WO2001014464A1 - Thermoplastic elastomer produced from waste rubber powder/plastic and the article made therefrom - Google Patents

Thermoplastic elastomer produced from waste rubber powder/plastic and the article made therefrom Download PDF

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Publication number
WO2001014464A1
WO2001014464A1 PCT/CN1999/000125 CN9900125W WO0114464A1 WO 2001014464 A1 WO2001014464 A1 WO 2001014464A1 CN 9900125 W CN9900125 W CN 9900125W WO 0114464 A1 WO0114464 A1 WO 0114464A1
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WO
WIPO (PCT)
Prior art keywords
rubber powder
thermoplastic elastomer
plastic
parts
waste rubber
Prior art date
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PCT/CN1999/000125
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French (fr)
Chinese (zh)
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WO2001014464A8 (en
Inventor
Yuxing Feng
Liqun Zhang
Yujun Zhu
Li Liu
Ming Tian
Original Assignee
Liu, Guixing
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Application filed by Liu, Guixing filed Critical Liu, Guixing
Priority to AU54059/99A priority Critical patent/AU5405999A/en
Priority to PCT/CN1999/000125 priority patent/WO2001014464A1/en
Publication of WO2001014464A1 publication Critical patent/WO2001014464A1/en
Publication of WO2001014464A8 publication Critical patent/WO2001014464A8/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a thermoplastic elastomer prepared by waste rubber powder / plastic reaction processing, and a shaped article prepared therefrom. More specifically, the present invention relates to waste rubber powder as a main raw material, through modification of the rubber powder, and adding a specific compatibilizing agent, using a reactive processing technology to prepare waste rubber powder / plastic thermoplastic elastomer, these materials have excellent Comprehensive physical and mechanical properties; and molded articles made from the thermoplastic elastomer through traditional plastic molding techniques, such as: sheets such as waterproof coils, pipes, rods, and various types can be produced by calendering, injection, and extrusion methods Injection products.
  • OLIVEIRA DA CUNHA LIMA, Luiz, Corlos discloses a method for preparing thermoplastic rubber, using waste rubber as a raw material, and using physical, chemical or physical and chemical methods to deboss the rubber and turn it into a uniform
  • the conventional batch is recycled rubber, and then the recycled rubber master batch is mixed with a thermoplastic resin to obtain a thermoplastic rubber for industrial use.
  • the desulfurization process that must be used in the method for producing recycled rubber takes a long time, consumes large energy, and generates pollution due to the use of solvents.
  • thermoplastic elastomer by using waste rubber powder instead of reclaimed rubber and blending with thermoplastic is another method of recycling and utilizing waste rubber. This method has the advantages of simple process, low energy consumption, and no environmental pollution.
  • EP 0649871 A2 Johnson, Lane D. discloses a mixture of polyolefin and rubber powder, which includes a functionalized olefin copolymer as a compatibilizer to improve the interfacial compatibility of rubber powder and polyolefin.
  • the functionalized olefin copolymer includes SEBS, polyethylene / acrylic copolymer, SEBS / maleic anhydride copolymer, and the like. Its role is mainly to improve plastics and rubber The physical compatibility between the powders may cause a small amount of chemical bonding with the rubber powder during processing due to high temperature and shear.
  • this functionalized olefin copolymer as a compatibilizer can improve the interfacial bonding between plastic and rubber powder, the effect is not ideal.
  • the physical properties of the blend of waste rubber powder and plastic prepared by this method The mechanical properties, especially the comprehensive physical and mechanical properties such as hardness, tensile strength, and elongation at break, are still unsatisfactory and need to be further improved, and the resins in the plastic system in this document can only be selected from polyolefin resins.
  • the purpose of the present invention is to obtain a thermoplastic elastomer with excellent comprehensive physical and mechanical properties from a waste rubber powder / plastic system, in particular to improve the utilization rate of the rubber powder, reduce the hardness of the thermoplastic elastomer, and increase the elongation at break and tensile strength. Expand the types of plastic resins in the building powder / plastic system, so as to diversify the types of building powder / plastic thermoplastic elastomers.
  • thermoplastic elastomer prepared by reaction processing of a complex comprising the following components:
  • plastic which is selected from one or more of polyolefin, ethylene / vinyl acetate copolymer (EVA), and polystyrene (PS),
  • Reactive compatibilizer which is a copolymer containing a hard segment region and a soft segment region in the molecular chain.
  • the hard segment region is composed of one or more of ethylene, propylene, butene, isobutylene, styrene and other monomers.
  • the soft segment area is formed by molecular chains of natural rubber, butadiene rubber, butyl rubber, butyl rubber, EPDM, etc., or polymerized by monomers such as isoprene and butadiene
  • Cross-linking system including cross-linking agent, cross-linking accelerator, cross-linking active agent, etc.
  • the preparation method includes the first step of modifying the waste rubber powder and one or more modifiers in an open mill, an internal mixer or a twin-screw extruder. Operating conditions: temperature 10-1001 :, time 3 -15 minutes; in the second step, add the modified waste rubber powder and plastic, reactive compatibilizer, cross-linking system, optional antioxidant, etc. to the open mill, internal mixer or twin screw extruder for reaction Processing, processing temperature 100'C ⁇ 200 "C, time 3-15 minutes.
  • the weight composition of each component in the complex is:
  • Waste rubber powder, plastic and compatibilizer 100 parts
  • Rubber powder modifier 0.1 ⁇ 5 parts by weight
  • Cross-linking system 0.1 to 3 parts by weight of cross-linking agent, 0.1 to 5 parts by weight of cross-linking accelerator, and 0.1 to 8 parts by weight of cross-linking active agent;
  • Optional antioxidant 0.5-3 parts by weight.
  • the complex may further include 0 to 10 parts by weight of a softening plasticizer.
  • the present invention also provides a molded article prepared from the thermoplastic elastomer by a conventional molding processing method.
  • reaction processing refers to the process of vulcanization of the rubber-plastic blend system while blending at a certain temperature, which significantly improves the mechanical properties of the combined body due to cross-linking.
  • the waste rubber powder used in the present invention is directly pulverized from waste rubber. It can be tire waste rubber powder, footwear waste rubber powder, miscellaneous waste rubber powder, etc. It is preferable to use tire waste rubber powder. Its particle size is less than 10 mesh, and the optimal particle size range is 30 mesh-80 mesh.
  • the plastic raw material used in the present invention may be either an unused resin or a waste plastic which is crushed and recovered. These include polyolefin resins, polystyrene or EVA. Different plastic raw materials are used because of their different structural characteristics, so the structure and performance characteristics of waste rubber powder / plastic thermoplastic elastomer prepared by different plastic systems are also necessarily different. Thereby, the variety of Xiajiao powder / plastic thermoplastic elastomer can be diversified.
  • the rubber powder modifier and the reactive compatibilizer are extremely important.
  • the base material waste rubber powder and plastic are selected, in order to prepare waste rubber powder / plastic thermoplastic elastomer with excellent comprehensive properties, it is necessary to ensure that the waste rubber powder and plastic have a good interface.
  • a large number of chemical bonds must be formed between the waste rubber powder and the plastic to ensure sufficient interface strength; on the other hand, sufficient thickness of the interface layer must be ensured to cushion the stress concentration of the material when it is stressed effect.
  • the waste rubber powder made from the crushed waste rubber has insufficient damage to the cross-linked network structure on the surface, is still dense, and has poor chain movement ability, which is not conducive to the movement of the rubber powder and plastic molecular chains to form a sufficient interface layer thickness. And there are fewer reactive points on the surface of the waste rubber powder, which does not Conducive to chemical bonding with the compatibilizer during processing to ensure sufficient interface strength. To this end, the waste rubber powder is subjected to activation modification treatment.
  • the rubber molecular chain is cut by the strong shearing action of the equipment; on the other hand, the modifiers are used. Chemical action breaks the molecular chain, further increasing the looseness of the rubber powder and generating a large number of reactive spots of the waste rubber powder. After such pretreatment, it is possible for the waste rubber powder to have a good interface with the plastic during the reaction process. Any modifier and modification method capable of causing reactive rubber spots to generate waste rubber powder are applicable to the present invention.
  • the rubber powder modifier used in the present invention is a kind of material capable of breaking the S-S-bond of waste rubber, including hexamethylenetetramine and resorcinol or their derivatives, thiols or thiophenols.
  • Classes such as xylylthiophenol, trichlorothiophenol, etc., or rubber powder modifier De-Link from DE-LINK Technologies China Co., whose main component is thioxo Carbamates such as zinc dimethyldithiocarbamate and 2-mercaptobenzothiazole or derivatives thereof such as zinc mercaptobenzothiazole.
  • De-Link also contains certain sulfur or sulfur-containing compounds.
  • modifiers are added together with the Xiajiao powder to equipment with high shear forces such as mixers, open mills or screw extruders.
  • the rubber molecular chain is cut by the strong shearing action of the equipment; on the other hand, the rubber molecular chain is cut by the chemical action of the modifier to improve the movement ability of the molecular chain on the surface of the rubber powder; Reactive points, these points can be re-crosslinked with cross-linking agents such as sulfur, sulfur compounds, and phenolic resins.
  • the waste rubber powder undergoes such a modification treatment to make it possible to produce a good interface with the matrix plastic.
  • thermoplastic elastomer or elastomer material that meets the above conditions can be used as the compatibilizer required for the present invention.
