WO2002026869A1 - Matiere plastique malleable et son procede de fabrication - Google Patents

Matiere plastique malleable et son procede de fabrication Download PDF

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Publication number
WO2002026869A1
WO2002026869A1 PCT/CN2001/001265 CN0101265W WO0226869A1 WO 2002026869 A1 WO2002026869 A1 WO 2002026869A1 CN 0101265 W CN0101265 W CN 0101265W WO 0226869 A1 WO0226869 A1 WO 0226869A1
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Prior art keywords
rubber
plastic
fully vulcanized
vulcanized powder
toughness
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Ceased
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PCT/CN2001/001265
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English (en)
French (fr)
Inventor
Jinliang Qiao
Shijun Zhang
Xiaohong Zhang
Yiqun Liu
Jianming Gao
Wei Zhang
Genshuan Wei
Jingbo Shao
Hua Yin
Renli Zhai
Zhihai Song
Fan Huang
Jiuqiang Li
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority claimed from CNB001235591A external-priority patent/CN1137194C/zh
Priority claimed from CNB001303872A external-priority patent/CN1137933C/zh
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to JP2002531245A priority Critical patent/JP5443661B2/ja
Priority to EP01982071A priority patent/EP1314752A4/en
Priority to AU2002213767A priority patent/AU2002213767A1/en
Priority to KR1020037002546A priority patent/KR100762500B1/ko
Publication of WO2002026869A1 publication Critical patent/WO2002026869A1/zh
Priority to US10/126,461 priority patent/US6998438B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to a toughened plastic and a preparation method thereof. More specifically, the present invention relates to a high toughness plastic prepared by blending powder rubber with a tough plastic and a blend prepared by blending low portion powder rubber with a crystalline plastic. High rigidity and high toughness plastic and preparation method of these plastics.
  • Plastics As a widely used material, plastics are receiving more and more attention. According to the article published by POLYMER INTERNATIONAL VOL. 29, No. 3, (1992) 229-247 by Souheng Wu of DuPont of the United States: Plastics can be divided into tough plastics and brittle plastics due to different characteristics of polymer chains. When the plastic chain entanglement density Ve ⁇ 0.15mmol / ml and the characteristic ratio C> ⁇ 7.5, the external impact energy is mainly dissipated by the formation of silver grains in the matrix, which is a brittle plastic.
  • the plastic chain entanglement density Ve> When it is ⁇ 0.15 mmol / ml and the characteristic ratio C » ⁇ 7.5, the external impact energy mainly dissipates energy through the shear yield of the matrix, which is a ductile plastic. Both tough and brittle plastics can be blended with rubber to further increase toughness.
  • Patent The United States Dupont company described in US4517319 selected isocyanurate-based copolymer elastomers to toughen polyoxymethylene, the German Hoechst company described in European patents EP120711 and EP121407 used diolefin graft polymer elastomers to toughen polyoxymethylene, European patent EP117664 The Japanese Asahi Kasei Company selected styrene block copolymer elastomer to toughen polyoxymethylene and the patents FR8519421, FR8803877, FR9512701, FR9609148 of France Ato Chemical Co., Ltd., JP127503 / 97 of Mitsui Chemical Co., Ltd., Japan Kishimoto Industry Co., Ltd.
  • inorganic rigid particles can also toughen some plastics (plastics with a certain toughness in the matrix), while maintaining their rigidity without decreasing, which is the so-called rigid particle toughening method (see Li Dongming and Qi Zongneng, "Calcium Carbonate Reinforcement” Fracture toughness of polypropylene composites ", Polymer Materials Science and Engineering, No. 2, 1991, pp. 18-25).
  • rigid particle toughening method see Li Dongming and Qi Zongneng, "Calcium Carbonate Reinforcement” Fracture toughness of polypropylene composites ", Polymer Materials Science and Engineering, No. 2, 1991, pp. 18-25.
  • the toughening effect is very limited. It has not yet obtained industrial application and is still in the experimental exploration stage.
  • inorganic nanoparticles can also toughen and maintain rigidity, such as the "Journal of Polymer", 2000, No. 1, pp. 99-104 reported that the use of nano-Si0 2 toughened polypropylene in the Si0 2 content of 1.5-5 % Has a room temperature toughening and strengthening effect on PP, but currently there are still some problems in industrialized production of inorganic nanoparticle-toughened plastics, such as poor dispersion in the resin matrix, which affects its final toughening effect.
  • the inventors found that a specific type of powder rubber different from the various toughening agents used as the rubber-based toughening agent has a size up to the nanometer level and is easily dispersed in the resin. Compared with ordinary rubber toughened and toughened plastics, the toughened plastics using this kind of rubber toughener have higher addition amount (10 parts by weight or more based on 100 parts by weight of plastics). The toughening effect of the rubber toughener is significantly better than other rubbers.
  • the addition amount of the rubber toughening agent of the present invention can be significantly less than other rubbers, so that the rigidity loss of the toughened plastic is lower than that of the ordinary rubber toughened plastic, which is conducive to obtaining a more ideal Rigid and tough balance effect.
  • the rubber toughener of the present invention can ensure good dispersion of powder rubber in plastic matrix for some resins, especially for some crystalline plastics, such as polypropylene, polyethylene, and PBT.
  • the toughness and rigidity of the plastic are improved at the same time, and the thermal deformation temperature and crystallization temperature of the material are also improved, thereby achieving an excellent rigid-tough balance. This shows that adding a small amount of ultra-fine powder rubber to crystalline plastics will not only function as a toughener, but also function as a reinforcing agent.
  • an object of the present invention is to provide a high-toughness plastic with a small average rubber particle size, a uniform rubber particle size, and stability. Even if its rubber content reaches 70% by weight, no reverse rotation occurs, and the rubber remains in a dispersed phase at all times.
  • the high-toughness plastic has higher toughness and better rigidity.
  • Another object of the present invention is to provide a high-rigidity and high-toughness plastic containing a small amount of ultrafine powder rubber toughener. Compared with the pure plastic matrix, the high rigidity and high toughness plastic has improved rigidity and toughness at the same time.
  • Another object of the present invention is to provide a method for preparing the high-toughness plastic and the high-rigidity and high-toughness plastic.
  • the method is simple in process and easy to operate.
  • a high-toughness plastic which includes the following components: a tough plastic with a polymer chain entanglement density Ve> ⁇ 0.15 mmol / ml, a characteristic ratio C » ⁇ 7.5, and an average particle size 20 to 200 nm rubber particles, where the weight ratio of rubber particles to plastic is 0.5: 99.5-70:30.
  • the toughened and modified plastic has good comprehensive properties of good rigidity and toughness balance.
  • a high-rigidity and high-toughness plastic which includes the following components: a crystalline plastic and rubber particles having an average particle diameter of 20 to 500 nm, wherein the amount of rubber particles added to the plastic matrix is based on 100 parts by weight of the plastic matrix is 0.3 5 parts by weight.
