WO2022188202A1 - Polytricyclopentadiene (ptcpd)/elastomer ipn alloy material and preparation method therefor - Google Patents

Polytricyclopentadiene (ptcpd)/elastomer ipn alloy material and preparation method therefor Download PDF

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WO2022188202A1
WO2022188202A1 PCT/CN2021/081899 CN2021081899W WO2022188202A1 WO 2022188202 A1 WO2022188202 A1 WO 2022188202A1 CN 2021081899 W CN2021081899 W CN 2021081899W WO 2022188202 A1 WO2022188202 A1 WO 2022188202A1
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elastomer
ptcpd
polytricyclopentadiene
alloy material
rubber
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PCT/CN2021/081899
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French (fr)
Chinese (zh)
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陈喆
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浙江沪通模具有限公司
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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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a polytricyclopentadiene PTCPD/elastomer IPN alloy material and a preparation method thereof.
  • IPN Interpenetrating Polymer Network
  • interpenetrating polymer network structure is a network structure formed by two or more blended polymers, the molecular chains penetrate each other, and at least one polymer molecular chain is cross-linked in the form of chemical bonds. .
  • IPN interpenetrating network that can play the role of "forced compatibility", and different polymer molecules are entangled with each other to form a whole, which cannot be released.
  • different polymers have their own phases, and there is no chemical combination. Therefore, IPN is different from graft or block copolymers, and also different from general polymer blends or polymer composites. Due to the existence of permanent irreversible entanglements in the IPN, some mechanical properties of the IPN may surpass the corresponding one-component polymers.
  • Polydicyclopentadiene is an engineering plastic with high impact resistance and high modulus, which is polymerized from monomer dicyclopentadiene DCPD under the action of catalyst.
  • Polydicyclopentadiene PDCPD has certain advantages to prepare IPN.
  • the DCPD ring-opening metathesis polymerization has strong exothermic and fast speed. No matter whether the polymer and DCPD are compatible or not, the hybrid system is due to the cross-linking polymerization of DCPD before the phase separation of DCPD occurs. Curing can form an IPN with forced mutual capacitance.
  • the embodiment of the present application solves the technical problem that the polydicyclopentadiene IPN material in the prior art has insufficient thermal deformation temperature performance, and makes the tricyclopentadiene IPN material insufficient.
  • the diene and the elastomer form an interpenetrating network structure to make a polytricyclopentadiene/elastomer IPN alloy material, which has both high impact strength and high heat distortion temperature.
  • the embodiment of the present application provides a polytricyclopentadiene PTCPD/elastomer IPN alloy material, and the IPN alloy material includes:
  • the elastomer is uniformly dispersed in the polytricyclopentadiene PTCPD resin system, and the cross-linked network of the polytricyclopentadiene PTCPD resin system is intertwined with the elastomer to form an interpenetrating polymer network.
  • the elastomer is a thermosetting elastomer
  • the linear molecular chains of the thermosetting elastomer are penetrated in the cross-linked network of the polytricyclopentadiene PTCPD resin system, and are interpenetrated and intertwined to form a semi-interconnected through the polymer network.
  • the elastomer is a thermoplastic elastomer, and the cross-linked network of the thermoplastic elastomer and the cross-linked network of the polytricyclopentadiene PTCPD resin system interpenetrate and interlock to form a fully interpenetrating polymer network.
  • thermosetting elastomer is natural rubber NR, isoprene rubber IR, polybutadiene rubber BR, styrene butadiene rubber SBR, nitrile nitrile rubber NBR, neoprene rubber CR, butyl rubber IIR, halogenated butyl rubber, EPDM, EPDM, chloroether rubber ECO, polyacrylate rubber ABR, silicone rubber MVQ, fluorosilicone rubber FVMQ, fluororubber FEPM, chlorosulfonated polyethylene CSM, hydrogenated nitrile rubber HNBR one or more of them.
  • thermoplastic elastomer is thermoplastic polyolefin elastomer TEO, thermoplastic styrene elastomer TES, polyurethane thermoplastic elastomer TPU, polyester thermoplastic elastomer TPE-E, polyamide thermoplastic elastomer TPE-A, Halogen-containing thermoplastic elastomer, ionic thermoplastic elastomer, ethylene copolymer thermoplastic elastomer EVA, 1,2 polybutadiene thermoplastic elastomer, trans-polyisoprene thermoplastic elastomer, melt processing thermoplastic elastomer Alcryn, One or more of thermoplastic vulcanizate TPV.
  • the polytricyclopentadiene PTCPD resin system comprises the following components:
  • Tricyclopentadiene TCPD Tricyclopentadiene
  • the weight percentage of the tricyclopentadiene TCPD in the polytricyclopentadiene resin system is greater than or equal to 50% and less than 100%.
  • the components of the polytricyclopentadiene resin system further include one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene and pentacyclopentadiene.
  • the resin polymerization catalyst comprises one or more of a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst;
  • the weight of the resin polymerization catalyst is 0.01% to 1% of the weight of the tricyclopentadiene TCPD.
  • the components of the IPN alloy material further include additives and/or fillers;
  • the auxiliary agent is one or more of antioxidants, ultraviolet absorbers, visible light absorbers, impact agents, flame retardants, pigments, and graphene;
  • the filler is one or more of silica, alumina, montmorillonite, silica lime, titanium dioxide and asphalt.
  • the embodiment of the present application also provides a preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material, the steps are:
  • the weight percentage of tricyclopentadiene TCPD in the liquid resin raw material is greater than or equal to 50% and less than 100%;
  • the mixture is formulated into two components A and B, and a catalyst is added to the A and/or B components;
  • the two components A and B are mixed in proportion, they are injected into the cavity of the closed mold; when heated, the two components A and B are polymerized and cross-linked to solidify and form;
  • the mold is opened and demolded to obtain a polytricyclopentadiene PTCPD/elastomer IPN alloy material product.
  • the catalysts added to the A and/or B components include resin material polymerization catalysts and elastomer material polymerization catalysts.
  • the resin raw material polymerization reaction catalyst includes one or more of a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst.
  • the elastomer raw material polymerization catalyst includes one or more of benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, and tert-butyl hydroperoxide.
  • This application is based on tricyclopentadiene and an elastomer, and is made into a polytricyclopentadiene/elastomer IPN alloy material, which has both high impact strength and high thermal deformation temperature, which solves the problem of existing The technical problem of insufficient thermal deformation temperature performance of polydicyclopentadiene IPN material in technology.
  • the polytricyclopentadiene/elastomer IPN alloy material provided in this application has a simple preparation method, convenient operation and high preparation efficiency, and is suitable for large-scale industrial production and application.
  • the polytricyclopentadiene/elastomer IPN alloy material provided in this application also has excellent properties such as acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance, etc., and has a wide range of applications.
  • the embodiments of the present application solve the technical problem of insufficient thermal deformation temperature performance of polydicyclopentadiene IPN materials in the prior art by providing a polytricyclopentadiene PTCPD/elastomer IPN alloy material.
  • the tricyclopentadiene and the elastomer form an interpenetrating network structure under the action of a catalyst to make a polytricyclopentadiene/elastomer IPN alloy material.
  • the IPN alloy materials include:
  • the elastomer is uniformly dispersed in the polytricyclopentadiene PTCPD resin system, and the cross-linked network of the polytricyclopentadiene PTCPD resin system is intertwined with the elastomer to form an interpenetrating polymer network.
  • the elastomer can also be a thermosetting elastomer.
  • the linear molecular chains of the thermosetting elastomer are punctured in the cross-linked network of the polytricyclopentadiene PTCPD resin system and interpenetrated and intertwined to form a semi-circular tether. Interpenetrating polymer network.
  • the elastomer can be a thermoplastic elastomer.
  • the cross-linked network of the thermoplastic elastomer and the cross-linked network of the polytricyclopentadiene PTCPD resin system are interpenetrating and interlocking to form a fully interpenetrating polymer network. .
  • thermosetting elastomers are natural rubber NR, isoprene rubber IR, polybutadiene rubber BR, styrene butadiene rubber SBR, nitrile nitrile rubber NBR, neoprene CR, butyl rubber IIR, halogenated butyl rubber, diethyl ether
  • thermoplastic elastomer is thermoplastic polyolefin elastomer TEO, thermoplastic styrene elastomer TES, polyurethane thermoplastic elastomer TPU, polyester thermoplastic elastomer TPE-E, polyamide thermoplastic elastomer TPE-A, halogen-containing thermoplastic elastomer Elastomers, ionic thermoplastic elastomers, ethylene copolymer thermoplastic elastomers EVA, 1,2 polybutadiene thermoplastic elastomers, trans-polyisoprene thermoplastic elastomers, melt processable thermoplastic elastomers Alcryn, thermoplastic vulcanizates One or more of TPVs.
