
其核磁氢谱图如附图1所示。
对比例3
在10L的聚合反应釜中加入2kg液态丙烯，氢气0.25MPa，30℃下依次加入二苯二甲氧基硅烷0.076g，三乙基铝0.36g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯990g。
将反应釜中残留的丙烯放空，再通入300g乙烯和300g丙烯的混合气，氢气0.15MPa，升温至80℃，反应40min，最终得到聚合产物1370g。
得到的产物中，乙烯质量含量为18.0％，丙烯质量含量为82.0％。产物结构与性能见表1。产物结构与性能见表1。
对比例4
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.076g，三乙基铝0.36g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯780g。
将反应釜中残留的丙烯放空，加入20g含呋喃取代基的烯烃单体A，再通入300g乙烯和300g丙烯的混合气，氢气0.1MPa，升温至80℃，反应40min，最终得到产物950g。
得到的产物中，乙烯质量含量为11.8％，丙烯质量含量为86.1％，单体A质量含量为2.1％。产物结构与性能见表1。
其核磁氢谱图如附图2所示。
实施例1
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.076g，三乙基铝0.36g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯780g。
将反应釜中残留的丙烯放空，加入20g含呋喃取代基的烯烃单体A，再通入300g乙烯和300g丙烯的混合气，氢气0.1MPa，升温至80℃，反应40min，最终得到聚合产物950g。
将聚合产物950g与50g偶联剂C混合后加入到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℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为11.2％，丙烯质量含量为81.8％，单体A质量含量为2.0％，偶联剂C质量含量5.0％。产物结构与性能见表1。
其核磁氢谱图如附图3所示。
实施例2
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.080g，三乙基铝0.45g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯780g。
将反应釜中残留的丙烯放空，加入40g含呋喃取代基的烯烃单体A，再通入300g乙烯和300g丙烯的混合气，氢气0.1MPa，升温至80℃，反应40min，最终得到聚合产物985g。
将聚合产物985g与90g偶联剂C混合后加入到35型双螺杆挤出机中进行熔融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为14.8％，丙烯质量含量为73.2％，单体A质量含 量为3.6％，偶联剂C质量含量8.4％。产物结构与性能见表1。
实施例3
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.076g，三乙基铝0.36g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯780g。
将反应釜中残留的丙烯放空，加入20g含呋喃取代基的烯烃单体A，再通入300g乙烯和300g丙烯的混合气，氢气0.1MPa，升温至80℃，反应40min，最终得到聚合产物950g。
将聚合产物950g与75g偶联剂D混合后加入到35型双螺杆挤出机中进行熔融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为10.4％，丙烯质量含量为80.3％，单体A质量含量为2.0％，偶联剂D质量含量7.3％。产物结构与性能见表1。
实施例4
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.076g，三乙基铝0.36g，Ziegler-Natta催化剂60mg，升温至75℃，反应90min。得到聚丙烯1120g。