  • the compatibilizer used in the present invention is a copolymer.
  • the molecular chain of the copolymer contains a hard segment region and a soft segment region.
  • the hard segment region is polymerized from monomers such as ethylene, propylene, and styrene.
  • the soft segment region is made of natural materials. Formed by molecular chains of rubber, butadiene rubber, butyl rubber, butyl rubber, ethylene propylene rubber, etc .; or polymerized from monomers such as isoprene and butadiene, which must be contained in the soft section It can be crosslinked with sulfur or sulfide-containing, phenolic resin and other cross-linking agents.
  • the molecular chain of the soft segment must be a certain length, and the number of C atoms must be greater than 50.
  • compatibilizers include: PS-g-natural rubber, PP-g-EPDM, PE-g-butyl rubber, SBS, SIS, etc. Adding such a compatibilizer in the present invention can improve the physical compatibility of the rubber powder and the plastic on the one hand, and on the other hand can make a large amount of chemical bonding between the rubber powder and the compatibilizer through the role of the crosslinking agent to ensure the rubber The strength of the interface between powder and plastic; At the same time, the molecular chain of the soft segment in the compatibilizer has a sufficient length, so that the stress concentration between the plastic and the rubber powder is greatly alleviated. Through these effects of the compatibilizer, the interface between the waste rubber powder and the plastic can be greatly improved.
  • Crosslinking agents are also extremely important in the present invention.
  • a cross-linking accelerator In order to improve the cross-linking efficiency of the cross-linking agent, a cross-linking accelerator, a cross-linking active agent, and the like must also be added to improve the cross-linking efficiency of the cross-linking agent.
  • Sulfur or sulfur-containing compounds are used as cross-linking agents.
  • Commonly used accelerators and active agents are suitable for this system, such as accelerator thiol benzothiazole, zinc aminothioformate, active agent zinc oxide, stearic acid, etc. .
  • an antioxidant is optionally added, and the antioxidant is added to improve the aging resistance of the material.
  • Various antioxidants for conventional rubber can be selected.
  • the present invention is an amine antioxidant 4010NA, whose composition is N-phenyl-N, -isopropyl p-diamine. The dosage should be controlled within the range of 0.5-4 parts.
  • auxiliaries and additives such as softening plasticizers, such as motor oil, naphthenic oil, etc., and fillers, such as carbon black, white carbon black, calcium carbonate, etc. may be added as needed; lubricants such as Calcium stearate, zinc stearate, etc.
  • softening plasticizers for conventional rubber can be selected, and naphthenic oil and motor oil are preferably used in the present invention. Dosage is controlled in the range of 0-10 parts.
  • the process of preparing waste rubber powder / plastic thermoplastic elastomer is performed in two steps. First, 100 parts of waste rubber powder and 0.1 to 5 parts of modifier are added to the mill or mixer to prepare modified rubber powder.
  • the processing temperature is between 10-100 ", and the processing time is controlled between 3-15 Second, add modified rubber powder and plastic, compatibilizer, antioxidant and other additives, additives to the mill, Reaction processing is performed in an internal mixer or extruder.
  • the processing temperature should be selected to ensure that the plastic can be melt-plasticized. At the same time, it should be determined according to the reaction characteristics of the cross-linking agent.
  • the processing temperature is between 100-200 X.
  • the selected processing time should not only ensure that the materials are uniformly mixed, but also be based on the cross-linking.
  • the type of crosslinking agent, reaction characteristics and amount are selected. Processing time is 3-15 minutes.
  • thermoplastic elastomer of the present invention Any known plastic molding processing method can be used to prepare a molded article from the thermoplastic elastomer of the present invention, and processing equipment adopts those commonly used in the art.
  • sheet materials such as waterproof coils, pipes, rods, and various injection products can be produced by molding methods such as calendering, injection, and extrusion.
  • the waste rubber powder used in the examples is tire waste rubber powder, the VA content in EVA is 14%, and the styrene content in SBS is 40%.
  • the EVA model 14/2 used in the examples can be purchased from Beijing (China) Organic Chemical Plant.
  • the rubber powder modifier used in Examples 2 to 16 is a rubber powder modifier De-link, which is available from DE-LINK Technologies China Co.
  • thermoplastic elastomer from 60 mesh modified tire waste rubber powder / EVA
  • Zinc oxide 2 servings
  • the modified rubber powder was prepared by adding 1.5 parts of hexamethylenetetramine and 1 part of resorcinol to 100 parts of tire rubber powder, and mixing in an open mill, and the temperature was controlled at It is less than about 80 "and the time is 6 minutes.
  • the materials in the formula of Example 1 are added to an internal mixer, and the waste rubber powder / plastic thermoplastic elastomer is prepared by reaction processing at a temperature of about 160 ° C for about 10 minutes.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 2 Preparation of thermoplastic elastomer from 60 mesh De-Link modified tire rubber powder / EVA
  • the modified rubber powder is prepared by mixing 100 parts of rubber powder and 5 parts of rubber powder modifier De-Link in an open mill or mixer for about 10 minutes, and the material temperature is controlled at about 60 :.
  • the rubber powder modifier De-Link used in the present invention itself contains a certain amount of cross-linking agent sulphur-breaking or sulfur-containing compound, cross-linking accelerator thiocarbamates, cross-linking active agent zinc oxide and stearic acid, so The use of the rubber powder modifier can eliminate the need for additional cross-linking agents, cross-linking accelerators and cross-linking active agents.
  • a waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 2 according to the procedure of Example 1.
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Example 3 Following the procedure in Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the materials in the formulation of Example 3.
  • thermoplastic elastomer from 30 mesh modified tire waste rubber powder / EVA Formula: parts by weight
  • EVA 10 servings N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
  • the modified rubber powder treatment method is the same as in Example 2.
  • a waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 4 according to the procedure of Example 1.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 5 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / EVA
  • the modified rubber powder treatment method is the same as in Example 2.
  • Example 1 Following the procedure of Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the materials in the formulation of Example 5.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are listed in Table 1.
  • Example 6 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PE
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Example 1 a rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 6.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 7 Preparation of a thermoplastic elastomer from 60 mesh modified tire rubber powder / PS
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Example 1 Following the procedure of Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the material in the formulation of Example 7.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 8 Preparation of thermoplastic elastomer from 40 mesh modified tire waste rubber powder / PS
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Example 1 Following the procedure of Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the materials in the formulation of Example 8.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 9 Preparation of thermoplastic elastomer from 40 mesh modified tire waste rubber powder / PS
  • the modified rubber powder is treated in the same manner as in Example 2.
  • a waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 9 according to the procedure of Example 1.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 10 Preparation of a thermoplastic elastomer from 40 mesh modified tire rubber powder / PS Formula: parts by weight 70 mesh modified tire waste rubber powder 70 parts
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 10 by following the procedure of Example 1.
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 11 by following the procedure of Example 1.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 12 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PS
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 12 by following the procedure of Example 1.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 13 Preparation of a thermoplastic elastomer from 80-mesh modified tire rubber powder / PS Formula: parts by weight
  • the modified rubber powder is treated in the same manner as in Example 2.
  • a waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 13 by following the procedure of Example 1.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 14 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PE
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Example 14 a rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 14.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are listed in Table 1.
  • Example 15 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PE
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 15 by following the procedure of Example 1.
  • thermoplastic elastomer The properties of the prepared rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 16 Preparation of a thermoplastic elastomer from 60 mesh modified tire rubber powder / EVA
  • the modified rubber powder is treated in the same manner as in Example 2.
  • Example 1 Following the procedure of Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the material in the formulation of Example 16.
  • thermoplastic elastomer The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
  • Example 17 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PS
  • the modified rubber powder is treated in the same manner as in Example 2.
  • a waste rubber powder / plastic thermoplastic elastomer was prepared from the material in the formulation of Example 17 by following the procedure of Example 1.
  • the modified rubber powder processing method is the same as that in Example 2.
  • a waste rubber powder / plastic thermoplastic elastomer was prepared from the material in the formulation of Example 17 by following the procedure of Example 1.
  • the materials in the comparative example formulation were used to prepare a waste rubber powder / plastic thermoplastic composition blend.
  • Comparative Example 2 (B) disclosed in EP 0, 649, 871 A2 was used as Comparative Example 2 of the present invention.
  • Example 2 (Ethylene / methacrylic acid copolymer (20% MMA))
  • the rubber powder was not modified, but the plastic PE was modified with EMMA to increase its Compatibility with rubber.
  • thermoplastic elastomer of the present invention is compared with that obtained in the prior art.
  • the mechanical properties have been greatly improved.
  • the tensile strength of the thermoplastic elastomer prepared in Example 6 of the present invention was improved by 41.4% compared with that of Comparative Example 1, the elongation at break was increased by 100%, and the tear strength was increased by 31.9%. .
  • thermoplastic elastomer prepared in Example 6 of the present invention is much lower than that obtained in Comparative Example 2 (Example 2 disclosed in EP 0, 649, 871 A2). Therefore, its elongation at break also improved a lot (increased by 85%), and the tensile strength also improved T3 ⁇ 4.
  • thermoplastic elastomer excellent in comprehensive physical and mechanical properties is obtained.
  • thermoplastic elastomer just obtained in Examples 2- 6, 9 was directly fed into a four-roll calender SY4F-1400 (available from Jiangsu Shuangxiang Group Company), and the roll temperature of the calender was controlled at 150 180'C. In between, the sheet sent out from the calender is cooled, coiled, cut, and a waterproof sheet is made.