  • the polytricyclopentadiene PTCPD resin system comprises the following components:
  • Tricyclopentadiene TCPD Tricyclopentadiene
  • the weight percentage of the tricyclopentadiene TCPD in the polytricyclopentadiene resin system is greater than or equal to 50% and less than 100%.
  • the components of the polytricyclopentadiene resin system further include one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene and pentacyclopentadiene.
  • the resin polymerization catalyst comprises one or more of a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst;
  • the resin polymerization catalyst also includes one or more of metal-organic compounds of aluminum, magnesium, tin, zinc, and silicon. Such as triethylaluminum, tributylaluminum, diethylaluminum monochloride, triisobutylaluminum, etc.
  • the resin polymerization catalyst also includes one or more of alcohol, phenol and BF 3 .
  • the tungsten-based catalyst includes one or more of tungsten element, tungsten oxide, tungsten halide (such as tungsten sulfide, tungsten chloride), tungsten hydroxyl compound, and heteropolytungstic acid;
  • the molybdenum-based catalyst includes one or more of molybdenum element, molybdenum oxide, molybdenum halide, molybdenum hydroxy compound, phosphomolybdic acid and ammonium molybdate;
  • the ruthenium-based catalyst is one or more of metal ruthenium and ruthenium compounds; such as Grubbs' I-generation and Grubbs' II-generation ruthenium catalysts.
  • the titanium-based catalyst is one or more of metal titanium, titanium oxide, titanium halide, and titanium hydroxy compound;
  • the rhenium-based catalyst is one or more of metal rhenium, rhenium oxide, rhenium halide, and rhenium hydroxy compound.
  • the weight of the resin polymerization catalyst is 0.01% to 1% of the weight of the tricyclopentadiene TCPD.
  • the weight of the elastomer is 1% to 70% of the weight of the tricyclopentadiene TCPD.
  • the components of the IPN alloy material also include additives and/or fillers
  • the auxiliary agent is one or more of antioxidants, ultraviolet absorbers, visible light absorbers, impact agents, flame retardants, pigments, and graphene;
  • the filler is one or more of silica, alumina, montmorillonite, silica lime, titanium dioxide and asphalt.
  • the weight percentage of tricyclopentadiene TCPD in the liquid resin raw material is greater than or equal to 50% and less than 100%;
  • the mixture is formulated into two components A and B, and a catalyst is added to the A and/or B components;
  • the two components A and B are mixed in proportion, they are injected into the cavity of the closed mold; when heated, the two components A and B are polymerized and cross-linked to solidify and form;
  • the mold is opened and demolded to obtain a polytricyclopentadiene PTCPD/elastomer IPN alloy material product.
  • the catalysts added in the A and/or B components only include resin raw material polymerization catalysts.
  • the catalysts added to the A and/or B components include a resin raw material polymerization catalyst and an elastomer raw material polymerization catalyst.
  • the resin raw material polymerization reaction catalyst includes one or more of tungsten-based catalysts, molybdenum-based catalysts, ruthenium-based catalysts, titanium-based catalysts, and rhenium-based catalysts.
  • the elastomer raw material polymerization catalyst includes one or more of benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, and tert-butyl hydroperoxide.
  • the polytricyclopentadiene PTCPD/elastomer IPN alloy material is composed of the following components by weight:
  • Tricyclopentadiene TCPD 98%
  • the preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material the steps are:
  • Step S1 configure liquid tricyclopentadiene TCPD and dicyclopentadiene DCPD resin raw materials
  • Step S2 dissolving the butyl rubber into the liquid resin raw material, and stirring at 75°C for 6 hours to obtain a mixture;
  • Step S3 the mixture is prepared into two components A and B, and a ruthenium carbene catalyst is added to the B component;
  • Step S4 After mixing the two components A and B, they are injected into the cavity of the closed mold; heated to 80° C., the two components A and B are rapidly polymerized and cross-linked to solidify and form;
  • Step S5 opening the mold, demoulding to obtain a polytricyclopentadiene PTCPD/SBS IPN alloy material product.
  • the molecular chain of the butyl rubber is highly entangled with the polytricyclopentadiene PTCPD cross-linked network during the formation of the cross-linked network, forming a Semi-interpenetrating polymer network.
  • the polytricyclopentadiene PTCPD/elastomer IPN alloy material is composed of the following components by weight:
  • Tricyclopentadiene TCPD 83%
  • the preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material the steps are:
  • Step S1 configure liquid tricyclopentadiene TCPD and dicyclopentadiene DCPD resin raw materials
  • Step S2 dissolving styrene and divinylbenzene in the liquid resin raw material, and stirring at 65° C. for 5 hours to obtain a uniform mixture;
  • Step S3 under nitrogen protection, the mixture is prepared into two components A and B, CpTiCl 2 and benzoyl peroxide are added to the A component, and CH 3 MgI is added to the B component;
  • Step S4 After mixing the two components A and B, they are injected into the cavity of the closed mold; heated to 75° C., the two components A and B are rapidly polymerized and cross-linked to solidify and form;
  • Step S5 opening the mold and demoulding to obtain a polytricyclopentadiene PTCPD/polystyrene IPN alloy material product.
  • polytricyclopentadiene PTCPD/polystyrene IPN alloy material prepared in this example tricyclopentadiene and a small amount of dicyclopentadiene form polytricyclopentadiene under the catalysis of CpTiCl 2 and CH 3 MgI Cross-linked network.
  • Styrene and divinylbenzene form a polystyrene cross-linked network under the catalysis of benzoyl peroxide.
  • the polytricyclopentadiene PTCPD cross-linked network and the polystyrene cross-linked network interpenetrate and interlock to form a fully interpenetrating polymer network.
  • the polytricyclopentadiene PTCPD/elastomer IPN alloy material is composed of the following components by weight:
  • Tricyclopentadiene TCPD 70%
  • the preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material the steps are:
  • Step S1 configure liquid tricyclopentadiene TCPD and tetracyclopentadiene DCPD resin raw materials
  • Step S2 put 2,4,6-tribromostyrene and divinylbenzene into the liquid resin raw material to dissolve, and stir at 70°C for 6 hours to obtain a uniform mixture;
  • Step S3 under nitrogen protection, the mixture is prepared into two components A and B, ReCls and azobisisobutyronitrile are added to the A component, and (CH 3 ) 4 Sn is added to the B component;
  • Step S4 After mixing the two components A and B, they are injected into the cavity of the closed mold; heated to 70° C., the two components A and B are rapidly polymerized and cross-linked to solidify and form;
  • Step S5 opening the mold and demoulding to obtain a polytricyclopentadiene PTCPD/poly2,4,6-tribromostyrene IPN alloy material product.
  • the polytricyclopentadiene PTCPD cross-linked network and the poly-2,4,6-tribromostyrene cross-linked network interpenetrate and interlock to form a fully interpenetrating polymer network.
  • the addition of poly-2,4,6-tribromostyrene makes the flame retardancy of the IPN alloy material significantly improved.
  • the polytricyclopentadiene PTCPD/elastomer IPN alloy material is composed of the following components by weight:
  • Tricyclopentadiene 50% by weight
  • Butadiene rubber 35% by weight
  • the preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material the steps are:
  • Step S1 configure liquid tricyclopentadiene TCPD and dicyclopentadiene DCPD resin raw materials
  • Step S2 dissolving the nitrile-butadiene rubber in the liquid resin raw material, and stirring at 70° C. for 7 hours to obtain a mixture;
  • Step S3 preparing the mixture into two components A and B, adding WCl 6 and C 6 H 2 Cl 4 O to the A component; adding AlEt 2 Cl to the B component;
  • Step S4 After mixing the two components A and B, they are injected into the cavity of the closed mold; heated to 80° C., the two components A and B are rapidly polymerized and cross-linked to solidify and form;
  • Step S5 opening the mold, demoulding, and obtaining a polytricyclopentadiene PTCPD/butadiene nitrile rubber IPN alloy material product.
  • the butadiene rubber molecular chain is highly entangled with the polytricyclopentadiene PTCPD cross-linked network during the formation of the cross-linked network, forming a semi-interpenetrating polymer network.
  • polydicyclopentadiene/elastomer IPN material was prepared by using dicyclopentadiene, which was used as Comparative Example 1 to Comparative Example 4.
  • the polydicyclopentadiene/elastomer IPN materials obtained in Comparative Examples 1 to 4 were tested, and the following results were obtained.