将反应釜中残留的丙烯放空，加入20g含呋喃取代基的烯烃单体A，再通入300g乙烯和300g丙烯的混合气，氢气0.1MPa，升温至80℃，反应30min，最终得到聚合产物1250g。
将聚合产物1250g与40g偶联剂C混合后加入到35型双螺杆挤出机中进行熔融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为6.7％，丙烯质量含量为88.8％，单体A质量含量为1.4％，偶联剂C质量含量3.1％。产物结构与性能见表1。
实施例5
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.080g，三乙基铝0.45g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯780g。
将反应釜中残留的丙烯放空，加入80g含呋喃取代基的烯烃单体B，再通入300g乙烯和300g丙烯的混合气，氢气0.1MPa，升温至80℃，反应60min，最终得到聚合产物1210g。
将聚合产物1210g与120g偶联剂D混合后加入到35型双螺杆挤出机中进行熔融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为21.0％，丙烯质量含量为65.6％，单体A质量含量为0.5％，单体B质量含量为3.9％，偶联剂D质量含量9.0％。产物结构与性能见表1。
实施例6
在10L的聚合反应釜中加入2kg液态丙烯，15g含呋喃取代基的烯烃单体B，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.080g，三乙基铝0.45g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯900g。
将反应釜中残留的丙烯放空，加入100g含呋喃取代基的烯烃单体B，再通入300g乙烯和300g丙烯的混合气，氢气0.1MPa，升温至80℃，反应60min，最终得到聚合产物1250g。
将聚合产物1250g与100g偶联剂C混合后加入到35型双螺杆挤出机中进行熔 融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为17.6％，丙烯质量含量为69.5％，单体B质量含量为5.5％，偶联剂C质量含量7.4％。产物结构与性能见表1。
实施例7
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.2MPa，30℃下依次加入二苯基二甲氧基硅烷0.070g，三异丁基铝0.45g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯880g。
将反应釜中残留的丙烯放空，加入40g含呋喃取代基的烯烃单体A，再通入300g乙烯和300g丙烯的混合气，氢气0.075MPa，升温至80℃，反应40min，最终得到聚合产物1220g。
将聚合产物1220g与50g偶联剂C混合后加入到35型双螺杆挤出机中进行熔融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为16.1％，丙烯质量含量为77.4％，单体A质量含量为2.6％，偶联剂C质量含量3.9％。产物结构与性能见表1。
实施例8
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.25MPa，30℃下依次加入二苯基二甲氧基硅烷0.070g，三异丁基铝0.45g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯980g。
将反应釜中残留的丙烯放空，加入40g含呋喃取代基的烯烃单体A，再通入300g乙烯和300g丙烯的混合气，氢气0.15MPa，升温至80℃，反应40min，最终得到聚合产物1350g。
将聚合产物1350g与60g偶联剂C混合后加入到35型双螺杆挤出机中进行熔融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为15.7％，丙烯质量含量为78.1％，单体A质量含量为1.9％，偶联剂C质量含量4.3％。产物结构与性能见表1。
实施例9
在10L的聚合反应釜中加入2kg液态丙烯，90g含呋喃取代基的烯烃单体A，氢气0.25MPa，30℃下依次加入二苯基二甲氧基硅烷0.070g，三异丁基铝0.80g，Ziegler-Natta催化剂80mg，升温至75℃，反应60min。得到聚丙烯980g。