  • thermoplastic elastomer obtained in Examples 2, 6, and 9 was pelletized or pelletized, and then fed to a single-screw extruder Brabender PLD 651 (commercially available from Brabender (Germany)).
  • the screw diameter is ⁇ 30, the aspect ratio is 24: 1, the barrel temperature is controlled at 120 "C, two 180, three 200X, and four 200X :, after passing a tube head, the head temperature is 190 to make a tube.
  • thermoplastic elastomer pellets in Examples 2, 6, and 9 were fed into the barrel of an injection machine.
  • the injection machine was a UM-8DiII injection molding machine (available from Dongguan Yiguang Precision Machinery Co., Ltd.), and the barrel temperature was controlled at One section of 140C, two sections of 180 ⁇ , three sections of 220TC, four sections of 2201, nozzle temperature is 200 ", mold temperature is controlled at 30", injection pressure is 8MPa, injection time is 2 seconds, and cooling and holding time is 30 seconds. .
  • thermoplastic elastomer of the present invention can be used to prepare a molded article from the thermoplastic elastomer of the present invention using processing equipment commonly used in the art.

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  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

In this invention, the thermoplastic elastomers of excellent physical mechanism performance are obtained from waste rubber powder/plastic. The process is as follows: first, the waste rubber powder is treated with one or several kinds of modifying agents. Secondly, the modified waste rubber powder, plastic, reactive compatilizer, crosslinking system and optional antioxidant and the like are added into rolling mill, mixer or twin screw extruder. These thermoplastic elastomers have excellent physical mechanism performance, and can be made into articles by traditional plastic process technique.

Description

由廈胶粉 /塑料反应加工制备的  Prepared from Xiamen gum powder / plastic reaction processing
热塑性弹性体及由其制备的制品 发明领域  Thermoplastic elastomers and articles made therefrom
本发明涉及由废胶粉 /塑料反应加工制备的热塑性弹性体， 及由其 制备的成型制品。 更具体地说， 本发明涉及以废胶粉作为主要原材料， 通过对胶粉进行改性， 及加入特定的相容剂， 利用反应加工技术制备废 胶粉 /塑料热塑性弹性体， 这些材料具有优良的综合物理机械性能； 以 及由该热塑性弹性体通过传统的塑料成型技术制备的成型制品， 例如： 可通过压延、 注射和挤出等方法生产片材如防水卷材、 管材、 棒材及各 种注射制品。  The present invention relates to a thermoplastic elastomer prepared by waste rubber powder / plastic reaction processing, and a shaped article prepared therefrom. More specifically, the present invention relates to waste rubber powder as a main raw material, through modification of the rubber powder, and adding a specific compatibilizing agent, using a reactive processing technology to prepare waste rubber powder / plastic thermoplastic elastomer, these materials have excellent Comprehensive physical and mechanical properties; and molded articles made from the thermoplastic elastomer through traditional plastic molding techniques, such as: sheets such as waterproof coils, pipes, rods, and various types can be produced by calendering, injection, and extrusion methods Injection products.
发明背景  Background of the invention
随着科技的迅猛发展， 橡胶制品的产量正不断提高， 但随之而来的 是大量的廈旧橡胶制品严重污染环境， 成为一大公害， 被称为 "黑色污 染" 。 为了保护环境， 目前世界各国已纷纷采取措施， 制定法律条文来 解决这一威胁人类环境的问题， 其作法是： 一、 尽可能以热塑性弹性体 代替传统橡胶材料制作制品， 以减小污染源的数量， 二、 积极开展废旧 橡胶的回收利用， 并使之再资源化。 以废胶粉为主体材料制备热塑性弹 性体无疑具有以上双重作用， 其环保意义非常重大。  With the rapid development of science and technology, the output of rubber products is continuously increasing, but with it, a large number of old rubber products have seriously polluted the environment and become a major nuisance, which is called "black pollution". In order to protect the environment, countries around the world have taken measures to formulate legal provisions to address this problem that threatens the human environment. The methods are as follows: 1. Thermoplastic elastomers are used to replace traditional rubber materials as much as possible to reduce the number of pollution sources. Second, actively carry out the recycling of waste rubber and make it re-recyclable. The preparation of thermoplastic elastomers with waste rubber powder as the main material undoubtedly has the above dual effects, and its environmental protection significance is of great significance.
在 W0 92/01745中， OLIVEIRA DA CUNHA LIMA, Luiz, Corlos (BR) 公开了一种制备热塑性橡胶的方法， 使用废橡胶作为原材料， 通过物理、 化学或物化方法使橡胶脱疏， 转变成均匀的常规批料（batch ) 再生胶， 然后使该再生胶母料与热塑性树脂混合， 获得用于工业用途的热塑性橡 胶。 但是该生产再生胶的方法中所必须采用的脱硫过程耗时长， 能耗大， 且因使用溶剂而产生污染。  In WO 92/01745, OLIVEIRA DA CUNHA LIMA, Luiz, Corlos (BR) discloses a method for preparing thermoplastic rubber, using waste rubber as a raw material, and using physical, chemical or physical and chemical methods to deboss the rubber and turn it into a uniform The conventional batch is recycled rubber, and then the recycled rubber master batch is mixed with a thermoplastic resin to obtain a thermoplastic rubber for industrial use. However, the desulfurization process that must be used in the method for producing recycled rubber takes a long time, consumes large energy, and generates pollution due to the use of solvents.
利用废胶粉代替再生胶与热塑性塑料共混而制备热塑性弹性体的方 法是另一种回收和利用废旧橡胶的方法。 该方法具有工艺简单， 能耗低， 无环境污染等优点。  The method of preparing thermoplastic elastomer by using waste rubber powder instead of reclaimed rubber and blending with thermoplastic is another method of recycling and utilizing waste rubber. This method has the advantages of simple process, low energy consumption, and no environmental pollution.
在 EP 0649871 A2 中， Johnson, Lane D.公开了一种聚烯烃与胶粉 的混合物， 其中包括一种官能化的烯烃共聚物作为相容剂， 以改善胶粉 与聚烯烃的界面相容性， 该官能化的烯烃共聚物包括 SEBS、 聚乙烯 /丙 烯酸共聚物、 SEBS/马来酸酐共聚物等等。 其作用主要是提高塑料与胶 粉之间的物理相容性， 并有可能在加工过程中由于高温和剪切的作用， 使之与胶粉产生少量的化学键合。 仅采用这种官能化的烯烃共聚物作相 容剂虽能改善塑料与胶粉之间的界面结合， 但效果并不理想， 通过这种 方法制备的废胶粉与塑料的共混物的物理机械性能， 尤其是硬度、 拉伸 强度、 断裂伸长率等综合物理机械性能还不能令人满意， 有待于进一步 提高， 而且在该文献中塑料体系中的树脂只能选用聚烯烃类树脂。 In EP 0649871 A2, Johnson, Lane D. discloses a mixture of polyolefin and rubber powder, which includes a functionalized olefin copolymer as a compatibilizer to improve the interfacial compatibility of rubber powder and polyolefin. The functionalized olefin copolymer includes SEBS, polyethylene / acrylic copolymer, SEBS / maleic anhydride copolymer, and the like. Its role is mainly to improve plastics and rubber The physical compatibility between the powders may cause a small amount of chemical bonding with the rubber powder during processing due to high temperature and shear. Although the use of this functionalized olefin copolymer as a compatibilizer can improve the interfacial bonding between plastic and rubber powder, the effect is not ideal. The physical properties of the blend of waste rubber powder and plastic prepared by this method The mechanical properties, especially the comprehensive physical and mechanical properties such as hardness, tensile strength, and elongation at break, are still unsatisfactory and need to be further improved, and the resins in the plastic system in this document can only be selected from polyolefin resins.
发明目的  Object of the invention
本发明的目的是从废胶粉 /塑料体系得到具有优良综合物理机械性 能的热塑性弹性体， 尤其是提高胶粉的利用率， 降低热塑性弹性体的硬 度， 提高断裂伸长率、 拉伸强度。 扩大廈胶粉 /塑料体系中塑料树脂的 种类， 从而得以使廈胶粉 /塑料热塑性弹性体的品种多样化。  The purpose of the present invention is to obtain a thermoplastic elastomer with excellent comprehensive physical and mechanical properties from a waste rubber powder / plastic system, in particular to improve the utilization rate of the rubber powder, reduce the hardness of the thermoplastic elastomer, and increase the elongation at break and tensile strength. Expand the types of plastic resins in the building powder / plastic system, so as to diversify the types of building powder / plastic thermoplastic elastomers.