  • a method for preparing a high-performance plastic of the present invention which includes a tough plastic and an average particle of a polymer chain entanglement density Ve> ⁇ 0.15mmol / ml and a characteristic ratio C » ⁇ 7.5
  • the rubber particles with a diameter of 20 ⁇ 200nm are blended, wherein the weight ratio of the rubber particles to the plastic is 0.5: 99.5-70:30.
  • a method for preparing the high rigidity and high toughness plastic of the present invention includes melt blending crystalline plastic and rubber particles having an average particle diameter of 20 to 500 nm, wherein the amount of rubber particles added to the plastic matrix is 0.3 to 5 parts based on 100 parts by weight of the plastic matrix.
  • FIG. 1 is an atomic force microscope photograph of the sample obtained in Example 5, with a magnification of 40,000 times.
  • the weight ratio of the rubber particles to the plastic is 0.5: 99.5-70:30, preferably 5:95-50:50.
  • the average particle diameter of the rubber particles is between 20 and 200 nm, and preferably between 50 and 150 nm.
  • the plastic as the continuous phase is a tough plastic having a polymer chain entanglement density Ve> to 0.15 mmol / ml and a characteristic ratio C ⁇ to 7.5, and may be selected from polypropylene, polyethylene, and polyamide. , Polyoxymethylene, polycarbonate, polyester, polyphenylene ether or polyurethane.
  • the rubber particles as the dispersed phase are preferably rubber particles having a homogeneous structure, and they are preferably crosslinked rubber particles having a gel content of> 60%.
  • This kind of rubber particles may be a fully vulcanized powder rubber prepared in accordance with Chinese Patent Application No.
  • This fully vulcanized powder rubber refers to discrete rubber powders with a gel content of more than 60%, which can flow freely without adding a release agent after drying.
  • the powder rubber is used to fix the particle diameter of rubber particles by radiation crosslinking.
  • the rubber phase contained in the high-toughness plastic of the present invention has a small particle size, and the particle size is uniform and stable, and it is easy to achieve a high rubber-plastic ratio; it has high toughness and good processability, and is suitable for a very wide range of fields.
  • the amount of the rubber particles is 0.3 to 5 parts by weight, preferably 0.5 to 2 parts by weight based on 100 parts by weight of the plastic matrix.
  • the average particle diameter of the rubber particles is 20 to 500 nm, preferably 50 to 300 nm.
  • the plastic as the continuous phase is a crystalline plastic, and may be selected from polypropylene, polyethylene, polyamide, polyoxymethylene, polybutylene terephthalate (PBT), and poly Poly (ethylene terephthalate) (PET), etc.
  • the rubber particles as the dispersed phase are preferably rubber particles having a homogeneous structure, and they are preferably crosslinked rubber particles having a gel content of not less than 60%.
  • This kind of rubber particles can be a fully vulcanized powder rubber prepared in accordance with Chinese Patent Application No. 99125530.5 filed by the inventor on December 3, 1999, as described above for the high toughness plastic.
  • This fully vulcanized powder rubber refers to discrete rubber powders with a gel content of more than 60%, which can flow freely without adding a release agent after drying.
  • the fully vulcanized powder rubber can be obtained by crosslinking the rubber emulsion by irradiation. When fully vulcanized powder rubber is mixed with plastic, these particles are easily and uniformly dispersed in the plastic, are not easy to aggregate, and can maintain a small particle size.
  • the high-rigidity and high-toughness plastic contained in the invention has a small particle diameter, and the particle size is uniform and stable; it has high rigidity, high toughness and higher heat distortion temperature, good processing and formability, and is applicable to a very wide range of fields.
  • the high toughness plastic of the present invention can be prepared by blending a tough plastic with a polymer chain entanglement density Ve> to 0.15 mmol / ml, a characteristic ratio C » ⁇ to 7.5, and the above-mentioned rubber particles having an average particle diameter of 20 to 200imi. .
  • the average particle diameter of the rubber particles is preferably between 50 and 150 nm.
  • the weight ratio of the rubber particles to the plastic is 0.5: 99.5-70:30, preferably 5:95-50:50.
  • the high-rigidity and high-toughness plastic of the present invention can be obtained by blending a crystalline plastic with the above-mentioned rubber particles having an average particle diameter of 20 to 500 nm.
  • the amount of rubber particles added to the plastic matrix is 0.3 to 5 parts, preferably 0.5 to 2 parts, based on 100 parts by weight of the plastic matrix.
  • the average particle diameter of the rubber particles is preferably between 50 and 300 nm.
  • the fully vulcanized powder rubber may be added in the form of a dry crosslinked powder or in the form of an undried crosslinked emulsion.
  • the blending temperature of the materials is the blending temperature used in ordinary plastic processing. It can be determined according to the melting temperature of the base plastic. It should be in a range that ensures that the base plastic is completely melted without decomposing the plastic. Select within.
  • conventional additives for plastics processing such as plasticizers, antioxidants, light stabilizers, and compatibilizers, can be added to the blended materials in appropriate amounts.
  • the blending equipment used in this method is a universal blending equipment in the rubber and plastics processing industry, and may be a single screw extruder, a screw extruder, an open mill or an internal mixer.
  • the method for preparing high-toughness plastics and high-rigidity and high-toughness plastics according to the present invention is simple, easy to operate, and suitable for toughening various plastics.
  • the fully vulcanized styrene-butadiene powder rubber (in the styrene-butadiene-50 emulsion in the Lanhua Latex Development Center) was added with 3% by weight of the dry rubber of the styrene-butadiene emulsion to the crosslinking auxiliary trimethylolpropane triacrylate, and then irradiated.
  • Adopt ZSK-25 twin screw of German WP company The extruder is blended and pelletized, and the temperature of each section of the extruder is: 170 ° C;, 185, 190 V, 190 ° C, 190 ° C and 190 ° C (head temperature).
  • the specific formula is shown in Table 1.
  • the content of the components of the fully vulcanized powdered styrene-butadiene rubber and polypropylene are both based on parts by weight, and the antioxidant is based on the weight percentage of the total of the components.
  • the pellets were made into standard splines by injection molding and tested for various mechanical properties. The test standards and results are shown in Table 1.
  • Example 1 The polypropylene powder and the antioxidant in Example 1 were both mixed and granulated by a twin-screw extruder, and the remaining conditions were the same as in Example 1.
  • the specific formula and mechanical test results are listed in Table 1.
  • Example 1 The fully vulcanized styrene-butadiene powder rubber (same as in Example 1) and polypropylene pellets (Jinan Refinery, brand T30S) and antioxidant 1010 (produced by Ciba Gage, Switzerland) were uniformly mixed and blended through an extruder Granulation and processing conditions were the same as in Example 1.
  • the specific formulations are shown in Table 1, where the component contents of the fully vulcanized powdered styrene-butadiene rubber and polypropylene are based on parts by weight, and the antioxidant is based on the weight percentage of the total of the components.
  • the obtained pellets are made into standard splines by injection molding, and tested for various mechanical properties. The test standards and results are shown in Table 1.