  • the polytricyclopentadiene PTCPD/elastomer IPN alloy material prepared in this application has improved its thermal deformation on the basis of ensuring its impact strength compared with the polydicyclopentadiene/elastomer IPN material.
  • the temperature makes the alloy material have more excellent comprehensive properties and meet the high performance requirements of materials in specific fields.
  • the polytricyclopentadiene/elastomer IPN alloy material provided in the present application also has excellent properties such as acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance, etc., and has a wide range of applications.

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Abstract

Disclosed in the present invention are a polytricyclopentadiene (PTCPD)/elastomer IPN alloy material and a preparation method therefor. The IPN alloy material comprises: a PTCPD resin system; and an elastomer, the elastomer being uniformly dispersed in the PTCPD resin system, and the cross-linked network of the PTCPD resin system being intertwined with the elastomer to form an interpenetrating polymer network. The PTCPD/elastomer IPN alloy material provided by the present invention has both high impact strength and high heat deformation temperature. Moreover, the preparation method for the alloy material provided by the present invention is simple, is convenient to operate, and has high preparation efficiency, and is suitable for large-scale industrial production and application. In addition, the alloy material also has excellent properties such as acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance, etc., and has an application wide range.

Description

聚三环戊二烯PTCPD/弹性体IPN合金材料及其制备方法Polytricyclopentadiene PTCPD/elastomer IPN alloy material and preparation method thereof 技术领域technical field
本发明涉及高分子材料技术领域，尤其涉及一种聚三环戊二烯PTCPD/弹性体IPN合金材料及其制备方法。The invention relates to the technical field of polymer materials, in particular to a polytricyclopentadiene PTCPD/elastomer IPN alloy material and a preparation method thereof.
背景技术Background technique
IPN，Interpenetrating Polymer Network，互穿聚合物网络结构，是两种或两种以上的共混聚合物，分子链相互贯穿，并至少一种聚合物分子链以化学键的方式交链而形成的网络结构。IPN, Interpenetrating Polymer Network, interpenetrating polymer network structure, is a network structure formed by two or more blended polymers, the molecular chains penetrate each other, and at least one polymer molecular chain is cross-linked in the form of chemical bonds. .
IPN的特点在于含有能起到“强迫相容”作用的互穿网络，不同聚合物分子相互缠结形成一个整体，不能解脱。在IPN中不同聚合物存在各自的相，亦未发生化学结合，因此，IPN不同于接枝或嵌段共聚物，亦不同于一般高分子共混物或高分子复合材料。由于在IPN内存在有永久性不能解脱的缠结，则使IPN的某些力学性能有可能超越相应的单组分聚合物。The characteristic of IPN is that it contains an interpenetrating network that can play the role of "forced compatibility", and different polymer molecules are entangled with each other to form a whole, which cannot be released. In IPN, different polymers have their own phases, and there is no chemical combination. Therefore, IPN is different from graft or block copolymers, and also different from general polymer blends or polymer composites. Due to the existence of permanent irreversible entanglements in the IPN, some mechanical properties of the IPN may surpass the corresponding one-component polymers.
聚双环戊二烯PDCPD，是由单体双环戊二烯DCPD在催化剂的作用下聚合而成的一种兼具高抗冲性和高模量的工程塑料。聚双环戊二烯PDCPD制备IPN有一定的优势，DCPD开环易位聚合时放热强且速度快，无论聚合物与DCPD是否相容，混合体系在DCPD出现分相之前由于DCPD的交联聚合固化可以形成强迫互容的IPN。Polydicyclopentadiene (PDCPD) is an engineering plastic with high impact resistance and high modulus, which is polymerized from monomer dicyclopentadiene DCPD under the action of catalyst. Polydicyclopentadiene PDCPD has certain advantages to prepare IPN. The DCPD ring-opening metathesis polymerization has strong exothermic and fast speed. No matter whether the polymer and DCPD are compatible or not, the hybrid system is due to the cross-linking polymerization of DCPD before the phase separation of DCPD occurs. Curing can form an IPN with forced mutual capacitance.
在聚双环戊二烯与弹性体制成的IPN合金材料中，随着弹性体的增加，材料的冲击强度会增加，但同时材料的热变形温度会降低。随 着社会的发展，工程塑料的应用领域也在不断的拓宽，相应对材料的性能提出了更高的要求，如何使材料同时具有较高的冲击强度和较高的热变形温度，是本领域技术人员致力于解决的难题。In the IPN alloy material made of polydicyclopentadiene and elastomer, with the increase of elastomer, the impact strength of the material will increase, but at the same time, the thermal deformation temperature of the material will decrease. With the development of society, the application fields of engineering plastics are also constantly expanding, and correspondingly higher requirements are put forward for the performance of materials. Technicians are dedicated to solving difficult problems.
发明内容SUMMARY OF THE INVENTION
本申请实施例通过提供一种聚三环戊二烯PTCPD/弹性体IPN合金材料，解决了现有技术中聚双环戊二烯IPN材料在热变形温度性能上不够的技术问题，使三环戊二烯和弹性体形成互穿网络结构，制成聚三环戊二烯/弹性体IPN合金材料，该材料同时具有较高的冲击强度和较高的热变形温度。By providing a polytricyclopentadiene PTCPD/elastomer IPN alloy material, the embodiment of the present application solves the technical problem that the polydicyclopentadiene IPN material in the prior art has insufficient thermal deformation temperature performance, and makes the tricyclopentadiene IPN material insufficient. The diene and the elastomer form an interpenetrating network structure to make a polytricyclopentadiene/elastomer IPN alloy material, which has both high impact strength and high heat distortion temperature.
本申请实施例提供了一种聚三环戊二烯PTCPD/弹性体IPN合金材料，所述IPN合金材料包括：The embodiment of the present application provides a polytricyclopentadiene PTCPD/elastomer IPN alloy material, and the IPN alloy material includes:
聚三环戊二烯树脂体系；Polytricyclopentadiene resin system;
弹性体；elastomer;
所述弹性体均匀分散于所述聚三环戊二烯PTCPD树脂体系中，所述聚三环戊二烯PTCPD树脂体系的交联网络与所述弹性体相互缠绕，形成互穿聚合物网络。The elastomer is uniformly dispersed in the polytricyclopentadiene PTCPD resin system, and the cross-linked network of the polytricyclopentadiene PTCPD resin system is intertwined with the elastomer to form an interpenetrating polymer network.
优选地，所述弹性体为热固性弹性体，所述热固性弹性体的线型分子链分穿在所述聚三环戊二烯PTCPD树脂体系的交联网络内，且互穿缠绕，形成半互穿聚合物网络。Preferably, the elastomer is a thermosetting elastomer, and the linear molecular chains of the thermosetting elastomer are penetrated in the cross-linked network of the polytricyclopentadiene PTCPD resin system, and are interpenetrated and intertwined to form a semi-interconnected through the polymer network.
优选地，所述弹性体为热塑性弹性体，所述热塑性弹性体的交联网络与所述聚三环戊二烯PTCPD树脂体系的交联网络互穿互锁，形成全互穿聚合物网络。Preferably, the elastomer is a thermoplastic elastomer, and the cross-linked network of the thermoplastic elastomer and the cross-linked network of the polytricyclopentadiene PTCPD resin system interpenetrate and interlock to form a fully interpenetrating polymer network.
进一步地，所述热固性弹性体为天然橡胶NR、异戊橡胶IR、聚丁二烯橡胶BR、丁苯橡胶SBR、丁睛橡胶NBR、氯丁橡胶CR、丁基橡胶IIR、卤化丁基橡胶、二元乙丙橡胶EPM、三元乙丙橡胶EPDM、 氯醚橡胶ECO、聚丙烯酸酯橡胶ABR、硅橡胶MVQ、氟硅橡胶FVMQ、氟橡胶FEPM、氯磺化聚乙烯CSM、氢化丁睛橡胶HNBR中的一种或几种。Further, the thermosetting elastomer is natural rubber NR, isoprene rubber IR, polybutadiene rubber BR, styrene butadiene rubber SBR, nitrile nitrile rubber NBR, neoprene rubber CR, butyl rubber IIR, halogenated butyl rubber, EPDM, EPDM, chloroether rubber ECO, polyacrylate rubber ABR, silicone rubber MVQ, fluorosilicone rubber FVMQ, fluororubber FEPM, chlorosulfonated polyethylene CSM, hydrogenated nitrile rubber HNBR one or more of them.