发明概述  Summary of invention
本发明提供一种热塑性弹性体， 其是通过反应加工包含以下组分的 配合物制备的：  The present invention provides a thermoplastic elastomer prepared by reaction processing of a complex comprising the following components:
①粒径小于 10目的废胶粉，  ①Waste rubber powder with particle size less than 10 mesh,
②胶粉改性剂，  ② rubber powder modifier,
③塑料， 其选自聚烯烃、 乙烯 /醋酸乙烯酯共聚物 （EVA ) 及聚笨乙 烯（PS ) 中的一种或多种，  ③ plastic, which is selected from one or more of polyolefin, ethylene / vinyl acetate copolymer (EVA), and polystyrene (PS),
④反应性相容剂， 其是分子链中含有硬段区和软段区的共聚物， 该 硬段区由乙烯、 丙烯、 丁烯、 异丁烯、 苯乙烯等单体中的一种或 几种聚合而成， 软段区由天然橡胶、 顺丁橡胶、 丁笨橡胶、 丁基 橡胶、 三元乙丙橡胶等的分子链形成， 或由异戊二烯、 丁二埽等 单体聚合而成， 其中在软段区中含有可用硫磺或含硫化合物、 酚 醛树脂等交联剂交联的 > C = C <结构， 同时软段区中分子链碳原 子数大于 50,  ④ Reactive compatibilizer, which is a copolymer containing a hard segment region and a soft segment region in the molecular chain. The hard segment region is composed of one or more of ethylene, propylene, butene, isobutylene, styrene and other monomers. Polymerized, the soft segment area is formed by molecular chains of natural rubber, butadiene rubber, butyl rubber, butyl rubber, EPDM, etc., or polymerized by monomers such as isoprene and butadiene Wherein the soft segment region contains> C = C <structure that can be cross-linked with crosslinking agents such as sulfur or sulfur-containing compounds, phenolic resins, and the number of carbon atoms in the molecular chain in the soft segment region is greater than 50,
⑤交联体系， 包括交联剂、 交联促进剂、 交联活性剂等，  ⑤ Cross-linking system, including cross-linking agent, cross-linking accelerator, cross-linking active agent, etc.
任选还有防老剂。  Optional antioxidants.
该制备方法包括第一步将废胶粉与一种或多种改性剂在开炼机、 密 炼机或双螺杆挤出机中进行改性， 操作条件： 温度 10 - 1001：， 时间 3 - 15分钟； 第二步将改性废胶粉与塑料、 反应性相容剂、 交联体系、 任 选的防老剂等加入到开炼机、 密炼机或双螺杆挤出机中进行反应加工， 加工温度 100'C ~ 200"C， 时间 3 - 15分钟。 优选， 所述的配合物中各组分的重量组成份数为： The preparation method includes the first step of modifying the waste rubber powder and one or more modifiers in an open mill, an internal mixer or a twin-screw extruder. Operating conditions: temperature 10-1001 :, time 3 -15 minutes; in the second step, add the modified waste rubber powder and plastic, reactive compatibilizer, cross-linking system, optional antioxidant, etc. to the open mill, internal mixer or twin screw extruder for reaction Processing, processing temperature 100'C ~ 200 "C, time 3-15 minutes. Preferably, the weight composition of each component in the complex is:
废胶粉、 塑料及相容剂： 100份；  Waste rubber powder, plastic and compatibilizer: 100 parts;
其中 废胶粉 50 - 90重量份  Of which 50-90 parts by weight of waste rubber powder
塑料 3 - 47重量份  Plastic 3-47 parts by weight
相容剂 3 - 47重量份  Compatibilizer 3-47 parts by weight
胶粉改性剂： 0. 1 ~ 5重量份；  Rubber powder modifier: 0.1 ~ 5 parts by weight;
交联体系： 交联剂 0. 1 ~ 3重量份、 交联促进剂 0. 1 ~ 5重量份、 交 联活性剂 0. 1 - 8重量份；  Cross-linking system: 0.1 to 3 parts by weight of cross-linking agent, 0.1 to 5 parts by weight of cross-linking accelerator, and 0.1 to 8 parts by weight of cross-linking active agent;
任选的防老剂： 0. 5 - 3重量份。  Optional antioxidant: 0.5-3 parts by weight.
所述的配合物还可包括 0 - 10重量份的软化增塑剂。  The complex may further include 0 to 10 parts by weight of a softening plasticizer.
本发明还提供由所述的热塑性弹性体通过传统的成型加工方法而制 备的成型制品。  The present invention also provides a molded article prepared from the thermoplastic elastomer by a conventional molding processing method.
发明详述  Detailed description of the invention
术语 "反应加工" 是指橡塑共混体系在一定温度下边共混边进行硫 化的过程， 因产生交联而显著改善了并用体的力学性能。  The term "reaction processing" refers to the process of vulcanization of the rubber-plastic blend system while blending at a certain temperature, which significantly improves the mechanical properties of the combined body due to cross-linking.
本发明所用的废胶粉， 为废旧橡胶直接粉碎而来， 可以是轮胎废胶 粉、 鞋类废胶粉、 杂品废胶粉等， 最好使用轮胎废胶粉。 其粒径小于 10 目， 最佳粒径范围在 30目 - 80目。  The waste rubber powder used in the present invention is directly pulverized from waste rubber. It can be tire waste rubber powder, footwear waste rubber powder, miscellaneous waste rubber powder, etc. It is preferable to use tire waste rubber powder. Its particle size is less than 10 mesh, and the optimal particle size range is 30 mesh-80 mesh.
本发明所用的塑料原材料， 其既可以是未用过的树脂， 也可以是废 旧塑料粉碎回收的。 其包括聚烯烃类树脂、 聚苯乙烯或 EVA等。 选用不 同的塑料原材料， 因为其自身的结构特点不同， 因此由不同塑料体系制 备的废胶粉 /塑料热塑性弹性体的结构、 性能特点也必然不同。 从而得 以使廈胶粉 /塑料热塑性弹性体的品种多样化。  The plastic raw material used in the present invention may be either an unused resin or a waste plastic which is crushed and recovered. These include polyolefin resins, polystyrene or EVA. Different plastic raw materials are used because of their different structural characteristics, so the structure and performance characteristics of waste rubber powder / plastic thermoplastic elastomer prepared by different plastic systems are also necessarily different. Thereby, the variety of Xiajiao powder / plastic thermoplastic elastomer can be diversified.
在本发明中， 胶粉改性剂与反应性相容剂是极其重要的。 在基体材 料废胶粉与塑料选定的情况下， 要制备综合性能优良的废胶粉 /塑料热 塑性弹性体必须保证废胶粉与塑料产生良好的界面结合。 要做到这一 点， 一方面必须使废胶粉与塑料间形成大量的化学键合， 保证足够的界 面强度； 另一方面， 必须保证足够的界面层厚度， 以緩冲材料受力时的 应力集中作用。  In the present invention, the rubber powder modifier and the reactive compatibilizer are extremely important. In the case where the base material waste rubber powder and plastic are selected, in order to prepare waste rubber powder / plastic thermoplastic elastomer with excellent comprehensive properties, it is necessary to ensure that the waste rubber powder and plastic have a good interface. To achieve this, on the one hand, a large number of chemical bonds must be formed between the waste rubber powder and the plastic to ensure sufficient interface strength; on the other hand, sufficient thickness of the interface layer must be ensured to cushion the stress concentration of the material when it is stressed effect.
由废旧橡胶粉碎后制得的废胶粉， 其表面的交联网结构破坏程度不 够， 仍比较密实， 链段运动能力差， 这不利于胶粉和塑料的分子链相互 运动形成足够的界面层厚度， 并且废胶粉表面的反应活性点较少， 这不 利于在加工过程中与相容剂产生化学键合以保证足够的界面强度。 为此 对废胶粉进行活化改性处理. The waste rubber powder made from the crushed waste rubber has insufficient damage to the cross-linked network structure on the surface, is still dense, and has poor chain movement ability, which is not conducive to the movement of the rubber powder and plastic molecular chains to form a sufficient interface layer thickness. And there are fewer reactive points on the surface of the waste rubber powder, which does not Conducive to chemical bonding with the compatibilizer during processing to ensure sufficient interface strength. To this end, the waste rubber powder is subjected to activation modification treatment.
通过将废胶粉与各种改性剂在密炼机或开炼机等剪切力较大的设备 中， 一方面靠设备的强剪切作用切断橡胶分子链； 一方面靠改性剂的化 学作用使分子链断裂， 进一步增加胶粉的疏松程度并使废胶粉产生大量 的反应活性点。 废胶粉经过这样的预处理， 使之与塑料在反应加工过程 中产生良好的界面结合成为可能。 凡是能使废胶粉产生反应活性点的改 性剂及改性方法均适用本发明。  By using waste rubber powder and various modifiers in equipment with large shearing forces such as internal mixers or open mills, on the one hand, the rubber molecular chain is cut by the strong shearing action of the equipment; on the other hand, the modifiers are used. Chemical action breaks the molecular chain, further increasing the looseness of the rubber powder and generating a large number of reactive spots of the waste rubber powder. After such pretreatment, it is possible for the waste rubber powder to have a good interface with the plastic during the reaction process. Any modifier and modification method capable of causing reactive rubber spots to generate waste rubber powder are applicable to the present invention.