  • Example 3 The polypropylene pellets and EPDM rubber pellets (manufactured by DuPont Dow, brand 3745) in Example 3 were uniformly mixed at a weight ratio of 9/1, and the antioxidant 1010 (same as in Example 1) was added and passed. The extruder was blended and pelletized, and the processing conditions were the same as in Example 1. The obtained pellets are made into standard splines by injection molding, and various mechanical properties tests are performed. The test standards and results are shown in Table 1. Table 1
  • the fully vulcanized powder carboxystyrene styrene-butadiene rubber (XSBRL-54B1 carboxy styrene-butadiene emulsion produced by Yanshan Petrochemical Co., Ltd. was mixed with 3% by weight of the dry weight of the carboxystyrene styrene-butadiene emulsion into the crosslinking assistant isooctyl acrylate, and then irradiated.
  • the components of the fully vulcanized powdered carboxylated butadiene rubber and nylon 6 are based on parts by weight, and other additives are based on the weight percentage of the total of the components.
  • the pellets are dried and made into a standard by injection molding.
  • the spline was tested for various mechanical properties.
  • the test standards and performance results are shown in Table 2.
  • the atomic force microscope photo of the sample in Example 5 is shown in Figure 1 (magnification: 40,000), where the black shade is distributed on nylon Particles of the fully vulcanized carboxylated styrene-butadiene rubber in 6.
  • Example 4 After the nylon 6 and calcium stearate and ultrafine talc powder in Example 4 were uniformly mixed, they were blended and pelletized by a twin-screw extruder, and the remaining conditions were the same as in Example 4. The specific formula, test standards and performance results are shown in Table 2.
  • the remaining conditions are the same as in Example 4.
  • the specific formulations are shown in Table 2.
  • the components of the acrylic rubber and nylon 6 are based on parts by weight, and the other additives are based on the weight percentage of the total of the components.
  • the test standards and performance results are shown in Table 2.
  • Example 4 POE grafted with nylon 6 and maleic anhydride in Example 4 (ie, POE-g-MAH, produced by United Carbon Chemical Corporation (UCC), brand name DFDA1373), and calcium stearate described in Example 4 and The ultra-fine talc powder was blended and pelletized by a twin-screw extruder after mixing, and the remaining conditions were the same as in Example 4.
  • the specific formulations are shown in Table 2.
  • the maleic anhydride-grafted POE and nylon 6 component contents are based on parts by weight, and other additives are based on the weight percentage of the total of the components. Test standards and performance results are shown in Table 2.
  • Example 6 Example 6
  • Example 4-5 The operations of Examples 4-5 were repeated, except that the ratio of the powdered carboxylated styrene-butadiene rubber to Nylon 6 was changed to 15:85.
  • the test standards and performance results are shown in Table 2.
  • the fully vulcanized powder carboxylated styrene-butadiene rubber (XSBRL-54B1 carboxylated styrene-butadiene emulsion produced by Yanshan Petrochemical Co., Ltd. was mixed with 3% by weight of the dry weight of the carboxylated styrene-butadiene emulsion and mixed with isooctyl acrylate, and then irradiated.
  • ZSK-25 screw extruder from Germany WP company was used for blending and pelletizing.
  • the temperatures of each section of the extruder were: 175 ° C :, 180 ⁇ , 185 ;, 185 ° C, 180 ° C and 175 ° C (head Temperature).
  • the specific formula is shown in Table 3.
  • the content of the components of the fully vulcanized carboxylated styrene-butadiene rubber and polyoxymethylene are based on parts by weight, and other additives are based on the weight percentage of the total of the components. After the pellets are dried, they are made into standard splines by injection molding and tested for various mechanical properties. Test standards and performance results are shown in Table 3.
  • Example 7 The polyformaldehyde and calcium stearate, antioxidant 1010, polyethylene wax and ultrafine talc powder in Example 7 were uniformly mixed and pelletized by a twin-screw extruder, and the remaining conditions were the same as those in Example 7.
  • the specific formula, test standards and performance results are shown in Table 3.
  • Example 7 After mixing the polyoxymethylene in Example 7 with acrylate rubber (Lucite44-N from DuPont, USA) and the calcium stearate, antioxidant 1010, polyethylene wax and ultrafine talc powder in Example 7, The pellets were blended through a screw pestle extruder, and the remaining conditions were the same as in Example 7.
  • the formulations are shown in Table 3, where the component content of the acrylate rubber and polyoxymethylene are based on parts by weight, and the other additives are based on the weight percentage of the total of the components. Test standards and performance results are shown in Table 3.
  • the temperature of each section of the machine is: 265 ° C, 270, 275 275 ° C, 270 and 265 ° C (head temperature). See Table 4 for specific recipes.
  • the component content of the fully vulcanized powder butyl acrylate rubber and the polycarbonate is calculated in parts by weight. After the pellets are dried, they are made into standard splines by injection molding and tested for various mechanical properties. The test standards and performance results are shown in Table 4.
  • Example 9 The polycarbonate in Example 9 was directly made into a standard spline by injection molding, and various mechanical properties were tested. The test standards and performance results are shown in Table 4.
  • Polypropylene pellets produced by Jinan Refinery, brand T30S
  • vulcanized polybutadiene powder rubber in polybutadiene emulsion of Jihua Synthetic Resin Plant, brand 0700
  • the crosslinking auxiliary trimethylolpropane triacrylate was added at 3% of the dry weight of the emulsion, and then cured by irradiation.
  • the irradiation dose was 2Mrad, which was obtained after spray drying.
  • the average particle size was 280nm and the gel content was 88.5%.
  • antioxidant 1010 (produced by Ciba Gaga, Switzerland), based on 100 parts by weight of plastic, the specific composition is: 100 parts of polypropylene, 0.5 parts of fully vulcanized polybutadiene powder rubber, antioxidant The agent is 0.5 parts.
  • ZSK-25 screw extruder from Germany WP company was used for blending and pelletizing. The temperatures of each section of the extruder were: 170 ° C; 185 ° C; 190 ° C; 190 ° C; 190 ° C and 190 ° C (head temperature).
  • the pellets were made into standard splines by injection molding and tested for various mechanical properties. The results are shown in Table 5.
  • Example 10 The amount of fully vulcanized polybutadiene powder rubber in Example 10 was changed to 1 part, and the remaining conditions were the same as in Example 10.
  • the pellets were made into standard splines by injection molding, and various mechanical properties were tested. The results of the mechanical tests are listed in table 5.
  • Example 10 The amount of fully vulcanized polybutadiene powder rubber in Example 10 was changed to 1.5 parts, and the remaining conditions were the same as in Example 10.
  • the pellets were made into standard splines by injection molding, and various mechanical properties were tested. The results of the mechanical tests are listed in table 5.
  • Example 10 The amount of fully vulcanized polybutadiene powder rubber in Example 10 was changed to 2 parts, and the conditions were the same as in Example 10. The pellets were made into standard splines by injection molding, and various mechanical properties were tested. ⁇ ⁇ 5 ⁇ In Table 5.