进一步地，所述热塑性弹性体为热塑性聚烯烃弹性体TEO、热塑性苯乙烯类弹性体TES、聚氨酯类热塑性弹性体TPU、聚酯类热塑性弹性体TPE-E、聚酰胺热塑性弹性体TPE-A、含卤素热塑性弹性体、离子型热塑性弹性体、乙烯共聚物热塑性弹性体EVA、1,2聚丁二烯热塑性弹性体、反式聚异戊二烯热塑性弹性体、熔融加工型热塑性弹性体Alcryn、热塑性硫化胶TPV中的一种或几种。Further, the thermoplastic elastomer is thermoplastic polyolefin elastomer TEO, thermoplastic styrene elastomer TES, polyurethane thermoplastic elastomer TPU, polyester thermoplastic elastomer TPE-E, polyamide thermoplastic elastomer TPE-A, Halogen-containing thermoplastic elastomer, ionic thermoplastic elastomer, ethylene copolymer thermoplastic elastomer EVA, 1,2 polybutadiene thermoplastic elastomer, trans-polyisoprene thermoplastic elastomer, melt processing thermoplastic elastomer Alcryn, One or more of thermoplastic vulcanizate TPV.
优选地，所述聚三环戊二烯PTCPD树脂体系包括以下组分制成：Preferably, the polytricyclopentadiene PTCPD resin system comprises the following components:
三环戊二烯TCPD；Tricyclopentadiene TCPD;
树脂聚合反应催化剂；resin polymerization catalyst;
所述三环戊二烯TCPD占所述聚三环戊二烯树脂体系的重量百分比大于等于50％且小于100％。The weight percentage of the tricyclopentadiene TCPD in the polytricyclopentadiene resin system is greater than or equal to 50% and less than 100%.
优选地，所述聚三环戊二烯树脂体系的组分还包括环戊二烯、双环戊二烯、四环戊二烯、五环戊二烯中的一种或几种。Preferably, the components of the polytricyclopentadiene resin system further include one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene and pentacyclopentadiene.
优选地，所述树脂聚合反应催化剂包含钨系催化剂、钼系催化剂、钌系催化剂、钛系催化剂、铼系催化剂中的一种或几种；Preferably, the resin polymerization catalyst comprises one or more of a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst;
所述树脂聚合反应催化剂的重量为所述三环戊二烯TCPD重量的0.01％～1％。The weight of the resin polymerization catalyst is 0.01% to 1% of the weight of the tricyclopentadiene TCPD.
优选地，所述IPN合金材料的组分还包括助剂和/或填料；Preferably, the components of the IPN alloy material further include additives and/or fillers;
所述助剂为抗氧化剂、紫外线吸收剂、可见光吸收剂、抗冲剂、阻燃剂、颜料、石墨烯中的一种或几种；The auxiliary agent is one or more of antioxidants, ultraviolet absorbers, visible light absorbers, impact agents, flame retardants, pigments, and graphene;
所述填料为二氧化硅、氧化铝、蒙脱土、硅石灰、钛白粉、沥青中的一种或几种。The filler is one or more of silica, alumina, montmorillonite, silica lime, titanium dioxide and asphalt.
本申请实施例还提供了一种聚三环戊二烯PTCPD/弹性体IPN合金材料的制备方法，步骤为：The embodiment of the present application also provides a preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material, the steps are:
配置液态的树脂原料，所述液态的树脂原料中三环戊二烯TCPD的重量百分比大于等于50％且小于100％；Configure a liquid resin raw material, the weight percentage of tricyclopentadiene TCPD in the liquid resin raw material is greater than or equal to 50% and less than 100%;
将弹性体原料放入液态的树脂原料中溶解，得到混合物；Dissolving the elastomer raw material into the liquid resin raw material to obtain a mixture;
将混合物配制成A、B两组分，在所述A和/或B组分中加入催化剂；The mixture is formulated into two components A and B, and a catalyst is added to the A and/or B components;
将所述A、B两组分按比例混合后，注射到闭合的模具的型腔中；加热，所述A、B两组分聚合并交联固化成型；After the two components A and B are mixed in proportion, they are injected into the cavity of the closed mold; when heated, the two components A and B are polymerized and cross-linked to solidify and form;
打开所述模具，脱模，得到聚三环戊二烯PTCPD/弹性体IPN合金材料产品。The mold is opened and demolded to obtain a polytricyclopentadiene PTCPD/elastomer IPN alloy material product.
优选地，在所述A和/或B组分中加入的催化剂包括树脂原料聚合反应催化剂和弹性体原料聚合反应催化剂。Preferably, the catalysts added to the A and/or B components include resin material polymerization catalysts and elastomer material polymerization catalysts.
进一步地，所述树脂原料聚合反应催化剂包含钨系催化剂、钼系催化剂、钌系催化剂、钛系催化剂、铼系催化剂中的一种或几种。Further, the resin raw material polymerization reaction catalyst includes one or more of a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst.
进一步地，所述弹性体原料聚合反应催化剂包括过氧化苯甲酰、过氧化二异丙苯、偶氮二异丁腈、叔丁基过氧化氢中的一种或几种。Further, the elastomer raw material polymerization catalyst includes one or more of benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, and tert-butyl hydroperoxide.
本申请实施例中提供的一个或多个技术方案，至少具有如下技术效果或优点：One or more technical solutions provided in the embodiments of this application have at least the following technical effects or advantages:
1、本申请基于三环戊二烯和弹性体，制成聚三环戊二烯/弹性体IPN合金材料，该材料同时具有较高的冲击强度和较高的热变形温度，解决了现有技术中聚双环戊二烯IPN材料热变形温度性能不足的技术问题。1. This application is based on tricyclopentadiene and an elastomer, and is made into a polytricyclopentadiene/elastomer IPN alloy material, which has both high impact strength and high thermal deformation temperature, which solves the problem of existing The technical problem of insufficient thermal deformation temperature performance of polydicyclopentadiene IPN material in technology.
2、本申请提供的聚三环戊二烯/弹性体IPN合金材料制备方法简单，操作方便，制备效率高，适于规模化工业生产及应用。2. The polytricyclopentadiene/elastomer IPN alloy material provided in this application has a simple preparation method, convenient operation and high preparation efficiency, and is suitable for large-scale industrial production and application.
3、本申请提供的聚三环戊二烯/弹性体IPN合金材料还具有耐酸、耐碱、耐盐水腐蚀、耐卤素气体腐蚀、耐疲劳等优异特性，应用范围广泛。3. The polytricyclopentadiene/elastomer IPN alloy material provided in this application also has excellent properties such as acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance, etc., and has a wide range of applications.
具体实施方式Detailed ways
本申请实施例通过提供一种聚三环戊二烯PTCPD/弹性体IPN合金材料，解决了现有技术中聚双环戊二烯IPN材料在热变形温度性能上不够的技术问题。The embodiments of the present application solve the technical problem of insufficient thermal deformation temperature performance of polydicyclopentadiene IPN materials in the prior art by providing a polytricyclopentadiene PTCPD/elastomer IPN alloy material.
本申请实施例中的技术方案为解决上述串扰的问题，总体思路如下：The technical solutions in the embodiments of the present application are to solve the above-mentioned problem of crosstalk, and the general idea is as follows:
基于聚三环戊二烯树脂体系，将三环戊二烯和弹性体在催化剂的作用下形成互穿网络结构，制成聚三环戊二烯/弹性体IPN合金材料。Based on the polytricyclopentadiene resin system, the tricyclopentadiene and the elastomer form an interpenetrating network structure under the action of a catalyst to make a polytricyclopentadiene/elastomer IPN alloy material.
所述IPN合金材料包括：The IPN alloy materials include:
聚三环戊二烯树脂体系；Polytricyclopentadiene resin system;
弹性体；elastomer;
所述弹性体均匀分散于所述聚三环戊二烯PTCPD树脂体系中，所述聚三环戊二烯PTCPD树脂体系的交联网络与所述弹性体相互缠绕，形成互穿聚合物网络。The elastomer is uniformly dispersed in the polytricyclopentadiene PTCPD resin system, and the cross-linked network of the polytricyclopentadiene PTCPD resin system is intertwined with the elastomer to form an interpenetrating polymer network.
所述弹性体也可以为热固性弹性体，此时，所述热固性弹性体的线型分子链分穿在所述聚三环戊二烯PTCPD树脂体系的交联网络内且互穿缠绕，形成半互穿聚合物网络。The elastomer can also be a thermosetting elastomer. In this case, the linear molecular chains of the thermosetting elastomer are punctured in the cross-linked network of the polytricyclopentadiene PTCPD resin system and interpenetrated and intertwined to form a semi-circular tether. Interpenetrating polymer network.