本发明所用的胶粉改性剂是一类能使废旧橡胶- S - S -键断裂的物 质， 包括六次甲基四胺和间苯二酚或它们的衍生物， 硫醇类或硫酚类如 二甲苯基硫酚， 三氯硫酚等， 或者得自迪连工业（中国）公司（DE - LINK Technologies China Co. ) 的胶粉改性剂 De- Link, 它的主要成分是硫 代氨基甲酸盐类如二甲基二疏代氨基甲酸锌及 2 -巯基苯并噻唑或其衍 生物如巯基笨并噻唑锌， 同时 De-Link 中还含有一定的硫磺或含硫化合 物。 将这类改性剂与廈胶粉一起加入到密炼机， 开炼机或螺杆挤出机等 剪切力较大的设备中。 一方面靠设备的强剪切作用切断橡胶分子链， 一 方面靠改性剂的化学作用切断橡胶分子链以提高胶粉表面分子链的运动 能力； 同时靠改性剂的化学作用增加胶粉表面的反应活性点， 这些活性 点可重新用硫磺、 含硫化合物、 及酚醛树脂等交联剂交联， 废胶粉经过 这样的改性处理， 使之与基体塑料产生良好的界面结合成为可能.  The rubber powder modifier used in the present invention is a kind of material capable of breaking the S-S-bond of waste rubber, including hexamethylenetetramine and resorcinol or their derivatives, thiols or thiophenols. Classes such as xylylthiophenol, trichlorothiophenol, etc., or rubber powder modifier De-Link from DE-LINK Technologies China Co., whose main component is thioxo Carbamates such as zinc dimethyldithiocarbamate and 2-mercaptobenzothiazole or derivatives thereof such as zinc mercaptobenzothiazole. De-Link also contains certain sulfur or sulfur-containing compounds. These modifiers are added together with the Xiajiao powder to equipment with high shear forces such as mixers, open mills or screw extruders. On the one hand, the rubber molecular chain is cut by the strong shearing action of the equipment; on the other hand, the rubber molecular chain is cut by the chemical action of the modifier to improve the movement ability of the molecular chain on the surface of the rubber powder; Reactive points, these points can be re-crosslinked with cross-linking agents such as sulfur, sulfur compounds, and phenolic resins. The waste rubber powder undergoes such a modification treatment to make it possible to produce a good interface with the matrix plastic.
要使废胶粉与塑料产生良好的界面结合， 仅使废胶粉改性还不够， 必须还要加入相容剂。 因废胶粉粒径粗大， 废胶粉 /塑料热塑性弹性体 材料在受力时， 在界面处产生的应力集中要比传统共混型热塑性弹性体 大的多， 因此对相容剂的要求较高， 一方面要与基体塑料具有良好的相 容性， 另一方面要与废胶粉表面的反应活性点产生化学键合， 从而保证 足够的界面强度； 同时相容剂本身必须含有足够长度的高分子柔性链， 在增加界面层厚度的同时， 大大减小界面处的应力集中。 凡是符合上述 条件热塑性弹性体或弹性体材料均可做为本发明所需的相容剂，  In order to make the waste rubber powder and plastic have a good interface, it is not enough to modify the waste rubber powder alone. A compatibilizer must be added. Due to the coarse particle size of the waste rubber powder, the stress concentration at the interface of the waste rubber powder / plastic thermoplastic elastomer material under stress is much larger than that of traditional blended thermoplastic elastomers when under stress, so the requirements for compatibilizers are relatively large. High, on the one hand, it must have good compatibility with the matrix plastic, on the other hand, it must have chemical bonding with the reactive points on the surface of the waste rubber powder, so as to ensure sufficient interface strength; at the same time, the compatibilizer itself must contain The molecular flexible chain, while increasing the thickness of the interface layer, greatly reduces the stress concentration at the interface. Any thermoplastic elastomer or elastomer material that meets the above conditions can be used as the compatibilizer required for the present invention.
本发明所用的相容剂是一种共聚物， 该共聚物分子链中含有硬段区 和软段区， 硬段区由乙烯、 丙烯、 苯乙烯等单体聚合而成， 软段区由天 然橡胶、 顺丁橡胶、 丁笨橡胶、 丁基橡胶、 三元乙丙橡胶等的分子链形 成； 或由异戊二烯、 丁二烯等单体聚合而成， 其中在软段区中必须含有 可用硫磺或含硫化物、 酚醛树脂等交联剂交联的〉 C = C〈结构， 同时软段 区的分子链必须保证一定的长度， C原子数要大于 50。 这种相容剂的例 子包括： PS - g -天然橡胶， PP - g - EPDM, PE - g -丁基橡胶， SBS, SIS 等等。 在本发明中加入这种相容剂， 一方面可以提高胶粉与塑料的物理 相容性， 另一方面通过交联剂的作用可以使胶粉与相容剂发生大量的化 学键合以保证胶粉与塑料之间的界面强度； 同时相容剂中软段区分子链 有足够的长度， 从而使塑料与胶粉之间的应力集中作用大为緩和。 通过 相容剂的这些作用， 可以大大提高废胶粉与塑料的界面结合。 The compatibilizer used in the present invention is a copolymer. The molecular chain of the copolymer contains a hard segment region and a soft segment region. The hard segment region is polymerized from monomers such as ethylene, propylene, and styrene. The soft segment region is made of natural materials. Formed by molecular chains of rubber, butadiene rubber, butyl rubber, butyl rubber, ethylene propylene rubber, etc .; or polymerized from monomers such as isoprene and butadiene, which must be contained in the soft section It can be crosslinked with sulfur or sulfide-containing, phenolic resin and other cross-linking agents. The structure is> C = C <. At the same time, the molecular chain of the soft segment must be a certain length, and the number of C atoms must be greater than 50. Examples of such compatibilizers include: PS-g-natural rubber, PP-g-EPDM, PE-g-butyl rubber, SBS, SIS, etc. Adding such a compatibilizer in the present invention can improve the physical compatibility of the rubber powder and the plastic on the one hand, and on the other hand can make a large amount of chemical bonding between the rubber powder and the compatibilizer through the role of the crosslinking agent to ensure the rubber The strength of the interface between powder and plastic; At the same time, the molecular chain of the soft segment in the compatibilizer has a sufficient length, so that the stress concentration between the plastic and the rubber powder is greatly alleviated. Through these effects of the compatibilizer, the interface between the waste rubber powder and the plastic can be greatly improved.
交联剂在本发明中也是极其重要的。 胶粉改性后形成的反应活性点 与相容剂中的〉 C = C<只有通过交联剂才能形成化学键合。 由于胶粉经过 改性， 产生了一部分能重新产生交联作用的游离硫， 因此， 即使不再加 入新的交联剂也能够进行一定程度交联， 但由于含量较少， 因此必须加 入具有交联作用的物质以保证废胶粉上的反应活性点与相容剂上的双键 得到充分的交联， 形成大量的化学键合从而使废胶粉和塑料之间的界面 结合的更好。 凡是能交联〉 C = C〈双键的交联剂均可适用本体系， 常用的 交联剂为硫磺或含硫化合物如二疏化四甲基秋兰姆， 酚醛树脂等等。  Crosslinking agents are also extremely important in the present invention. The reactive point formed after the modification of the rubber powder is> C = C <in the compatibilizer. Only through the cross-linking agent can a chemical bond be formed. Because the rubber powder is modified, a part of the free sulfur that can regenerate cross-linking is generated. Therefore, even if no new cross-linking agent is added, the cross-linking can be carried out to a certain extent. Substances that interact to ensure that the reactive points on the waste rubber powder and the double bonds on the compatibilizer are fully cross-linked, forming a large number of chemical bonds so that the interface between the waste rubber powder and the plastic is better. Any cross-linking agent capable of cross-linking> C = C <double bond can be applied to this system. Commonly used cross-linking agents are sulfur or sulfur-containing compounds such as dilute tetramethylthiuram, phenolic resin, and the like.
为了提高交联剂的交联效率， 还必须加入交联促进剂、 交联活性剂 等以提高交联剂的交联效率。 使用硫磺或含硫化合物作交联剂， 常用的 促进剂、 活性剂均适用于本体系， 如促进剂硫醇基苯并噻唑， 氨基硫代 甲酸锌， 活性剂氧化锌、 硬脂酸等等。  In order to improve the cross-linking efficiency of the cross-linking agent, a cross-linking accelerator, a cross-linking active agent, and the like must also be added to improve the cross-linking efficiency of the cross-linking agent. Sulfur or sulfur-containing compounds are used as cross-linking agents. Commonly used accelerators and active agents are suitable for this system, such as accelerator thiol benzothiazole, zinc aminothioformate, active agent zinc oxide, stearic acid, etc. .
本发明中， 任选加入防老剂， 防老剂的加入是为了提高材料的耐老 化性能。 可以选用常规橡胶用各种防老剂， 本发明优逸是胺类防老剂 4010NA, 其成分是 N -苯基 - N，-异丙基对笨二胺。 用量宜控制在 0. 5-4 份范围内。  In the present invention, an antioxidant is optionally added, and the antioxidant is added to improve the aging resistance of the material. Various antioxidants for conventional rubber can be selected. The present invention is an amine antioxidant 4010NA, whose composition is N-phenyl-N, -isopropyl p-diamine. The dosage should be controlled within the range of 0.5-4 parts.
在本发明中， 根据需要还可以加入其它助剂、 添加剂， 例如软化增 塑剂， 如机油， 环烷油等， 填充补强剂， 如炭黑、 白炭黑、 碳酸钙等； 润滑剂如硬脂酸钙、 硬脂酸锌等等。 可以选用常规橡胶用各种软化增塑 剂， 本发明优选使用环烷油、 机油。 用量控制在 0 - 10份的范围内。  In the present invention, other auxiliaries and additives, such as softening plasticizers, such as motor oil, naphthenic oil, etc., and fillers, such as carbon black, white carbon black, calcium carbonate, etc. may be added as needed; lubricants such as Calcium stearate, zinc stearate, etc. Various softening plasticizers for conventional rubber can be selected, and naphthenic oil and motor oil are preferably used in the present invention. Dosage is controlled in the range of 0-10 parts.