  • Example 10 The polypropylene pellets in Example 10 were directly injection-molded into a standard spline and tested for various mechanical properties. The mechanical test results are shown in Table 5.
  • the styrene-butadiene rubber (Jihua Organic Synthesis Plant, brand name: 1502) was used in place of the fully vulcanized polybutadiene powder rubber in Example 11, and the remaining conditions were the same as in Example 11.
  • the standard spline was made by injection molding and tested for various mechanical properties. The mechanical test results are shown in Table 5.
  • Polypropylene powder produced by Tianjin No. 2 Petrochemical Plant, type 3-1
  • fully vulcanized styrene-butadiene powder rubber emulsion (Dingben-50 emulsion in Lanhua Latex Development Center, with a solid content of 45%, dried as the emulsion 3% of the weight of the gum was added with cross-linking aid trimethylolpropane triacrylate, and then cured by irradiation.
  • the irradiation dose was 2.5Mrad
  • the average particle size of the emulsion particles was 100nm
  • the gel content was 90.4%.
  • Example 14 The polypropylene powder in Example 14 was mixed with the antioxidant, and then extruded and injection-molded to produce a standard spline, and tested for various mechanical properties. The mechanical test results are shown in Table 5.
  • Vulcanized by irradiation the irradiation dose is 2.5Mrad, obtained by spray drying, the average particle size is 100nm, the gel content is 87.7%) and polyethylene terephthalate (produced by Yanshan Petrochemical, intrinsic viscosity 0.76) and Calcium stearate (Beijing Changyang Chemical Plant, chemically pure), ultra-fine talc (Hebei Luquan Building Material Factory, 1250 mesh) are mixed together, and the specific composition in terms of parts by weight is: fully vulcanized powder butyl acrylate rubber 0.5 parts, polyethylene terephthalate 100 parts, calcium stearate 0.3 parts, ultra fine talc 0.3 parts.
  • Example 15 The group distribution ratio in Example 15 was changed to: 1 part of fully vulcanized powder butyl acrylate rubber and 100 parts of polyethylene terephthalate. The conditions were the same as those in Example 15, and the pellets were made standard by injection molding. The splines were tested for various mechanical properties. The results of the mechanical tests are listed in Table 6.
  • Example 15 The group distribution ratio in Example 15 was changed to: 2 parts of fully vulcanized butyl acrylate rubber and 100 parts of polyethylene terephthalate. The remaining conditions were the same as in Example 15. The pellets were made into a standard sample by injection molding. The test results are shown in Table 6.
  • Example 15 The group distribution ratio in Example 15 was changed to: 5 parts of fully vulcanized powder butyl acrylate rubber and 100 parts of polyethylene terephthalate. The remaining conditions were the same as in Example 15. The pellets were made into a standard sample by injection molding. The test results are shown in Table 6.
  • Polyethylene terephthalate (same as Example 15) was made into a standard spline by injection molding and tested for various mechanical properties. The mechanical test results are shown in Table 6.
  • a fully vulcanized powder butyl acrylate rubber (same as Example 15), polybutylene terephthalate (BASF, brand 4500, intrinsic viscosity 1.02), and calcium stearate (Beijing Changyang Chemical Plant, chemically pure), Fine talc powder (Hebei Luquan City Building Material Factory, 1250 mesh) is mixed together, and the specific composition is calculated as parts by weight: 0.5 part of fully vulcanized powder butyl rubber, 100 parts of polybutylene terephthalate, 0.3 parts of calcium stearate and 0.3 parts of super fine talc. ZSK-25 twin-screw extruder from Germany WP company was used for blending and pelletizing.
  • the temperatures of each section of the extruder were: 220 ", 240 ° C, 240 V, 240V, 245 X and 240 ° C (head temperature) After the pellets are dried, they are made into standard splines by injection molding and tested for various mechanical properties. The test standards and performance results are shown in Table 7.
  • Example 19 The group distribution ratio in Example 19 was changed to: 1 part of fully vulcanized butyl acrylate rubber and 100 parts of polybutylene terephthalate. The remaining conditions were the same as in Example 19, and the pellets were made into a standard sample by injection molding. Strip, perform various mechanical property tests, mechanical tests The results are shown in Table 7.
  • Example 19 The group distribution ratio in Example 19 was changed to: 2 parts of fully vulcanized powder butyl acrylate rubber and 100 parts of polybutylene terephthalate. The remaining conditions were the same as in Example 19, and the pellets were made into a standard sample by injection molding. The test results are shown in Table 7.
  • Example 19 The group distribution ratio in Example 19 was changed to: 5 parts of fully vulcanized powder butyl acrylate rubber and 100 parts of polybutylene terephthalate. The conditions were the same as in Example 19, and the pellets were made standard by injection molding. The spline was tested for various mechanical properties. The results of the mechanical tests are listed in Table 7.
  • Polybutylene terephthalate (same as Example 19) was made into a standard spline by injection molding, and various mechanical properties were tested. The mechanical test results are shown in Table 7.