将反应釜中残留的丙烯放空，加入200g含呋喃取代基的烯烃单体A，再通入400g乙烯和400g丙烯的混合气，氢气0.15MPa，升温至80℃，反应40min，最终得到聚合产物1220g。
将聚合产物1220g与250g偶联剂C混合后加入到35型双螺杆挤出机中进行熔融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为10.6％，丙烯质量含量为56.6％，单体A质量含量为15.8％，偶联剂C质量含量17.0％。产物结构与性能见表1。
实施例10
在10L的聚合反应釜中加入2kg液态丙烯，10g含呋喃取代基的烯烃单体A，氢气0.1MPa，30℃下依次加入二苯基二甲氧基硅烷0.076g，三乙基铝0.36g，Ziegler-Natta催化剂60mg，升温至75℃，反应60min。得到聚丙烯780g。
将反应釜中残留的丙烯放空，加入20g含呋喃取代基的烯烃单体A，再通入400g乙烯和200g丙烯的混合气，氢气0.1MPa，升温至80℃，反应40min，最终得到聚 合产物1070g。
将聚合产物1070g与75g偶联剂D混合后加入到35型双螺杆挤出机中进行熔融，挤出机的熔融段温度为160℃，熔体输送段温度为200℃，出料口温度为180℃，挤出产物经过循环水浴冷却和切粒，得到目标产物。
得到的产物中，乙烯质量含量为19.8％，丙烯质量含量为71.9％，单体A质量含量为1.7％，偶联剂D质量含量6.6％。产物结构与性能见表1。
表1聚合物组成和性能
Figure PCTCN2019125861-appb-000007
注a：未断指在该冲击测试条件下，试样没有完全断裂。
表1列出了丙烯共聚物的性能数据。其中二甲苯可溶物代表共聚物中的乙丙共聚物弹性体真实含量，己烷可溶物代表与聚丙烯树脂之间没有化学键连接的乙丙共聚物弹性体的含量。
首先，与对比例相比，由于本发明的共聚物中加入了呋喃烯烃和偶联剂，使制备的聚丙烯树脂和制备的乙丙共聚物弹性体之间实现化学键连接，形成交联网络结构， 这可以从产物中未进行化学键链接的乙丙共聚物含量(沸腾己烷可溶物)显著低于乙丙共聚物总含量(二甲苯可溶物)得到证实：在对比例2、对比例3和对比例4中，由于制备的聚丙烯树脂和制备的乙丙共聚物弹性体之间没有化学键接，沸腾己烷可溶物含量接近乙丙共聚物总含量(二甲苯可溶物)；对比例4和实施例3的断面刻蚀照片(如附图3所示)也可得出同样的结论，即对比例4中的乙丙共聚物弹性体可以被己烷溶出形成大量孔洞，而实施例3中的乙丙共聚物弹性体则基本没有溶出。上述结果证明本发明制备的丙烯共聚物是一种具有交联网络结构的新型丙烯共聚物，并且由于两相之间的化学链接(从附图2的红外光谱可观察到交联键的形成)，从根本上增强两相之间的作用力，最终使材料的性能得到明显提升。
其次，本发明的共聚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(利用呋喃和马来酰亚胺基团之间的热可逆Diels-Alder反应)，使材料具有热塑性，能够实现反复加工。所有实施例样品均可以进行熔融指数测定，表面该材料具有热塑性；同时，比较对比例3和实施例8的结果可以看出，两种共聚物的熔融指数相近(即加工性能相近)，但实施例8的性能显著优于对比例3，这表明本发明制备的丙烯共聚物在加工成型后降温至通常使用条件，可以再次产生交联网络结构，大大提高材料的性能。
综上，本发明所述的丙烯共聚物，是一种具有可逆交联网络结构的新型材料，其具有加工时解交联、易加工，而成型后交联形成、高性能的显著特点。

Claims (10)

  1. 一种丙烯共聚物，其特征在于：所述丙烯共聚物中，丙烯质量含量为49～95％，乙烯质量含量为3～49％，呋喃取代烯烃单体质量含量为1～30％，偶联剂质量含量0.1～30％。
  2. 根据权利要求1所述的丙烯共聚物，其特征在于：所述呋喃取代烯烃单体具有如下结构：
    Figure PCTCN2019125861-appb-100001
    其中，R 1、R 2和R 3可以相同或者不同，R 1、R 2和R 3各自独立的选自氢、甲基、乙基、异丙基；m为1～12之间的整数。
  3. 根据权利要求1所述的丙烯共聚物，其特征在于：所述偶联剂为两端含有马来酰亚胺取代基的脂肪族或芳香族烃类，具有如下结构：
    Figure PCTCN2019125861-appb-100002