所述弹性体可以为热塑性弹性体，此时，所述热塑性弹性体的交联网络与所述聚三环戊二烯PTCPD树脂体系的交联网络互穿互锁，形成全互穿聚合物网络。The elastomer can be a thermoplastic elastomer. In this case, the cross-linked network of the thermoplastic elastomer and the cross-linked network of the polytricyclopentadiene PTCPD resin system are interpenetrating and interlocking to form a fully interpenetrating polymer network. .
所述热固性弹性体为天然橡胶NR、异戊橡胶IR、聚丁二烯橡胶BR、丁苯橡胶SBR、丁睛橡胶NBR、氯丁橡胶CR、丁基橡胶IIR、 卤化丁基橡胶、二元乙丙橡胶EPM、三元乙丙橡胶EPDM、氯醚橡胶ECO、聚丙烯酸酯橡胶ABR、硅橡胶MVQ、氟硅橡胶FVMQ、氟橡胶FEPM、氯磺化聚乙烯CSM、氢化丁睛橡胶HNBR中的一种或几种。The thermosetting elastomers are natural rubber NR, isoprene rubber IR, polybutadiene rubber BR, styrene butadiene rubber SBR, nitrile nitrile rubber NBR, neoprene CR, butyl rubber IIR, halogenated butyl rubber, diethyl ether One of propylene rubber EPM, EPDM EPDM, chloroether rubber ECO, polyacrylate rubber ABR, silicone rubber MVQ, fluorosilicone rubber FVMQ, fluorine rubber FEPM, chlorosulfonated polyethylene CSM, hydrogenated nitrile rubber HNBR species or several.
所述热塑性弹性体为热塑性聚烯烃弹性体TEO、热塑性苯乙烯类弹性体TES、聚氨酯类热塑性弹性体TPU、聚酯类热塑性弹性体TPE-E、聚酰胺热塑性弹性体TPE-A、含卤素热塑性弹性体、离子型热塑性弹性体、乙烯共聚物热塑性弹性体EVA、1,2聚丁二烯热塑性弹性体、反式聚异戊二烯热塑性弹性体、熔融加工型热塑性弹性体Alcryn、热塑性硫化胶TPV中的一种或几种。The thermoplastic elastomer is thermoplastic polyolefin elastomer TEO, thermoplastic styrene elastomer TES, polyurethane thermoplastic elastomer TPU, polyester thermoplastic elastomer TPE-E, polyamide thermoplastic elastomer TPE-A, halogen-containing thermoplastic elastomer Elastomers, ionic thermoplastic elastomers, ethylene copolymer thermoplastic elastomers EVA, 1,2 polybutadiene thermoplastic elastomers, trans-polyisoprene thermoplastic elastomers, melt processable thermoplastic elastomers Alcryn, thermoplastic vulcanizates One or more of TPVs.
所述聚三环戊二烯PTCPD树脂体系包括以下组分制成：The polytricyclopentadiene PTCPD resin system comprises the following components:
三环戊二烯TCPD；Tricyclopentadiene TCPD;
树脂聚合反应催化剂；resin polymerization catalyst;
所述三环戊二烯TCPD占所述聚三环戊二烯树脂体系的重量百分比大于等于50％且小于100％。The weight percentage of the tricyclopentadiene TCPD in the polytricyclopentadiene resin system is greater than or equal to 50% and less than 100%.
所述聚三环戊二烯树脂体系的组分还包括环戊二烯、双环戊二烯、四环戊二烯、五环戊二烯中的一种或几种。The components of the polytricyclopentadiene resin system further include one or more of cyclopentadiene, dicyclopentadiene, tetracyclopentadiene and pentacyclopentadiene.
所述树脂聚合反应催化剂包含钨系催化剂、钼系催化剂、钌系催化剂、钛系催化剂、铼系催化剂中的一种或几种；The resin polymerization catalyst comprises one or more of a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst;
所述树脂聚合反应催化剂还包含铝、镁、锡、锌、硅的金属有机化合物中的一种或几种。如三乙基铝、三丁基铝、一氯二乙基铝、三异丁基铝等。The resin polymerization catalyst also includes one or more of metal-organic compounds of aluminum, magnesium, tin, zinc, and silicon. Such as triethylaluminum, tributylaluminum, diethylaluminum monochloride, triisobutylaluminum, etc.
所述树脂聚合反应催化剂还包含醇、酚、BF 3中的一种或几种。 The resin polymerization catalyst also includes one or more of alcohol, phenol and BF 3 .
所述钨系催化剂包括钨单质、钨的氧化物、钨的卤化物(如钨的硫化物、钨的氯化物)、钨的羟基化合物、杂多钨酸中的一种或几种；The tungsten-based catalyst includes one or more of tungsten element, tungsten oxide, tungsten halide (such as tungsten sulfide, tungsten chloride), tungsten hydroxyl compound, and heteropolytungstic acid;
所述钼系催化剂包括钼单质、钼的氧化物、钼的卤化物、钼的羟基化合物、磷钼酸、钼酸铵中的一种或几种；The molybdenum-based catalyst includes one or more of molybdenum element, molybdenum oxide, molybdenum halide, molybdenum hydroxy compound, phosphomolybdic acid and ammonium molybdate;
所述钌系催化剂为金属钌、钌的化合物中的一种或几种；如Grubbs’I代、Grubbs’II代钌催化剂。The ruthenium-based catalyst is one or more of metal ruthenium and ruthenium compounds; such as Grubbs' I-generation and Grubbs' II-generation ruthenium catalysts.
所述钛系催化剂为金属钛、钛的氧化物、钛的卤化物、钛的羟基化合物中的一种或几种；The titanium-based catalyst is one or more of metal titanium, titanium oxide, titanium halide, and titanium hydroxy compound;
所述铼系催化剂为金属铼、铼的氧化物、铼的卤化物、铼的羟基化合物中的一种或几种。The rhenium-based catalyst is one or more of metal rhenium, rhenium oxide, rhenium halide, and rhenium hydroxy compound.
所述树脂聚合反应催化剂的重量为所述三环戊二烯TCPD重量的0.01％～1％。The weight of the resin polymerization catalyst is 0.01% to 1% of the weight of the tricyclopentadiene TCPD.
所述弹性体的重量为所述三环戊二烯TCPD重量的1％～70％。The weight of the elastomer is 1% to 70% of the weight of the tricyclopentadiene TCPD.
IPN合金材料的组分还包括助剂和/或填料；The components of the IPN alloy material also include additives and/or fillers;
所述助剂为抗氧化剂、紫外线吸收剂、可见光吸收剂、抗冲剂、阻燃剂、颜料、石墨烯中的一种或几种；The auxiliary agent is one or more of antioxidants, ultraviolet absorbers, visible light absorbers, impact agents, flame retardants, pigments, and graphene;
所述填料为二氧化硅、氧化铝、蒙脱土、硅石灰、钛白粉、沥青中的一种或几种。The filler is one or more of silica, alumina, montmorillonite, silica lime, titanium dioxide and asphalt.
上述的聚三环戊二烯PTCPD/弹性体IPN合金材料的制备方法，步骤为：The preparation method of above-mentioned polytricyclopentadiene PTCPD/elastomer IPN alloy material, the steps are:
配置液态的树脂原料，所述液态的树脂原料中三环戊二烯TCPD的重量百分比大于等于50％且小于100％；Configure a liquid resin raw material, the weight percentage of tricyclopentadiene TCPD in the liquid resin raw material is greater than or equal to 50% and less than 100%;
将弹性体原料放入液态的树脂原料中溶解，得到混合物；Dissolving the elastomer raw material into the liquid resin raw material to obtain a mixture;
将混合物配制成A、B两组分，在所述A和/或B组分中加入催化剂；The mixture is formulated into two components A and B, and a catalyst is added to the A and/or B components;
将所述A、B两组分按比例混合后，注射到闭合的模具的型腔中；加热，所述A、B两组分聚合并交联固化成型；After the two components A and B are mixed in proportion, they are injected into the cavity of the closed mold; when heated, the two components A and B are polymerized and cross-linked to solidify and form;
打开所述模具，脱模，得到聚三环戊二烯PTCPD/弹性体IPN合金材料产品。The mold is opened and demolded to obtain a polytricyclopentadiene PTCPD/elastomer IPN alloy material product.
当弹性体不发生聚合反应时，在所述A和/或B组分中加入的催化剂仅包括树脂原料聚合反应催化剂。When the elastomer does not undergo polymerization, the catalysts added in the A and/or B components only include resin raw material polymerization catalysts.
在弹性体发生聚合反应时，在所述A和/或B组分中加入的催化剂包括树脂原料聚合反应催化剂和弹性体原料聚合反应催化剂。When the elastomer undergoes a polymerization reaction, the catalysts added to the A and/or B components include a resin raw material polymerization catalyst and an elastomer raw material polymerization catalyst.