制备废胶粉 /塑料热塑性弹性体的工艺过程分两步进行。 首先是 100 份废胶粉与 0. 1 ~ 5 份改性剂加入到开炼机或密炼机中制备改性胶粉， 加工温度在 10 - 100" 之间， 加工时间控制在 3 - 15 分钟。 其次， 将 改性胶粉与塑料、 相容剂、 防老剂及其它助剂、 添加剂加入到开炼机、 密炼机或挤出机中进行反应加工。 选取的加工温度应保证塑料能够熔融 塑化， 同时还要根据交联剂的反应特性来决定, 加工温度在 100 - 200 X之间， 选取的加工时间不仅要保证物料混合均匀， 同时应根据交联剂 的类型、 反应特性及用量来选定。 加工时间在 3 - 15分钟。 The process of preparing waste rubber powder / plastic thermoplastic elastomer is performed in two steps. First, 100 parts of waste rubber powder and 0.1 to 5 parts of modifier are added to the mill or mixer to prepare modified rubber powder. The processing temperature is between 10-100 ", and the processing time is controlled between 3-15 Second, add modified rubber powder and plastic, compatibilizer, antioxidant and other additives, additives to the mill, Reaction processing is performed in an internal mixer or extruder. The processing temperature should be selected to ensure that the plastic can be melt-plasticized. At the same time, it should be determined according to the reaction characteristics of the cross-linking agent. The processing temperature is between 100-200 X. The selected processing time should not only ensure that the materials are uniformly mixed, but also be based on the cross-linking. The type of crosslinking agent, reaction characteristics and amount are selected. Processing time is 3-15 minutes.
可以采用任何已知的塑料成型加工方法， 由本发明的热塑性弹性体 制备成型制品， 加工设备采用本领域中常用的那些。 例如可通过压延、 注射、 挤出等成型方法， 生产片材如防水卷材、 管材、 棒材及各种注射 制品。  Any known plastic molding processing method can be used to prepare a molded article from the thermoplastic elastomer of the present invention, and processing equipment adopts those commonly used in the art. For example, sheet materials such as waterproof coils, pipes, rods, and various injection products can be produced by molding methods such as calendering, injection, and extrusion.
实施例  Examples
以下通过实施例进一步说明本发明， 但本发明不受实施例限制。  The present invention is further described below through examples, but the present invention is not limited by the examples.
除非另有说明， 实施例中所有份数都是重量份数。  Unless otherwise stated, all parts in the examples are parts by weight.
实施例中所使用的废胶粉是轮胎废胶粉， EVA中的 VA含量为 14 % , SBS中苯乙烯含量为 40% 。  The waste rubber powder used in the examples is tire waste rubber powder, the VA content in EVA is 14%, and the styrene content in SBS is 40%.
实施例中所使用的 EVA 型号 14/2， 可从北京 （中国） 有机化工厂 购得.  The EVA model 14/2 used in the examples can be purchased from Beijing (China) Organic Chemical Plant.
实施例 2 - 16 中所使用的胶粉改性剂是胶粉改性剂 De- link, 得自 迪连工业（中国） 公司 （ DE - LINK Technologies China Co. ) 。  The rubber powder modifier used in Examples 2 to 16 is a rubber powder modifier De-link, which is available from DE-LINK Technologies China Co.
实施例 1 由 60目改性轮胎废胶粉 /EVA制备热塑性弹性体  Example 1 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / EVA
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 70份  60 mesh modified tire waste rubber powder 70 parts
EVA 15份  EVA 15 servings
SBS 15份  15 servings of SBS
硫磺 1份  Sulfur 1 serving
硫醇基笨并噻唑 1份  Thiol Benzothiazole 1 part
氧化锌 2份  Zinc oxide 2 servings
硬脂酸 0. 5份  0.5 parts of stearic acid
N -笨基 - N， -异丙基对苯二胺 1份  N-benzyl-N, -isopropyl-p-phenylenediamine 1 part
在实例 1配方中， 改性胶粉是通过 100份轮胎胶粉中加入 1. 5份六 次甲基四胺和 1份间苯二酚， 在开炼机中混炼制得， 温度控制在约 80" 以下， 时间为 6分钟。 将实例 1配方中的物料加入到密炼机中， 在约 160 °C温度下， 反应加工约 10分钟制得了废胶粉 /塑料热塑性弹性体。  In the formula of Example 1, the modified rubber powder was prepared by adding 1.5 parts of hexamethylenetetramine and 1 part of resorcinol to 100 parts of tire rubber powder, and mixing in an open mill, and the temperature was controlled at It is less than about 80 "and the time is 6 minutes. The materials in the formula of Example 1 are added to an internal mixer, and the waste rubber powder / plastic thermoplastic elastomer is prepared by reaction processing at a temperature of about 160 ° C for about 10 minutes.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 2 由 60目被 De-Link改性的轮胎废胶粉 /EVA制备热塑性弹 性体 The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 2 Preparation of thermoplastic elastomer from 60 mesh De-Link modified tire rubber powder / EVA
配方： 重量份  Formula: parts by weight
60目改性轮胎廈胶粉 90份  60 mesh modified tire rubber powder 90 parts
EVA 5份  5 EVA
SBS 5份  5 servings of SBS
N -苯基- N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉系将 100份胶粉与 5份胶粉改性剂 De- Link在开炼机或密 炼机中混炼约 10分钟制得的， 料温控制在约 60 :。 本发明所用的胶粉 改性剂 De- Link本身含有一定量的交联剂破磺或含硫化合物、 交联促进 剂硫代氨基甲酸盐类、 交联活性剂氧化锌和硬脂酸， 因此使用该胶粉改 性剂可不用再另加交联剂、 交联促进剂及交联活性剂„  The modified rubber powder is prepared by mixing 100 parts of rubber powder and 5 parts of rubber powder modifier De-Link in an open mill or mixer for about 10 minutes, and the material temperature is controlled at about 60 :. The rubber powder modifier De-Link used in the present invention itself contains a certain amount of cross-linking agent sulphur-breaking or sulfur-containing compound, cross-linking accelerator thiocarbamates, cross-linking active agent zinc oxide and stearic acid, so The use of the rubber powder modifier can eliminate the need for additional cross-linking agents, cross-linking accelerators and cross-linking active agents.
按照实施例 1 的步骤由实例 2 配方中的物料制得废胶粉 /塑料热塑 性弹性体。  A waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 2 according to the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 3 由 60目改性轮胎废胶粉 /EVA制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 3 Preparation of Thermoplastic Elastomer from 60 Mesh Modified Tire Waste Rubber Powder / EVA
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 85份  60 mesh modified tire waste rubber powder 85 parts
EVA 8份  EVA 8 servings
SBS 7份  7 copies of SBS
N -苯基 - N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1 的步骤由实例 3 配方中的物料制备废胶粉 /塑料热塑 性弹性体.  Follow the procedure in Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the materials in the formulation of Example 3.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 4 由 30目改性轮胎废胶粉 /EVA制备热塑性弹性体 配方： 重量份  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 4 Preparation of thermoplastic elastomer from 30 mesh modified tire waste rubber powder / EVA Formula: parts by weight
30目改性轮胎废胶粉 80份  30 mesh modified tire waste rubber powder 80 parts
EVA 10份 N -苯基 - N，-异丙基对苯二胺 1份 EVA 10 servings N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同.  The modified rubber powder treatment method is the same as in Example 2.
按照实施例 1 的步骤由实例 4 配方中的物料制备废胶粉 /塑料热塑 性弹性体。  A waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 4 according to the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 5 由 60目改性轮胎废胶粉 /EVA制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 5 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / EVA
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 80份  60 mesh modified tire waste rubber powder 80 parts
EVA 10份  EVA 10 servings
SIS 10份  10 copies of SIS
N -苯基 - N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同.  The modified rubber powder treatment method is the same as in Example 2.