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Description

增韧塑料及其制备方法 技术领域
本发明涉及增韧塑料及其制备方法， 更具体地说， 本发明涉 及利用粉末橡胶与韧性塑料共混而制得的高韧性塑料和利用低份 数粉末橡胶与结晶型塑料共混而制得的高刚高韧性塑料以及这些 塑料的制备方法。
发明背景
塑料作为一种应用广泛的材料越来越受到人们的重视。 根据 美 国 杜 邦 公 司 的 Souheng Wu 发表 于 POLYMER INTERNATIONAL VOL. 29， No.3, ( 1992 ) 229 - 247上的文章 所述： 塑料由于高分子链特征属性不同可分为韧性塑料和脆性塑 料。 当塑料的链缠结密度 Ve< ~ 0.15mmol/ml、 特征比 C > ~ 7.5 时， 对于外来冲击能主要以基体形成银紋来耗散， 属于脆性塑料； 当塑料的链缠结密度 Ve> ~ 0.15mmol/ml、 特征比 C»< ~ 7.5时， 对于外来冲击能主要以基体产生剪切屈服来耗散能量， 属于韧性 塑料。 无论韧性塑料还是脆性塑料均可通过与橡胶共混来进一步 提高韧性。
许多科学家对塑料增韧理论和增韧方法进行了广泛的研究。 八十年代 Souheng Wu提出了塑料增韧的逾渗理论， 指出在橡胶 增韧塑料中， 塑料发生脆韧转变的条件是： 橡胶作为分散相其粒 子之间的距离 τ小于一特定的临界距离^时， 即发生脆韧转变。 由 于橡胶相的粒子之间距离 τ与橡胶相的粒子直径 d 之间存在关系 式： α - τΠ υ/φι ^-ΙΓ1, 故当橡胶粒子直径 d 小于临界直径 dc 时， 即发生脆韧转变。 也就是说分散的橡胶相其粒径越小， 增韧 塑料越容易发生脆韧转变。 现有的橡胶增韧塑料的技术中， 将橡 胶作为增韧剂与塑料共混而得到增韧塑料。 如美国专利 US4517319所述的美国 Dupont公司选用异氰酸聚氨酯类共聚物 弹性体增韧聚甲醛、欧洲专利 EP120711和 EP121407所记载的德 国 Hoechst公司选用二烯烃接枝聚合物弹性体增韧聚甲醛、 欧洲 专利 EP117664所迷的日本旭化成公司选用苯乙烯嵌段共聚物弹 性体增韧聚甲醛以及法国阿托化学公司的专利 FR8519421、 FR8803877, FR9512701, FR9609148, 日本三井化学株式会社的 专利 JP127503/97、 日本岸本产业抹式会社的专利 JP190634/97、 JP90635/97记载的用马来酸酐接枝乙丙胶增韧聚酰胺等橡胶增韧 塑料的技术。 其存在如下不足之处： （1 )在目前的橡塑加工的共 混条件下， 作为分散相的橡胶粒径难以控制在较小的范围， 一般 平均橡胶相粒子直径大于 200nm。 若要实现脆韧转变， 则需要较 大份数的橡胶， 从而造成增韧塑料刚性的降低； （2 )橡胶相粒径 不稳定， 随着加工过程中剪切速率等因素的变化， 增韧塑料中的 橡胶相粒径一直在变化中； （3 ) 橡胶相粒径很不均匀； （4 ) 橡 胶含量不能超过 40 % , 否则易出现 "海-海" 相态结构， 甚至出 现相反转， 使增韧塑料的性能变差。
另外， 由于韧性和刚性是塑料的两个重要的力学性能指标， 如何大幅度地提高塑料的韧性而同时保持其应有的刚性， 即获得 刚韧平衡的材料， 一直是人们不断追求的目标。 目前较能有效地 提高塑料韧性的方法是将橡胶类弹性体材料作为增韧剂分散于塑 料基质中进行增韧， 如采用 EPR、 EPDM增韧 PP, 采用丙烯酸 酯橡胶增韧聚酯等， 但使用橡胶等弹性体在增韧的同时会使塑料 的弯曲强度、 弯曲模量等刚性力学指标下降， 目前还未见有只使 用橡胶类弹性材料能同时提高韧性和刚性的报道。
为了提高塑料韧性又要保持其刚性， 人们通常将橡胶和刚性 的无机填料（云母、 滑石粉等） 并用来改性塑料。 即通过弹性的 橡胶相来提高塑料的韧性， 同时通过所加入的无机填料来弥补橡 胶相加入所引起的刚性下降。 但用无机填料来增强时， 其加入量 一般均较大（基于 100重量份塑料为 20重量份以上 ) , 这会给增 韧塑料带来种种不利的影响， 如增加塑料的密度， 使其加工性能 变差等等。
另外， 采用无机刚性粒子对部分塑料（基体具有一定韧性的 塑料） 也可增韧， 同时可保持其刚性不下降， 即所谓的刚性粒子 增韧方法（参见李东明和漆宗能， "碳酸钙增强聚丙烯复合材料 的断裂韧性"， 高分子材料科学与工程， 1991年第 2期， 第 18-25 页）。 但对这种刚性粒子增韧的方法而言， 其增韧效果非常有限， 尚未获得工业应用， 仍处于实验探索阶段。
采用无机纳米粒子也可增韧并能保持刚性，如"高分子学报"， 2000年第 1期， 第 99-104页所报道的采用纳米 Si02增韧聚丙烯 在 Si02含量为 1.5-5%时对 PP具有室温增韧增强的效果， 但目前 采用无机纳米粒子增韧塑料在工业化生产上仍存在一定问题， 如 在树脂基体中的分散较差， 从而影响其最终的增韧效果。
发明概迷
本发明人经过长期深入的研究后发现， 使用有别于上迷各种 增韧剂的一类特定粉末橡胶作为橡胶类增韧剂， 其尺寸可达纳米 级， 在树脂中极易分散。 使用该类橡胶增韧剂增韧韧性塑料与使 用普通橡胶增韧韧性塑料相比， 在添加量较高 （基于 100重量份 塑料为 10重量份以上）时， 同样的添加份数下， 本发明的橡胶增 韧剂的增韧效果要明显优于其他橡胶。在达到相同的增韧指标时， 本发明的橡胶增韧剂的添加量可明显少于其他橡胶， 从而使增韧 塑料的刚性损失要低于普通橡胶增韧的塑料， 因而有利于获得较 理想的刚韧平衡效果。 尤其是在添加量较低的情况下， 本发明的 橡胶增韧剂对部分树脂， 尤其是对于一些结晶型塑料， 如聚丙烯、 聚乙烯、 PBT等， 在保证粉末橡胶在塑料基质中分散良好时， 可 使塑料的韧性和刚性同时提高， 而且材料的热变形温度、 结晶温 度也得到提高， 从而达到优异的刚韧平衡。 这说明， 在结晶型塑 料中添加很少量的超细粉末橡胶不但会起到增韧剂的作用， 同时 也会起到补强剂的作用。
因此，本发明的一个目的是提供一种所含橡胶相平均粒径小， 且橡胶粒径均句、 稳定的高韧性塑料。 即使其橡胶含量达 70重量 %也不出现相反转， 橡胶始终保持为分散相。 该高韧性塑料在具 有较高韧性的同时也具有较好的刚性。