所述树脂原料聚合反应催化剂包含钨系催化剂、钼系催化剂、钌系催化剂、钛系催化剂、铼系催化剂中的一种或几种。The resin raw material polymerization reaction catalyst includes one or more of tungsten-based catalysts, molybdenum-based catalysts, ruthenium-based catalysts, titanium-based catalysts, and rhenium-based catalysts.
所述弹性体原料聚合反应催化剂包括过氧化苯甲酰、过氧化二异丙苯、偶氮二异丁腈、叔丁基过氧化氢中的一种或几种。The elastomer raw material polymerization catalyst includes one or more of benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, and tert-butyl hydroperoxide.
为了更好的理解上述技术方案，下面将结合说明书附图以及具体的实施方式对上述技术方案进行详细的说明。In order to better understand the above technical solutions, the above technical solutions will be described in detail below with reference to the accompanying drawings and specific embodiments.
实施例一Example 1
本实施例中，聚三环戊二烯PTCPD/弹性体IPN合金材料由以下重量百分比的组分组成：In this embodiment, the polytricyclopentadiene PTCPD/elastomer IPN alloy material is composed of the following components by weight:
三环戊二烯TCPD，98％；Tricyclopentadiene TCPD, 98%;
双环戊二烯DCPD，0.2％；Dicyclopentadiene DCPD, 0.2%;
丁基橡胶，1％。Butyl rubber, 1%.
钌卡宾催化剂，0.8％；Ruthenium carbene catalyst, 0.8%;
本实施例中，聚三环戊二烯PTCPD/弹性体IPN合金材料的制备方法，步骤为：In the present embodiment, the preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material, the steps are:
步骤S1：配置液态的三环戊二烯TCPD和双环戊二烯DCPD树脂原料；Step S1: configure liquid tricyclopentadiene TCPD and dicyclopentadiene DCPD resin raw materials;
步骤S2：将丁基橡胶放入液态树脂原料中溶解，在75℃下，搅 拌6小时，得到混合物；Step S2: dissolving the butyl rubber into the liquid resin raw material, and stirring at 75°C for 6 hours to obtain a mixture;
步骤S3：将混合物配制成A、B两组分，在B组分中加入钌卡宾催化剂；Step S3: the mixture is prepared into two components A and B, and a ruthenium carbene catalyst is added to the B component;
步骤S4：将A、B两组分混合后，注射到闭合的模具的型腔中；加热至80℃，A、B两组分迅速聚合并交联固化成型；Step S4: After mixing the two components A and B, they are injected into the cavity of the closed mold; heated to 80° C., the two components A and B are rapidly polymerized and cross-linked to solidify and form;
步骤S5：打开所述模具，脱模，得到聚三环戊二烯PTCPD/SBS IPN合金材料产品。Step S5: opening the mold, demoulding to obtain a polytricyclopentadiene PTCPD/SBS IPN alloy material product.
本实施例制备的聚三环戊二烯PTCPD/丁基橡胶IPN合金材料中，丁基橡胶的分子链在聚三环戊二烯PTCPD交联网络形成的过程中与其产生高度缠结，形成了半互穿聚合物网络。In the polytricyclopentadiene PTCPD/butyl rubber IPN alloy material prepared in this example, the molecular chain of the butyl rubber is highly entangled with the polytricyclopentadiene PTCPD cross-linked network during the formation of the cross-linked network, forming a Semi-interpenetrating polymer network.
实施例二Embodiment 2
本实施例中，聚三环戊二烯PTCPD/弹性体IPN合金材料由以下重量百分比的组分组成：In this embodiment, the polytricyclopentadiene PTCPD/elastomer IPN alloy material is composed of the following components by weight:
三环戊二烯TCPD，83％；Tricyclopentadiene TCPD, 83%;
双环戊二烯，2.7％；Dicyclopentadiene, 2.7%;
苯乙烯，13.38％；Styrene, 13.38%;
二乙烯苯，0.16％；Divinylbenzene, 0.16%;
过氧化苯甲酰，0.16％；Benzoyl peroxide, 0.16%;
CpTiCl 2，0.15％； CpTiCl 2 , 0.15%;
CH 3MgI，0.43％。 CH3MgI , 0.43%.
本实施例中，聚三环戊二烯PTCPD/弹性体IPN合金材料的制备方法，步骤为：In the present embodiment, the preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material, the steps are:
步骤S1：配置液态的三环戊二烯TCPD和双环戊二烯DCPD树脂原料；Step S1: configure liquid tricyclopentadiene TCPD and dicyclopentadiene DCPD resin raw materials;
步骤S2：将苯乙烯和二乙烯苯放入液态树脂原料中溶解，在65℃下，搅拌5小时，得到均匀的混合物；Step S2: dissolving styrene and divinylbenzene in the liquid resin raw material, and stirring at 65° C. for 5 hours to obtain a uniform mixture;
步骤S3：在氮气保护下，将混合物配制成A、B两组分，在A组分中加入CpTiCl 2和过氧化苯甲酰，在B组分中加入CH 3MgI； Step S3: under nitrogen protection, the mixture is prepared into two components A and B, CpTiCl 2 and benzoyl peroxide are added to the A component, and CH 3 MgI is added to the B component;
步骤S4：将A、B两组分混合后，注射到闭合的模具的型腔中；加热至75℃，A、B两组分迅速聚合并交联固化成型；Step S4: After mixing the two components A and B, they are injected into the cavity of the closed mold; heated to 75° C., the two components A and B are rapidly polymerized and cross-linked to solidify and form;
步骤S5：打开所述模具，脱模，得到聚三环戊二烯PTCPD/聚苯乙烯IPN合金材料产品。Step S5 : opening the mold and demoulding to obtain a polytricyclopentadiene PTCPD/polystyrene IPN alloy material product.
本实施例制备的聚三环戊二烯PTCPD/聚苯乙烯IPN合金材料中，三环戊二烯及少量双环戊二烯在CpTiCl 2、CH 3MgI的催化作用下形成聚三环戊二烯交联网络。苯乙烯和二乙烯苯在过氧化苯甲酰的催化作用下形成聚苯乙烯交联网络。聚三环戊二烯PTCPD交联网络和聚苯乙烯交联网络互穿互锁，形成全互穿聚合物网络。 In the polytricyclopentadiene PTCPD/polystyrene IPN alloy material prepared in this example, tricyclopentadiene and a small amount of dicyclopentadiene form polytricyclopentadiene under the catalysis of CpTiCl 2 and CH 3 MgI Cross-linked network. Styrene and divinylbenzene form a polystyrene cross-linked network under the catalysis of benzoyl peroxide. The polytricyclopentadiene PTCPD cross-linked network and the polystyrene cross-linked network interpenetrate and interlock to form a fully interpenetrating polymer network.
实施例三Embodiment 3
本实施例中，聚三环戊二烯PTCPD/弹性体IPN合金材料由以下重量百分比的组分组成：In this embodiment, the polytricyclopentadiene PTCPD/elastomer IPN alloy material is composed of the following components by weight:
三环戊二烯TCPD，70％；Tricyclopentadiene TCPD, 70%;
四环戊二烯，2.65％；Tetracyclopentadiene, 2.65%;
2,4,6-三溴苯乙烯，20％；2,4,6-Tribromostyrene, 20%;
二乙烯苯，3.9％；Divinylbenzene, 3.9%;
偶氮二异丁腈，3.1％；Azobisisobutyronitrile, 3.1%;
ReCls，重量百分比0.085％；ReCls, 0.085% by weight;
(CH 3) 4Sn，重量百分比0.265％。 (CH 3 ) 4 Sn, 0.265% by weight.
本实施例中，聚三环戊二烯PTCPD/弹性体IPN合金材料的制备方法，步骤为：In the present embodiment, the preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material, the steps are:
步骤S1：配置液态的三环戊二烯TCPD和四环戊二烯DCPD树脂原料；Step S1: configure liquid tricyclopentadiene TCPD and tetracyclopentadiene DCPD resin raw materials;
步骤S2：将2,4,6-三溴苯乙烯和二乙烯苯放入液态树脂原料中溶解，在70℃下，搅拌6小时，得到均匀的混合物；Step S2: put 2,4,6-tribromostyrene and divinylbenzene into the liquid resin raw material to dissolve, and stir at 70°C for 6 hours to obtain a uniform mixture;
步骤S3：在氮气保护下，将混合物配制成A、B两组分，在A组分中加入ReCls和偶氮二异丁腈，在B组分中加入(CH 3) 4Sn； Step S3: under nitrogen protection, the mixture is prepared into two components A and B, ReCls and azobisisobutyronitrile are added to the A component, and (CH 3 ) 4 Sn is added to the B component;
步骤S4：将A、B两组分混合后，注射到闭合的模具的型腔中；加热至70℃，A、B两组分迅速聚合并交联固化成型；Step S4: After mixing the two components A and B, they are injected into the cavity of the closed mold; heated to 70° C., the two components A and B are rapidly polymerized and cross-linked to solidify and form;
步骤S5：打开所述模具，脱模，得到聚三环戊二烯PTCPD/聚2,4,6-三溴苯乙烯IPN合金材料产品。Step S5 : opening the mold and demoulding to obtain a polytricyclopentadiene PTCPD/poly2,4,6-tribromostyrene IPN alloy material product.