按照实施例 1 的步骤由实例 5 配方中的物料制备废胶粉 /塑料热塑 性弹性体。  Follow the procedure of Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the materials in the formulation of Example 5.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1. 实施例 6 由 60目改性轮胎废胶粉 /PE制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are listed in Table 1. Example 6 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PE
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 80份  60 mesh modified tire waste rubber powder 80 parts
PE 10份  PE 10
SBS 10份  10 servings of SBS
N -苯基 - N， -异丙基对苯二胺 1份  N -phenyl-N, -isopropyl p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1 的步骤由实例 6 配方中的物料制备廈胶粉 /塑料热塑 性弹性体。  According to the procedure of Example 1, a rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 6.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 7 由 60目改性轮胎废胶粉 /PS制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 7 Preparation of a thermoplastic elastomer from 60 mesh modified tire rubber powder / PS
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 80份 SBS 10份 60 mesh modified tire waste rubber powder 80 parts 10 servings of SBS
N -苯基 - N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1 的步骤由实例 7 配方中的物料制备废胶粉 /塑料热塑 性弹性体。  Follow the procedure of Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the material in the formulation of Example 7.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 8 由 40目改性轮胎废胶粉 /PS制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 8 Preparation of thermoplastic elastomer from 40 mesh modified tire waste rubber powder / PS
配方： 重量份  Formula: parts by weight
40目改性轮胎废胶粉 70份  70 mesh modified tire waste rubber powder 70 parts
PS 25份  PS 25 servings
SBS 5份  5 servings of SBS
N -苯基- N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1 的步骤由实例 8 配方中的物料制备废胶粉 /塑料热塑 性弹性体。  Follow the procedure of Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the materials in the formulation of Example 8.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 9 由 40目改性轮胎废胶粉 /PS制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 9 Preparation of thermoplastic elastomer from 40 mesh modified tire waste rubber powder / PS
配方： 重量份  Formula: parts by weight
40目改性轮胎废胶粉 70份  70 mesh modified tire waste rubber powder 70 parts
PS 20份  PS 20 servings
SBS 10份  10 servings of SBS
N -笨基 - N，-异丙基对苯二胺 1份  N-benzyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1 的步骤由实例 9 配方中的物料制备废胶粉 /塑料热塑 性弹性体。  A waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 9 according to the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 10 由 40目改性轮胎废胶粉 /PS制备热塑性弹性体 配方： 重量份 40目改性轮胎废胶粉 70份 The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 10 Preparation of a thermoplastic elastomer from 40 mesh modified tire rubber powder / PS Formula: parts by weight 70 mesh modified tire waste rubber powder 70 parts
PS 15份  15 servings
SBS 15份  15 servings of SBS
N -苯基 - N， -异丙基对苯二胺 1份  N -phenyl-N, -isopropyl p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1的步骤由实例 10配方中的物料制备废胶粉 /塑料热塑 性弹性体。  Waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 10 by following the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
实施例 11 由 40目改性轮胎废胶粉 /PS制备热塑性弹性体 Example 11 Preparation of thermoplastic elastomer from 40 mesh modified tire waste rubber powder / PS
配方： 重量份  Formula: parts by weight
40目改性轮胎废胶粉 70份  70 mesh modified tire waste rubber powder 70 parts
PS 10份  10 servings
SBS 20份  SBS 20 servings
N -苯基- N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1的步骤由实例 11配方中的物料制备废胶粉 /塑料热塑 性弹性体。  Waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 11 by following the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 12 由 60目改性轮胎废胶粉 /PS制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 12 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PS
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 70份  60 mesh modified tire waste rubber powder 70 parts
PS 15份  15 servings
SBS 15份  15 servings of SBS
N -苯基 - N， -异丙基对苯二胺 1份  N -phenyl-N, -isopropyl p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1的步骤由实例 12配方中的物料制备废胶粉 /塑料热塑 性弹性体。  Waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 12 by following the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 13 由 80目改性轮胎废胶粉 /PS制备热塑性弹性体 配方： 重量份 The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 13 Preparation of a thermoplastic elastomer from 80-mesh modified tire rubber powder / PS Formula: parts by weight
80目改性轮胎废胶粉 70份  80 mesh modified tire waste rubber powder 70 parts
PS 15份  15 servings
SBS 15份  15 servings of SBS
N -苯基 - N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1的步骤由实例 13配方中的物料制备废胶粉 /塑料热塑 性弹性体。  A waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 13 by following the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 14 由 60目改性轮胎废胶粉 /PE制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 14 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PE
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 70份  60 mesh modified tire waste rubber powder 70 parts
PE 15份  PE 15
SBS 15份  15 servings of SBS
N -苯基- N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1的步骤由实例 14配方中的物料制备廈胶粉 /塑料热塑 性弹性体。  According to the procedure of Example 1, a rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 14.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1. 实施例 15 由 60目改性轮胎废胶粉 /PE制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are listed in Table 1. Example 15 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PE
重量份  Parts by weight
60目改性轮胎废胶粉 70份  60 mesh modified tire waste rubber powder 70 parts
PE 15份  PE 15
SBS 15份  15 servings of SBS
0. 3份  0.3 copies
ZnO 2份  ZnO 2 parts
硬脂酸 0. 5份  0.5 parts of stearic acid
硫醇基苯并噻唑 0. 5份 N -笨基- N，-异丙基对苯二胺 1份 Thiol benzothiazole 0.5 parts N-benzyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1的步骤由实例 15配方中的物料制备废胶粉 /塑料热塑 性弹性体。  Waste rubber powder / plastic thermoplastic elastomer was prepared from the materials in the formulation of Example 15 by following the procedure of Example 1.
所制备的廈胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 16 由 60目改性轮胎废胶粉 /EVA制备热塑性弹性体  The properties of the prepared rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 16 Preparation of a thermoplastic elastomer from 60 mesh modified tire rubber powder / EVA
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 60份  60 mesh modified tire waste rubber powder 60 parts
EVA 25份  EVA 25 servings
SBS 15份  15 servings of SBS
N -苯基 - N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1的步骤由实例 16配方中的物料制备废胶粉 /塑料热塑 性弹性体.  Follow the procedure of Example 1 to prepare waste rubber powder / plastic thermoplastic elastomer from the material in the formulation of Example 16.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 17 由 60目改性轮胎废胶粉 /PS制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 17 Preparation of thermoplastic elastomer from 60 mesh modified tire waste rubber powder / PS
配方： 重量份  Formula: parts by weight
60目改性轮胎废胶粉 60份  60 mesh modified tire waste rubber powder 60 parts
PS 20份  PS 20 servings
SBS 20份  SBS 20 servings
N -苯基 - N， _异丙基对苯二胺 1份  N-phenyl-N, _isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同。  The modified rubber powder is treated in the same manner as in Example 2.
按照实施例 1的步骤由实例 17配方中的物料制备废胶粉 /塑料热塑 性弹性体。  A waste rubber powder / plastic thermoplastic elastomer was prepared from the material in the formulation of Example 17 by following the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。 实施例 18 由 40目改性轮胎废胶粉 /PE制备热塑性弹性体  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1. Example 18 Preparation of Thermoplastic Elastomer from 40 Mesh Modified Tire Waste Rubber Powder / PE
配方： 重量份  Formula: parts by weight
40目改性轮胎废胶粉 60份  60 mesh modified tire waste rubber powder 60 parts
PE 15份 SBS 25份 PE 15 25 copies of SBS
N -苯基 - N，-异丙基对苯二胺 1份  N-phenyl-N, -isopropyl-p-phenylenediamine 1 part
改性胶粉处理方法与实施例 2相同，  The modified rubber powder processing method is the same as that in Example 2.
按照实施例 1的步骤由实例 17配方中的物料制备废胶粉 /塑料热塑 性弹性体。  A waste rubber powder / plastic thermoplastic elastomer was prepared from the material in the formulation of Example 17 by following the procedure of Example 1.
所制备的废胶粉 /塑料热塑性弹性体的性能列于表 1。  The properties of the prepared waste rubber powder / plastic thermoplastic elastomer are shown in Table 1.
比较例 1 由 60目未改性的轮胎廈胶粉 /PE制备热塑性共混物 Comparative Example 1 Thermoplastic blend prepared from 60 mesh unmodified tire rubber powder / PE
配方： 重量份  Formula: parts by weight
60目轮胎废胶粉 80份  60 mesh tire waste rubber powder 80 copies
PE 10份  PE 10
SBS 10份 不对轮胎废胶粉进行改性， 而采用 EP 0649871 A2 中公开的方法由 份份份份  SBS 10 parts Do not modify tire rubber powder, but use the method disclosed in EP 0649871 A2
比较例配方中的物料制备废胶粉 /塑料热塑性组合物共混物. The materials in the comparative example formulation were used to prepare a waste rubber powder / plastic thermoplastic composition blend.
所制备的废胶粉 /塑料热塑性組合物共混物的性能也列于表 1。 比较例 2 采用 EP 0, 649, 871 A2 中公开的实施例 2 ( B ) 作为本发 明的比较例 2  The properties of the prepared waste rubber powder / plastic thermoplastic composition blend are also shown in Table 1. Comparative Example 2 Example 2 (B) disclosed in EP 0, 649, 871 A2 was used as Comparative Example 2 of the present invention.
配方： 重量  Recipe: Weight
橡胶 60  Rubber 60
PE 15  PE 15
EMMA 25  EMMA 25
(乙烯 /甲基丙烯酸共聚物 （20%MMA) ) 在 EP 0, 649, 871 A2 中公开的实施例 2 中， 不对胶粉进行改性， 而 是用 EMMA对塑料 PE进行改性， 增加其与橡胶的相容性. (Ethylene / methacrylic acid copolymer (20% MMA)) In Example 2 disclosed in EP 0, 649, 871 A2, the rubber powder was not modified, but the plastic PE was modified with EMMA to increase its Compatibility with rubber.
所制备的橡胶 /塑料热塑性组合物共混物的性能也列于表 1。 表 1.废胶粉 /塑料热塑性弹性体的性能 The properties of the prepared rubber / plastic thermoplastic composition blends are also listed in Table 1. Table 1. Properties of waste rubber powder / plastic thermoplastic elastomer
Figure imgf000016_0001
Figure imgf000016_0001
根据 GB/7531-92中国国家标准测得  Measured according to GB / 7531-92 Chinese National Standard
②根据 GB/7 528-92中国国家标准测得  ②Measured according to GB / 7 528-92 Chinese National Standard
®根据 GB/729-91中国国家标准测得 从上表可以看出， 在橡塑比相同的情况下， 本发明的热塑性弹性体 的性能与现有技术中制得的相比， 其综合物理机械性能有很大提高。 在橡塑比相同的情况下， 由本发明实施例 6制得的热塑性弹性体比 对比例 1 中制得的拉伸强度提高 41.4%; 扯断伸长率提高 100%; 撕裂 强度提高 31.9%. Measured according to Chinese National Standard GB / 729-91. It can be seen from the table above that, under the same rubber-to-plastic ratio, the performance of the thermoplastic elastomer of the present invention is compared with that obtained in the prior art. The mechanical properties have been greatly improved. In the case of the same rubber-plastic ratio, the tensile strength of the thermoplastic elastomer prepared in Example 6 of the present invention was improved by 41.4% compared with that of Comparative Example 1, the elongation at break was increased by 100%, and the tear strength was increased by 31.9%. .