本发明的另一目的是提供一种含有少量超细粉末橡胶增韧剂 的高刚高韧性塑料。 该高刚高韧性塑料与纯的塑料基质相比， 其 刚性和韧性同时提高。
本发明的又一目的是提供所述高韧性塑料和所迷高刚高韧性 塑料的制备方法， 该方法工艺筒单， 易于操作。
在本发明的第一方面， 提供了一种高韧性塑料， 其包含以下 组分： 高分子链缠结密度 Ve> ~ 0.15mmol/ml、 特征比 C»< ~ 7.5 的韧性塑料和平均粒径为 20 ~ 200nm的橡胶粒子， 其中橡胶粒子 和塑料的重量比为 0.5:99.5 - 70:30。 该种增韧改性的塑料具有良 好的刚韧平衡的综合性能。
在本发明的第二方面， 提供了一种高刚高韧性塑料， 其包含 以下组分： 结晶型塑料和平均粒径为 20 ~ 500nm的橡胶粒子， 其 中橡胶粒子在塑料基质中的添加量基于 100 重量份塑料基质为 0.3 5重量份。
在本发明的第三方面， 提供了一种制备本发明高 性塑料的 方法， 包括将高分子链缠结密度 Ve> ~ 0.15mmol/ml、 特征比 C» < ~ 7.5 的韧性塑料和平均粒径为 20 ~ 200nm 的橡胶粒子进行共 混， 其中橡胶粒子和塑料的重量比为 0.5:99.5 - 70:30。
在本发明的第四方面， 提供了一种制备本发明高刚高韧性塑 料的方法， 包括将结晶型塑料和平均粒径 20 ~ 500nm的橡胶粒子 进行熔融共混， 其中橡胶粒子在塑料基质中的添加量基于 100 重量份塑料基质为 0.3 ~ 5份。
附图简迷
图 1为实施例 5所得样品的原子力显微镜照片， 放大倍数为 4万倍。
发明详迷
在本发明的高韧性塑料中， 橡胶粒子和塑料的重量比为 0.5:99.5 - 70:30, 优选 5:95 - 50:50。 橡胶粒子的平均粒径为 20 ~ 200nm之间， 优选为 50 ~ 150nm之间。
在本发明的高韧性塑料中， 作为连续相的塑料是高分子链缠 结密度 Ve> ~ 0.15mmol/ml、 特征比 C < ~ 7.5的韧性塑料， 可以 选自聚丙烯、 聚乙烯、 聚酰胺、 聚甲醛、 聚碳酸酯、 聚酯、 聚苯 醚或聚氨酯等。
在本发明的高韧性塑料中， 作为分散相的橡胶粒子优选为均 相结构的橡胶粒子， 其最好为凝胶含量 > 60 %的交联橡胶粒子。 该种橡胶粒子可采用按照本发明人于 1999年 12月 3 日提交的中 国专利申请 99125530.5 (其公开内容全部引入本文供参考） 所制 备的全硫化粉末橡胶， 具体包括但不限于以下全硫化粉末橡胶的 至少一种： 全硫化粉末天然橡胶、 全硫化粉末丁苯橡胶、 全硫化 粉末羧基丁苯橡胶、 全硫化粉末丁腈橡胶、 全硫化粉末羧基丁腈 橡胶， 全硫化粉末氯丁橡胶、 全硫化粉末聚丁二烯橡胶、 全硫化 粉末硅橡胶或全硫化粉末丙烯酸酯橡胶等， 其制备方法参考前面 提到的中国专利申请 99125530.5。 该种全硫化粉末橡胶是指凝胶 含量达 60 %以上， 干燥后无需加隔离剂即可自由流动的离散的橡 胶微粉。 该粉末橡胶是通过辐照交联将橡胶粒子粒径固定的。 当 全硫化粉末橡胶与塑料混合时， 这些粒子极易均勾稳定地分散在 塑料中， 不易凝聚， 能保持很小的粒径。
本发明的高韧性塑料所含橡胶相粒径小， 且粒径均匀、 稳定， 也易于达到高橡塑比； 其具有高韧性及良好的加工成型性， 适用 于非常广泛的领域。
在本发明的高刚高韧性塑料中， 橡胶粒子的用量基于 100重 量份塑料基质为 0.3 ~ 5重量份， 优选 0.5 ~ 2重量份。 橡胶粒子的 平均粒径为 20 ~ 500nm, 优选为 50 ~ 300nm。
在本发明的高刚高韧性塑料中， 作为连续相的塑料是结晶型 塑料， 可以选自聚丙烯、 聚乙烯、 聚酰胺、 聚甲醛、 聚对苯二甲 酸丁二醇酯 （PBT ) 、 聚对笨二甲酸乙二醇酯（PET )等。
在本发明的高刚高韧性塑料中， 作为分散相的橡胶粒子优选 为均相结构的橡胶粒子， 其最好为凝胶含量不小于 60 %的交联橡 胶粒子。 该种橡胶粒子可采用按照本发明人于 1999年 12月 3 曰 提交的中国专利申请 99125530.5所制备的全硫化粉末橡胶， 具体 如上面对高韧性塑料所述。 该种全硫化粉末橡胶是指凝胶含量达 60 %以上，干燥后无需加隔离剂即可自由流动的离散的橡胶微粉。 该种全硫化粉末橡胶可以通过将橡胶乳液辐照交联而得到。 当全 硫化粉末橡胶与塑料混合时， 这些粒子极易均句稳定地分散在塑 料中， 不易凝聚， 能保持很小的粒径。
本发明的高刚高韧性塑料所含橡胶相粒径小， 且粒径均匀、 稳定； 其具有高刚高韧性及更高的热变形温度， 良好的加工成型 性， 适用于非常广泛的领域。
通过将高分子链缠结密度 Ve> ~ 0.15mmol/ml、特征比 C»< ~ 7.5的韧性塑料和平均粒径为 20 ~ 200imi的上述橡胶粒子共混即 可制得本发明的高韧性塑料。 橡胶粒子的平均粒径优选为 50 ~ 150nm之间。 橡胶粒子和塑料的重量比为 0.5:99.5 - 70:30, 优选 5:95 - 50:50。 通过将结晶型塑料和平均粒径为 20 ~ 500nm的上述橡胶粒子 共混即可制得本发明的高刚高韧性塑料。 橡胶粒子在塑料基质中 的添加量基于 100重量份塑料基质为 0.3 ~ 5份，优选 0.5 ~ 2份 。 橡胶粒子的平均粒径优选为 50 ~ 300nm之间。
在本发明高韧性塑料和高刚高韧性塑料的制备方法中， 全硫 化粉末橡胶可以以干燥的交联粉末形态加入或以未干燥的交联乳 液形态加入。
在上迷制备方法中， 物料的共混温度即为普通塑料加工中所 用的共混温度， 可根据基体塑料的熔融温度而定， 应该在既保证 基体塑料完全熔融又不会使塑料分解的范围内选择。 此外， 根据 加工需要， 可在共混物料中适量加入塑料加工的常规助剂， 例如 增塑剂、 抗氧剂、 光稳定剂和增容剂等助剂。
本方法所使用的共混设备为橡塑加工业中的通用共混设备， 可以是单螺杆挤出机、 螺杆挤出机、 开炼机或密炼机等。
本发明的制备高韧性塑料和高刚高韧性塑料的方法工艺筒 单、 易于操作， 适用于各种塑料的增韧。
实施例
下面结合实施例进一步描述本发明， 本发明的范围不受这些 实施例的限制。 本发明的范围在权利要求书中给出。
高韧性塑料的制备实施例
实施例 1 - 2:
将全硫化丁苯粉末橡胶（在兰化胶乳研制中心的丁苯 - 50乳 液中， 按丁苯乳液干胶重量的 3 %加入交联助剂三羟甲基丙烷三 丙烯酸酯后， 进行辐照硫化， 辐照剂量为 2.5Mrad, 经喷雾干燥 后得到， 平均粒径为 lOOnm, 凝胶含量为 90.4 % ) 和聚丙烯粉料 (天津第二石化厂生产， 牌号为 3 - 1型）及抗氧剂 1010 (瑞士 汽巴加基生产）均匀混合。 采用德国 WP公司的 ZSK - 25双螺杆 挤出机共混造粒， 挤出机各段温度分别为： 170°C；、 185 、 190 V、 190°C、 190°C和 190°C (机头温度）。 具体配方见表 1， 其中 全硫化粉末丁苯橡胶与聚丙烯的组分含量均以重量份数计， 抗氧 剂以占各组分总和的重量百分数计。粒料经注塑法制成标准样条， 进行各项力学性能测试， 测试标准及结果如表 1所示。
对比例 1:
将实施例 1 中的聚丙烯粉料、 抗氧剂均勾混合后经双螺杆挤 出机造粒， 其余条件与实施例 1相同。 具体配方及力学测试结果 列于表 1。
实施例 3: „
将全硫化丁苯粉末橡胶（同实施例 1 ) 和聚丙烯粒料（济南 炼油厂， 牌号为 T30S )及抗氧剂 1010 (瑞士汽巴加基生产） 均 匀混合， 并通过挤出机共混造粒， 加工条件与实施例 1 中相同。 具体配方见表 1, 其中全硫化粉末丁苯橡胶与聚丙烯的组分含量 均以重量份数计， 抗氧剂以占各組分总和的重量百分数计。 所得 粒料经注塑法制成标准样条， 进行各项力学性能测试， 测试标准 及结果如表 1所示。
对比例 2:
将实施例 3中的聚丙烯粒料和三元乙丙橡胶粒料（杜邦 Dow 生产， 牌号 3745 ) 以 9/1的重量比均匀混合， 再加入抗氧剂 1010 (同实施例 1 ) 后通过挤出机共混造粒， 加工条件与实施例 1 中 相同。 所得粒料经注塑法制成标准样条， 进行各项力学性能测试， 测试标准及结果如表 1所示。 表 1
Figure imgf000011_0001
实施例 4 - 5：
将全硫化粉末羧基丁苯橡胶 （在燕山石化生产的牌号为 XSBRL - 54B1 羧基丁苯乳液中， 按羧基丁苯乳液干胶重量的 3 %混入交联助剂丙烯酸异辛酯后， 进行辐照硫化， 辐照剂量为 2.5Mrad, 经喷雾干燥得到， 平均粒径为 150nm， 凝胶含量为 92.6 % )与尼龙 6 ( 日本宇部兴产株式会社， 牌号 1013B )及硬脂酸钙 (北京长阳化工厂生产， 化学纯） 和超细滑石粉（河北鹿泉市建 筑材料厂生产， 1250 目） 均匀混合。 采用德国 WP公司的 ZSK - 25 双螺杆挤出机共混造粒， 挤出机各段温度分别为： 230°C、 235°C、 240 "€、 245°C、 240Ό和 235°C (机头温度） 。 具体配方 见表 2， 其中全硫化粉末羧基丁笨橡胶与尼 6的组分含量均以重 量份数计， 其它助剂以占各组分总和的重量百分数计。 粒料烘千 后经注塑法制成标准样条， 进行各项力学性能测试。 测试标准及 性能结果如表 2所示。 实施例 5样品的原子力显微镜照片如图 1 所示（放大倍数： 40， 000 ) , 其中黑色阴影为分布在尼龙 6中的 全硫化粉末羧基丁苯橡胶的粒子。
对比例 3:
将实施例 4中的尼龙 6及硬脂酸钙和超细滑石粉均匀混合后 经双螺杆挤出机共混造粒， 其余条件与实施例 4相同。 具体配方、 测试标准及性能结果如表 2所示。
对比例 4
将实施例 4 中的尼龙 6 与丙烯酸酯橡胶（美国杜邦公司 Lucite44-N )及实施例 4 中所述的硬脂酸钙和超细滑石粉均匀混 合后经 螺杆挤出机共混造粒， 其余条件与实施例 4相同。 具体 配方见表 2， 其中丙烯酸酯橡胶与尼龙 6的组分含量均以重量份 数计， 其它助剂以占各组分总和的重量百分数计。 测试标准及性 能结果如表 2所示。
对比例 5
将实施例 4中的尼龙 6与马来酸酐接枝的 POE (即 POE - g - MAH, 美国联碳化学公司 （UCC )生产， 牌号 DFDA1373 )及 实施例 4中所述的硬脂酸钙和超细滑石粉均句混合后经双螺杆挤 出机共混造粒， 其余条件与实施例 4相同。 具体配方见表 2, 其 中马来酸酐接枝的 POE与尼龙 6的組分含量均以重量份数计，其 它助剂以占各组分总和的重量百分数计。 测试标准及性能结果如 表 2所示。 实施例 6
重复实施例 4-5的搡作， 不同的是将粉末羧基丁苯橡胶与尼 龙 6的配比变为 15: 85。 测试标准及性能结果如表 2 示。
表 2
Figure imgf000013_0001
实施例 7-8
将全硫化粉末羧基丁苯橡胶 （在燕山石化生产的牌号为 XSBRL - 54B1 羧基丁笨乳液中， 按羧基丁苯乳液干胶重量的 3 %混入交联助剂丙烯酸异辛酯后， 进行辐照硫化， 辐照剂量为 2.5Mrad, 经喷雾干燥得到， 平均粒径为 150nm, 凝胶含量为 92.6 % ) 与聚甲醛（ 日本旭化成株式会社生产， 共聚型， 牌号 4520 ) 及硬脂酸钙 （北京长阳化工厂生产， 化学纯） 、 聚乙烯蜡（北京 化工大学生产， 化学纯）、 抗氧剂 1010 (汽巴加基生产） 和超细 滑石粉（河北鹿泉市建筑材料厂生产， 1250目） 均匀混合。 采用 德国 WP公司的 ZSK - 25 螺杆挤出机共混造粒，挤出机各段温 度分别为： 175°C：、 180Π、 185 ；、 185 °C , 180°C和 175°C (机头 温度） 。 具体配方见表 3， 其中全硫化粉末羧基丁苯橡胶与聚甲 醛的組分含量均以重量份数计， 其它助剂以占各組分总和的重量 百分数计。 粒料烘干后经注塑法制成标准样条， 进行各项力学性 能测试。 测试标准及性能结果如表 3所示。
对比例 6:
将实施例 7中的聚甲醛及硬脂酸钙、 抗氧剂 1010、 聚乙烯蜡 和超细滑石粉均匀混合后经双螺杆挤出机共混造粒， 其余条件与 实施例 7相同。 具体配方、 测试标准及性能结果如表 3所示。
对比例 7:
将实施例 7 中的聚甲醛与丙烯酸酯橡胶（美国杜邦公司 Lucite44-N ) 及实施例 7中所迷的硬脂酸钙、 抗氧剂 1010、 聚乙 烯蜡和超细滑石粉均勾混合后经 螺杵挤出机共混造粒， 其余条 件与实施例 7相同。 配方见表 3， 其中丙烯酸酯橡胶与聚甲醛的 组分含量均以重量份数计， 其它助剂以占各组分总和的重量百分 数计。 测试标准及性能结果如表 3所示。
表 3