    其中，R 4选自含1～20个碳的烷基。
  4. 权利要求1-3任一项所述丙烯共聚物的制备方法，其特征在于包括如下步骤：
    1)将Ziegler-Natta催化剂、助催化剂、丙烯与呋喃取代烯烃单体混合进行聚合反应；
    2)在所述步骤1)反应完毕后，将残留的丙烯放空，向步骤1)的反应体系中通入乙烯、丙烯和呋喃取代烯烃单体组成的混合物进行聚合反应；
    3)在所述步骤2)反应完毕后，将聚合产物与偶联剂混合得到预混合原料，加入到挤出设备中，进行熔融挤出得到所述丙烯共聚物。
  5. 根据权利要求4所述的方法，其特征在于：
    所述步骤1)中Ziegler-Natta催化剂的用量为丙烯质量的0.0005～0.1％，呋喃取代烯烃单体的用量为丙烯质量的0.1～5％；所述步骤1)的聚合反应的反应温度为-20～120℃；反应时间为0.1～10小时；反应压力为0.01～6MPa；
    所述步骤2)中，聚合反应中乙烯的加入量为步骤1)中所述丙烯加入质量的1～100％；步骤2)中丙烯的加入量为步骤1)中所述丙烯加入质量的1～100％；呋喃取代烯烃的加入量为步骤2)中所述乙烯和丙烯加入总质量的1～40％；所述步骤2)中的聚合反应温度为-20～120℃；聚合反应时间为0.1～10小时；聚合反应压力为0.01～6MPa；
    所述步骤3)中偶联剂加入量为步骤2)产物质量的0.1～40％；所述步骤3)中熔融挤出的温度为160～250℃。
  6. 根据权利要求4所述的方法，其特征在于：在步骤1)所述聚合反应之前，向反应体系中加入氢气；所述氢气的加入量为步骤1)所述丙烯重量的0.01～0.5％；
    在步骤2)所述聚合反应之前，向反应体系中加入氢气；所述氢气的加入量为所述乙烯和α-烯烃单体总重的0.001～5％。
  7. 根据权利要求4所述的方法，其特征在于：所述Ziegler-Natta催化剂包括如下组分I至组分Ⅲ；
    组分I：Ti的氯化物，其中，Ti元素在所述Ziegler-Natta催化剂中的重量百分含量为0.5～10％；其中，所述Ti的氯化物选自TiCl 3、TiCl 4、TiOCl 3中的至少一种；
    组分II：氯化镁，其中，金属元素Mg在所述Ziegler-Natta催化剂中的重量百分含量为5～25％；
    组分Ⅲ：内给电子体，所述内给电子体在所述Ziegler-Natta催化剂中的重量百分含量为1～30％；其中，所述内给电子体包括丁二酸二乙酯、己二酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二正丁酯、邻苯二甲酸二异丁酯、琥珀酸酯或2,2-二异丁基 -1,3-二甲氧基丙烷或9,9-二(甲氧基甲基)芴。
  8. 根据权利要求4所述的方法，其特征在于：所述步骤1)中的助催化剂为烷基铝或烷基铝氧烷中的一种；
    其中，所述烷基铝为三烷基铝、或由三烷基铝与卤代烷基铝或多卤代烷基铝组成的混合物，其中，所述三烷基铝为三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝、三烷基铝中至少一种；所述卤代烷基铝包括AlEt 2Cl；所述多卤代烷基铝包括Al 2Et 3Cl 3；所述烷基铝氧烷为甲基铝氧烷、异丁基铝氧烷中至少一种；
    所述助催化剂的添加量为助催化剂中的Al与Ziegler-Natta催化剂中的Ti的摩尔比为Al：Ti＝10～20000。
  9. 根据权利要求4所述的方法，其特征在于：步骤1)所述聚合反应之前，向反应体系中加入外给电子体；
    所述外给电子体为与权利要求8所述内给电子体相同或为结构如R 1R 2Si(OR) 2所示的化合物，其中，R 1和R 2均为碳原子数为1～18的烷基、碳原子数为3～18的环烷基或碳原子数为6～18的芳基，R为碳原子数为1～5的烷基；
    所述外给电子体为四甲氧基硅烷、二甲基二甲氧基硅烷、四乙氧基硅烷、三乙氧基乙基硅烷、二环戊氧基二乙基硅烷、二苯基二甲氧基硅烷和二苯基二乙氧基硅烷中的至少一种；
    所述外给电子体的摩尔用量为所述Ziegler-Natta催化剂中金属Ti元素摩尔用量的0.01～100倍。
  10. 权利要求1-3中任意一项所述的丙烯共聚物在作为抗冲聚合物树脂材料中的应用。
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