在橡塑比相同的情况下， 由本发明实施例 6制得的热塑性弹性体的 硬度比对比例 2 (在 EP 0, 649, 871 A2 中公开的实施例 2) 中所获得的 要低的多， 因此其扯断伸长率也提高很多 （提高 85% ) , 而拉伸强度也 有提 T¾。  With the same rubber-plastic ratio, the hardness of the thermoplastic elastomer prepared in Example 6 of the present invention is much lower than that obtained in Comparative Example 2 (Example 2 disclosed in EP 0, 649, 871 A2). Therefore, its elongation at break also improved a lot (increased by 85%), and the tensile strength also improved T¾.
因此， 根据本发明得到了综合物理机械性能优良的热塑性弹性体。 实施例 18  Therefore, according to the present invention, a thermoplastic elastomer excellent in comprehensive physical and mechanical properties is obtained. Example 18
将在实施例 2- 6, 9中刚刚制得的热塑性弹性体， 直接送入四辊压 延机 SY4F- 1400 (可从江苏双象集团公司购得）， 压延机辊温控制在 150 180'C之间， 从压延机中送出的片材经冷却、 卷取、 裁断、 制得防 水片材。  The thermoplastic elastomer just obtained in Examples 2- 6, 9 was directly fed into a four-roll calender SY4F-1400 (available from Jiangsu Shuangxiang Group Company), and the roll temperature of the calender was controlled at 150 180'C. In between, the sheet sent out from the calender is cooled, coiled, cut, and a waterproof sheet is made.
实施例 19  Example 19
将在实施例 2, 6, 9 中制得的热塑性弹性体经切粒或造粒后， 送入 单螺杆挤出机 Brabender PLD 651 (可从 Brabender公司（德国）购得）。 螺杆直径 φ30醒， 长径比 24: 1, 机筒温度控制在一段 120"C, 二段 180 , 三段 200X , 四段 200X:, 经过一个管机头， 机头温度 190 ， 制成 管材。  The thermoplastic elastomer obtained in Examples 2, 6, and 9 was pelletized or pelletized, and then fed to a single-screw extruder Brabender PLD 651 (commercially available from Brabender (Germany)). The screw diameter is φ30, the aspect ratio is 24: 1, the barrel temperature is controlled at 120 "C, two 180, three 200X, and four 200X :, after passing a tube head, the head temperature is 190 to make a tube.
实施例 20  Example 20
将实施例 2、 6、 9 中的热塑性弹性体粒料送入注射机料筒中， 注射 机为 UM- 8DiII型注塑机（可从东莞贻光精密机械有限公司购得） ， 机 筒温度控制在一段 140C 二段 180Ό, 三段 220TC、 四段 2201， 喷嘴 温度为 200" , 模具温度控制在 30" ， 注射压力 8MPa, 注射时间 2秒， 冷却保压时间 30秒， 得到了注射制的密封團.  The thermoplastic elastomer pellets in Examples 2, 6, and 9 were fed into the barrel of an injection machine. The injection machine was a UM-8DiII injection molding machine (available from Dongguan Yiguang Precision Machinery Co., Ltd.), and the barrel temperature was controlled at One section of 140C, two sections of 180Ό, three sections of 220TC, four sections of 2201, nozzle temperature is 200 ", mold temperature is controlled at 30", injection pressure is 8MPa, injection time is 2 seconds, and cooling and holding time is 30 seconds. .
因此可以采用已知的塑料成型加工方法， 采用本领域中常用的加工 设备由本发明的热塑性弹性体制备成型制品。  Therefore, a known plastic molding processing method can be used to prepare a molded article from the thermoplastic elastomer of the present invention using processing equipment commonly used in the art.

Claims

权 利 要 求 Rights request
1.一种热塑性弹性体， 其是通过反应加工包含以下組分的配合物制 备的： What is claimed is: 1. A thermoplastic elastomer prepared by reaction processing of a complex comprising:
①粒径小于 10目的废胶粉，  ①Waste rubber powder with particle size less than 10 mesh,
②胶粉改性剂，  ② rubber powder modifier,
③塑料， 其选自聚烯烃、 EVA及 PS中的一种或多种，  ③ plastic, which is selected from one or more of polyolefin, EVA and PS,
④反应性相容剂， 其是分子链中含有硬段区和软段区的共聚物， 该 硬段区由乙烯、 丙烯、 丁烯、 异丁烯、 苯乙烯等单体中的一种或 几种聚合而成， 软段区由天然橡胶、 顺丁橡胶、 丁苯橡胶、 丁基 橡胶、 三元乙丙橡胶等的分子链形成， 或由异戊二烯、 丁二烯等 单体聚合而成， 其中在软段区中含有可用硫磺或含硫化合物、 酚 醛树脂等交联剂交联的〉 c = c <结构， 同时软段区中分子链碳原 子数大于 50,  ④ Reactive compatibilizer, which is a copolymer containing a hard segment region and a soft segment region in the molecular chain. The hard segment region is composed of one or more of ethylene, propylene, butene, isobutylene, styrene and other monomers. Polymerized, the soft segment area is formed by molecular chains of natural rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, ethylene propylene diene rubber, etc., or polymerized by monomers such as isoprene and butadiene Wherein the soft segment region contains a structure that can be crosslinked with a crosslinking agent such as sulfur or a sulfur-containing compound, a phenolic resin, and the like. C = c <structure, and the number of carbon atoms in the molecular chain in the soft segment region is greater than 50,
⑤交联体系， 包括交联剂、 交联促进剂、 交联活性剂等；  ⑤ Cross-linking system, including cross-linking agent, cross-linking accelerator, cross-linking active agent, etc .;
该制备方法包括第一步将废胶粉与一种或多种改性剂在开炼机、 密炼机 或双螺杆挤出机中进行改性， 操作条件： 温度 10 - lOOC 时间 3 - 15 分钟； 第二步将改性废胶粉与塑料、 反应性相容剂、 交联体系等加入到 开炼机、 密炼机或双螺杵挤出机中进行反应加工， 加工温度 100" ~ 200 时间 3 - 15分钟。 The preparation method includes the first step of modifying the waste rubber powder and one or more modifiers in an open mill, an internal mixer or a twin-screw extruder, and the operating conditions are: temperature 10-100C time 3-15 Minutes; the second step is to add modified waste rubber powder and plastic, reactive compatibilizer, cross-linking system, etc. into the open mill, mixer or twin screw pestle extruder for reaction processing, processing temperature 100 "~ 200 time 3-15 minutes.
2.权利要求 1 的热塑性弹性体， 其中， 所述的配合物还可包括防老 剂。  The thermoplastic elastomer according to claim 1, wherein the complex further comprises an antioxidant.
3.权利要求 1 的热塑性弹性体， 其中， 所述的配合物中各組分的重 量组成份数为：  The thermoplastic elastomer according to claim 1, wherein the weight composition of each component in the complex is:
废胶粉、 塑料及相容剂： 100份  Waste rubber powder, plastic and compatibilizer: 100 parts
其中 废胶粉 50 - 90重量份  Of which 50-90 parts by weight of waste rubber powder
塑料 3 - 47重量份  Plastic 3-47 parts by weight
相容剂 3 - 47重量份  Compatibilizer 3-47 parts by weight
胶粉改性剂： 0. 1 - 5重量份  Rubber powder modifier: 0.1-5 parts by weight
交联体系： 交联剂 0. 1 - 3重量份、 交联促进剂 0. 1 - 5重量份、 交 联活性剂 0. 1 - 8重量份。 Crosslinking system: 0.1 to 3 parts by weight of a crosslinking agent, 0.1 to 5 parts by weight of a crosslinking accelerator, and 0.1 to 8 parts by weight of a crosslinking active agent.
4.权利要求 1 的热塑性弹性体， 其中， 所述的配合物还可包括防老 剂： 0. 5 3重量份. 4. The thermoplastic elastomer according to claim 1, wherein said complex further comprises an antioxidant: 0.5 3 parts by weight.
5.权利要求 1的热塑性弹性体， 其中， 所述的配合物还可包括 0 - 10 重量份的软化增塑剂.  5. The thermoplastic elastomer according to claim 1, wherein said complex further comprises 0 to 10 parts by weight of a softening plasticizer.
6.由上述权利要求 1 - 5 热塑性弹性体通过传统的成型加工方法而 制备的成型制品。  6. A molded article prepared from the thermoplastic elastomer according to claims 1 to 5 by a conventional molding processing method.
7. 权利要求 6的成型制品， 其是通过压延方法制备的，  7. The shaped article according to claim 6, which is prepared by a calendering method,
8. 权利要求 6的成型制品， 其是通过挤塑方法制备的。  8. The shaped article of claim 6, which is prepared by an extrusion method.
9- 权利要求 6的成型制品， 其是通过注塑方法制备的。  9- The shaped article according to claim 6, which is prepared by an injection molding method.
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