本实施例制备的聚三环戊二烯PTCPD/聚2,4,6-三溴苯乙烯IPN合金材料中，三环戊二烯及少量四环戊二烯在ReCls、(CH 3) 4Sn的催化作用下形成聚三环戊二烯交联网络。2,4,6-三溴苯乙烯和二乙烯苯在偶氮二异丁腈的催化作用下形成聚2,4,6-三溴苯乙烯交联网络。聚三环戊二烯PTCPD交联网络和聚2,4,6-三溴苯乙烯交联网互穿互锁，形成全互穿聚合物网络。同时，聚2,4,6-三溴苯乙烯的加入，使得IPN合金材料的阻燃性明显提高。 In the polytricyclopentadiene PTCPD/poly2,4,6-tribromostyrene IPN alloy material prepared in this example, tricyclopentadiene and a small amount of tetracyclopentadiene are in ReCls, (CH 3 ) 4 Sn The formation of polytricyclopentadiene cross-linked network under the catalysis. 2,4,6-Tribromostyrene and divinylbenzene were catalyzed by azobisisobutyronitrile to form a poly-2,4,6-tribromostyrene cross-linked network. The polytricyclopentadiene PTCPD cross-linked network and the poly-2,4,6-tribromostyrene cross-linked network interpenetrate and interlock to form a fully interpenetrating polymer network. At the same time, the addition of poly-2,4,6-tribromostyrene makes the flame retardancy of the IPN alloy material significantly improved.
实施例四Embodiment 4
本实施例中，聚三环戊二烯PTCPD/弹性体IPN合金材料由以下重量百分比的组分组成：In this embodiment, the polytricyclopentadiene PTCPD/elastomer IPN alloy material is composed of the following components by weight:
三环戊二烯，重量百分比50％；Tricyclopentadiene, 50% by weight;
双环戊二烯，重量百分比14.49％；Dicyclopentadiene, 14.49% by weight;
丁睛橡胶，重量百分比35％；Butadiene rubber, 35% by weight;
WCl 6，重量百分比0.127％； WCl 6 , 0.127% by weight;
AlEt 2Cl，重量百分比0.382％； AlEt 2 Cl, 0.382% by weight;
C 6H 2Cl 4O，重量百分比0.001％； C 6 H 2 Cl 4 O, 0.001% by weight;
本实施例中，聚三环戊二烯PTCPD/弹性体IPN合金材料的制备方法，步骤为：In the present embodiment, the preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material, the steps are:
步骤S1：配置液态的三环戊二烯TCPD和双环戊二烯DCPD树脂原料；Step S1: configure liquid tricyclopentadiene TCPD and dicyclopentadiene DCPD resin raw materials;
步骤S2：将丁睛橡胶放入液态树脂原料中溶解，在70℃下，搅拌7小时，得到混合物；Step S2: dissolving the nitrile-butadiene rubber in the liquid resin raw material, and stirring at 70° C. for 7 hours to obtain a mixture;
步骤S3：将混合物配制成A、B两组分，在A组分中加入WCl 6、C 6H 2Cl 4O；在B组分中加入AlEt 2Cl； Step S3: preparing the mixture into two components A and B, adding WCl 6 and C 6 H 2 Cl 4 O to the A component; adding AlEt 2 Cl to the B component;
步骤S4：将A、B两组分混合后，注射到闭合的模具的型腔中；加热至80℃，A、B两组分迅速聚合并交联固化成型；Step S4: After mixing the two components A and B, they are injected into the cavity of the closed mold; heated to 80° C., the two components A and B are rapidly polymerized and cross-linked to solidify and form;
步骤S5：打开所述模具，脱模，得到聚三环戊二烯PTCPD/丁睛橡胶IPN合金材料产品。Step S5: opening the mold, demoulding, and obtaining a polytricyclopentadiene PTCPD/butadiene nitrile rubber IPN alloy material product.
本实施例制备的聚三环戊二烯PTCPD/SBS IPN合金材料中，丁睛橡胶分子链在聚三环戊二烯PTCPD交联网络形成的过程中与其产生高度缠结，形成了半互穿聚合物网络。In the polytricyclopentadiene PTCPD/SBS IPN alloy material prepared in this example, the butadiene rubber molecular chain is highly entangled with the polytricyclopentadiene PTCPD cross-linked network during the formation of the cross-linked network, forming a semi-interpenetrating polymer network.
性能测试Performance Testing
针对上述各实施例得到的聚三环戊二烯PTCPD/弹性体IPN合金材料产品，对其性能进行测试，测试部分选取平面中间部分，得到如下结果：For the polytricyclopentadiene PTCPD/elastomer IPN alloy material product obtained for the above-mentioned embodiments, its performance is tested, and the test part selects the plane middle part to obtain the following results:
Figure PCTCN2021081899-appb-000001
Figure PCTCN2021081899-appb-000001
Figure PCTCN2021081899-appb-000002
Figure PCTCN2021081899-appb-000002
由上表可知，随着三环戊二烯TCPD的含量增加，合金材料的热变形温度升高，冲击强度降低。It can be seen from the above table that with the increase of the content of tricyclopentadiene TCPD, the thermal deformation temperature of the alloy material increases, and the impact strength decreases.
在弹性体材料及比例相同的情况下，利用双环戊二烯制备聚双环戊二烯/弹性体IPN材料，作为对比实施例一～对比实施例四。对对比实施例一～对比实施例四得到的聚双环戊二烯/弹性体IPN材料，进行测试，得到如下结果。Under the condition of the same elastomer material and proportion, polydicyclopentadiene/elastomer IPN material was prepared by using dicyclopentadiene, which was used as Comparative Example 1 to Comparative Example 4. The polydicyclopentadiene/elastomer IPN materials obtained in Comparative Examples 1 to 4 were tested, and the following results were obtained.
Figure PCTCN2021081899-appb-000003
Figure PCTCN2021081899-appb-000003
由上表数据可知，本申请制备的聚三环戊二烯PTCPD/弹性体IPN合金材料相比聚双环戊二烯/弹性体IPN材料，在保证其冲击强度的基础上，提高了其热变形温度，使合金材料具有更优异的综合性能，满足特定领域对材料的高性能要求。As can be seen from the data in the above table, the polytricyclopentadiene PTCPD/elastomer IPN alloy material prepared in this application has improved its thermal deformation on the basis of ensuring its impact strength compared with the polydicyclopentadiene/elastomer IPN material. The temperature makes the alloy material have more excellent comprehensive properties and meet the high performance requirements of materials in specific fields.
此外，本申请提供的聚三环戊二烯/弹性体IPN合金材料还具有耐酸、耐碱、耐盐水腐蚀、耐卤素气体腐蚀、耐疲劳等优异特性，应用范围广泛。In addition, the polytricyclopentadiene/elastomer IPN alloy material provided in the present application also has excellent properties such as acid resistance, alkali resistance, salt water corrosion resistance, halogen gas corrosion resistance, fatigue resistance, etc., and has a wide range of applications.
以上所述，仅为本申请的较佳实施例，并非对本申请任何形式上 和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本申请方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本申请的保护范围。凡熟悉本专业的技术人员，在不脱离本申请的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本申请的等效实施例；同时，凡依据本申请的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本申请的技术方案的范围内。The above are only preferred embodiments of the present application, and are not intended to limit the present application in any form or substance. Several improvements and additions can be made, and these improvements and additions should also be regarded as the protection scope of the present application. For those skilled in the art, without departing from the spirit and scope of the present application, the equivalent changes that can be made by using the technical content disclosed above are some changes, modifications and evolutions of the present application. Equivalent embodiments; at the same time, any modification, modification and evolution of any equivalent changes made to the above embodiments according to the essential technology of the present application still fall within the scope of the technical solutions of the present application.

Claims (10)

  1. 一种聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述IPN合金材料包括：A polytricyclopentadiene PTCPD/elastomer IPN alloy material, characterized in that the IPN alloy material comprises:
    聚三环戊二烯树脂体系；Polytricyclopentadiene resin system;
    弹性体；elastomer;
    所述弹性体均匀分散于所述聚三环戊二烯PTCPD树脂体系中，所述聚三环戊二烯PTCPD树脂体系的交联网络与所述弹性体相互缠绕，形成互穿聚合物网络。The elastomer is uniformly dispersed in the polytricyclopentadiene PTCPD resin system, and the cross-linked network of the polytricyclopentadiene PTCPD resin system is intertwined with the elastomer to form an interpenetrating polymer network.
  2. 如权利要求1所述的聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述弹性体为热固性弹性体，所述热固性弹性体的线型分子链分穿在所述聚三环戊二烯PTCPD树脂体系的交联网络内，且互穿缠绕，形成半互穿聚合物网络。The polytricyclopentadiene PTCPD/elastomer IPN alloy material according to claim 1, wherein the elastomer is a thermosetting elastomer, and the linear molecular chains of the thermosetting elastomer penetrate through the polymer In the cross-linked network of the tricyclopentadiene PTCPD resin system, and interpenetrating entanglement, a semi-interpenetrating polymer network is formed.
  3. 如权利要求1所述的聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述弹性体为热塑性弹性体，所述热塑性弹性体的交联网络与所述聚三环戊二烯PTCPD树脂体系的交联网络互穿互锁，形成全互穿聚合物网络。The polytricyclopentadiene PTCPD/elastomer IPN alloy material according to claim 1, wherein the elastomer is a thermoplastic elastomer, and the cross-linked network of the thermoplastic elastomer and the polytricyclopenta The cross-linked network of the diene PTCPD resin system interpenetrates and interlocks to form a fully interpenetrating polymer network.
  4. 如权利要求2所述的聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述热固性弹性体为天然橡胶NR、异戊橡胶IR、聚丁二烯橡胶BR、丁苯橡胶SBR、丁睛橡胶NBR、氯丁橡胶CR、丁基橡胶IIR、卤化丁基橡胶、二元乙丙橡胶EPM、三元乙丙橡胶EPDM、氯醚橡胶ECO、聚丙烯酸酯橡胶ABR、硅橡胶MVQ、氟硅橡胶FVMQ、氟橡胶FEPM、氯磺化聚乙烯CSM、氢化丁睛橡胶HNBR中的一种或几种。The polytricyclopentadiene PTCPD/elastomer IPN alloy material according to claim 2, wherein the thermosetting elastomer is natural rubber NR, isoprene rubber IR, polybutadiene rubber BR, styrene-butadiene rubber SBR, nitrile rubber NBR, neoprene CR, butyl rubber IIR, halogenated butyl rubber, ethylene propylene diene rubber EPM, ethylene propylene diene propylene diene rubber EPDM, chloroether rubber ECO, polyacrylate rubber ABR, silicone rubber MVQ , One or more of fluorosilicone rubber FVMQ, fluorine rubber FEPM, chlorosulfonated polyethylene CSM, hydrogenated nitrile butadiene rubber HNBR.
  5. 如权利要求3所述的聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述热塑性弹性体为热塑性聚烯烃弹性体TEO、 热塑性苯乙烯类弹性体TES、聚氨酯类热塑性弹性体TPU、聚酯类热塑性弹性体TPE-E、聚酰胺热塑性弹性体TPE-A、含卤素热塑性弹性体、离子型热塑性弹性体、乙烯共聚物热塑性弹性体EVA、1,2聚丁二烯热塑性弹性体、反式聚异戊二烯热塑性弹性体、熔融加工型热塑性弹性体Alcryn、热塑性硫化胶TPV中的一种或几种。The polytricyclopentadiene PTCPD/elastomer IPN alloy material according to claim 3, wherein the thermoplastic elastomer is thermoplastic polyolefin elastomer TEO, thermoplastic styrene elastomer TES, polyurethane thermoplastic elastomer Body TPU, polyester thermoplastic elastomer TPE-E, polyamide thermoplastic elastomer TPE-A, halogen-containing thermoplastic elastomer, ionic thermoplastic elastomer, ethylene copolymer thermoplastic elastomer EVA, 1,2 polybutadiene thermoplastic One or more of elastomer, trans-polyisoprene thermoplastic elastomer, melt-processable thermoplastic elastomer Alcryn, and thermoplastic vulcanizate TPV.
  6. 如权利要求1所述的聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述聚三环戊二烯PTCPD树脂体系包括以下组分制成：The polytricyclopentadiene PTCPD/elastomer IPN alloy material according to claim 1, wherein the polytricyclopentadiene PTCPD resin system comprises the following components:
    三环戊二烯TCPD；Tricyclopentadiene TCPD;
    树脂聚合反应催化剂；resin polymerization catalyst;
    所述三环戊二烯TCPD占所述聚三环戊二烯树脂体系的重量百分比大于等于50％且小于100％。The weight percentage of the tricyclopentadiene TCPD in the polytricyclopentadiene resin system is greater than or equal to 50% and less than 100%.
  7. 如权利要求6所述的聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述聚三环戊二烯树脂体系的组分还包括环戊二烯、双环戊二烯、四环戊二烯、五环戊二烯中的一种或几种。The polytricyclopentadiene PTCPD/elastomer IPN alloy material according to claim 6, wherein the components of the polytricyclopentadiene resin system further comprise cyclopentadiene, dicyclopentadiene, One or more of tetracyclopentadiene and pentacyclopentadiene.
  8. 如权利要求6所述的聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述树脂聚合反应催化剂包含钨系催化剂、钼系催化剂、钌系催化剂、钛系催化剂、铼系催化剂中的一种或几种；The polytricyclopentadiene PTCPD/elastomer IPN alloy material according to claim 6, wherein the resin polymerization catalyst comprises a tungsten-based catalyst, a molybdenum-based catalyst, a ruthenium-based catalyst, a titanium-based catalyst, and a rhenium-based catalyst One or more of the catalysts;
    所述树脂聚合反应催化剂的重量为所述三环戊二烯TCPD重量的0.01％～1％。The weight of the resin polymerization catalyst is 0.01% to 1% of the weight of the tricyclopentadiene TCPD.
  9. 如权利要求1所述的聚三环戊二烯PTCPD/弹性体IPN合金材料，其特征在于，所述IPN合金材料的组分还包括助剂和/或填料；The polytricyclopentadiene PTCPD/elastomer IPN alloy material according to claim 1, wherein the components of the IPN alloy material further include additives and/or fillers;
    所述助剂为抗氧化剂、紫外线吸收剂、可见光吸收剂、抗冲剂、阻燃剂、颜料、石墨烯中的一种或几种；The auxiliary agent is one or more of antioxidants, ultraviolet absorbers, visible light absorbers, impact agents, flame retardants, pigments, and graphene;
    所述填料为二氧化硅、氧化铝、蒙脱土、硅石灰、钛白粉、沥青 中的一种或几种。The filler is one or more of silica, alumina, montmorillonite, silica lime, titanium dioxide and asphalt.
  10. 一种聚三环戊二烯PTCPD/弹性体IPN合金材料的制备方法，其特征在于，步骤为：A preparation method of polytricyclopentadiene PTCPD/elastomer IPN alloy material, characterized in that the steps are:
    配置液态的树脂原料，所述液态的树脂原料中三环戊二烯TCPD的重量百分比大于等于50％且小于100％；Configure a liquid resin raw material, the weight percentage of tricyclopentadiene TCPD in the liquid resin raw material is greater than or equal to 50% and less than 100%;
    将弹性体原料放入液态的树脂原料中溶解，得到混合物；Dissolving the elastomer raw material into the liquid resin raw material to obtain a mixture;
    将混合物配制成A、B两组分，在所述A和/或B组分中加入催化剂；The mixture is formulated into two components A and B, and a catalyst is added to the A and/or B components;
    将所述A、B两组分按比例混合后，注射到闭合的模具的型腔中；加热，所述A、B两组分聚合并交联固化成型；After the two components A and B are mixed in proportion, they are injected into the cavity of the closed mold; when heated, the two components A and B are polymerized and cross-linked to solidify and form;
    打开所述模具，脱模，得到聚三环戊二烯PTCPD/弹性体IPN合金材料产品。The mold is opened and demolded to obtain a polytricyclopentadiene PTCPD/elastomer IPN alloy material product.
PCT/CN2021/081899 2021-03-12 2021-03-19 Polytricyclopentadiene (ptcpd)/elastomer ipn alloy material and preparation method therefor WO2022188202A1 (en)

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