Figure imgf000015_0001
实施例 9
将全硫化粉末丙烯酸丁酯橡胶（在北京东方化工厂生产的牌 号为 BC - 01 的丙烯酸丁酯乳液中， 按丙烯酸丁酯乳液干胶重量 的 3 %混入交联助剂丙烯酸异辛酯后， 进行辐照硫化， 辐照剂量 为 2.5Mrad, 经喷雾干燥得到， 平均粒径为 lOOnm, 凝胶含量为 87.7 % ) 与聚碳酸酯（美国通用电气公司生产， 牌号 141R) 均匀 混合。 采用德国 WP公司的 ZSK - 25双螺杆挤出机共混造粒， 挤 出机各段温度分别为： 265°C、 270 、 275 275°C、 270 和 265 °C (机头温度）。 具体配方见表 4。 其中全硫化粉末丙烯酸丁 酯橡胶与聚碳酸酯的组分含量均以重量份数计。 粒料烘干后经注 塑法制成标准样条， 进行各项力学性能测试。 测试标准及性能结 果如表 4所示。
对比例 8
将实施例 9中的聚碳酸酯直接经注塑法制成标准样条， 进行 各项力学性能测试。 测试标准及性能结果如表 4所示。
表 4
Figure imgf000016_0001
高刚高韧性塑料的制备实施例
实施例 10
将聚丙烯粒料（济南炼油厂生产， 牌号 T30S )和耷硫化聚丁 二烯粉末橡胶（在吉化合成树脂厂的聚丁二烯乳液中，牌号 0700, 按乳液干胶重量的 3 %加入交联助剂三羟甲基丙烷三丙烯酸酯后， 辐照硫化， 辐照剂量为 2Mrad, 经喷雾干燥后得到， 平均粒径 280nm, 凝胶含量 88.5 % )及抗氧剂 1010 (瑞士汽巴加基生产 ) 混合配料， 以塑料的重量份数为 100份计， 其具体组成为： 聚丙 烯 100份， 全硫化聚丁二烯粉末橡胶 0.5份， 抗氧剂为 0.5份。 采 用德国 WP公司的 ZSK - 25 螺杆挤出机共混造粒，挤出机各段 温度分别为： 170°C；、 185°C、 190 °C、 190 °C；、 190°C和 190°C (机 头温度）。 粒料经注塑法制成标准样条， 进行各项力学性能测试， 其结果如表 5所示。
实施例 11
将实施例 10中的全硫化聚丁二烯粉末橡胶用量改为 1份，其 余条件与实施例 10相同， 粒料经注塑法制成标准样条， 进行各项 力学性能测试， 力学测试结果列于表 5。
实施例 12
将实施例 10中的全硫化聚丁二烯粉末橡胶用量改为 1.5份， 其余条件与实施例 10相同， 粒料经注塑法制成标准样条， 进行各 项力学性能测试， 力学测试结果列于表 5。
实施例 13
将实施例 10中的全硫化聚丁二烯粉末橡胶用量改为 2份，其 佘条件与实施例 10相同， 粒料经注塑法制成标准样条， 进行各项 力学性能测试， 力学测试结果列于表 5。
对比例 9
将实施例 10中的聚丙烯粒料直接注塑制成标准样条，进行各 项力学性能测试， 力学测试结果列于表 5。
对比例 10
用丁苯橡胶（吉化有机合成厂， 牌号： 1502 )代替实施例 11 中的全硫化聚丁二烯粉末橡胶， 其余条件与实施例 11相同， 粒料 经注塑法制成标准样条， 进行各项力学性能测试， 力学测试结果 列于表 5。
实施例 14
将聚丙烯粉料（天津第二石化厂生产， 牌号 3 - 1型）和全硫 化丁苯粉末橡胶乳液（在兰化胶乳研制中心的丁笨- 50乳液中， 固含量 45 % , 按乳液干胶重量的 3 %加入交联助剂三羟甲基丙烷 三丙烯酸酯后， 辐照硫化， 辐照剂量为 2.5Mrad, 乳液粒子平均 粒径 lOOnm, 凝胶含量 90.4 % )及抗氧剂 1010 (瑞士汽巴加基生 产） 混合配料， 具体组成以重量份数计为： 聚丙烯 100份， 全琉 化丁苯粉末橡胶乳液 2份（以干胶计算） ， 抗氧剂为 0.5份。 采 用德国 WP公司的 ZSK - 25双螺杆挤出机共混造粒，挤出机各段 温度分别为 170°C；、 185°C；、 190°C、 190 °C 1901：和 190°C (机头 温度） 。 粒料经注塑法制成标准样条， 进行各项力学性能测试， 其结果如表 5所示。
对比例 11
将实施例 14中的聚丙烯粉料和抗氧剂混合后， 经挤出， 注塑 制成标准样条， 进行各项力学性能测试， 力学测试结果列于表 5。
表 5
Figure imgf000019_0001
实施例 15
将全硫化粉末丙烯酸丁酯橡胶（在北京东方化工厂生产的牌 号为 BC - 01 的丙烯酸丁酯乳液中， 按丙烯酸丁酯乳液干胶重量 的 3 %混入交联助剂丙烯酸异辛酯后， 进行辐照硫化， 辐照剂量 为 2.5Mrad， 经喷雾干燥得到， 平均粒径为 100nm， 凝胶含量为 87.7 % )与聚对苯二甲酸乙二醇酯（燕山石化生产，特性粘度 0.76 ) 及硬脂酸钙 （北京长阳化工厂， 化学纯） 、 超细滑石粉（河北鹿 泉市建筑材料厂， 1250目）均勾混合， 具体組成以重量份数计为： 全硫化粉末丙烯酸丁酯橡胶 0.5份， 聚对笨二甲酸乙二醇酯 100 份， 硬脂酸钙为 0.3份， 超细滑石粉 0.3份。 采用德国 WJP公司的 ZSK - 25 双螺杆挤出机共混造粒， 挤出机各段温度分别为： 260 °C、 280 °C、 280*C、 280 °C , 285°C和 2801 (机头温度） 。 粒料 烘干后经注塑法制成标准样条， 进行各项力学性能测试。 测试标 准及性能结果如表 6所示。
实施例 16
将实施例 15中的组分配比改为：全硫化粉末丙烯酸丁酯橡胶 1份, 聚对苯二甲酸乙二醇酯 100份，其佘条件与实施例 15相同， 粒料经注塑法制成标准样条， 进行各项力学性能测试， 力学测试 结果列于表 6。
实施例 17
将实施例 15中的组分配比改为：全硫化粉末丙烯酸丁酯橡胶 2份， 聚对苯二甲酸乙二醇酯 100份，其余条件与实施例 15相同， 粒料经注塑法制成标准样条， 进行各项力学性能测试， 力学测试 结果列于表 6。
实施例 18
将实施例 15中的组分配比改为：全硫化粉末丙烯酸丁酯橡胶 5份， 聚对苯二甲酸乙二醇酯 100份，其余条件与实施例 15相同， 粒料经注塑法制成标准样条， 进行各项力学性能测试， 力学测试 结果列于表 6。
对比例 12
将聚对苯二甲酸乙二醇酯（同实施例 15 )经注塑法制成标准 样条， 进行各项力学性能测试， 力学测试结果列于表 6。
表 6
Figure imgf000021_0001
实施例 19
将全硫化粉末丙烯酸丁酯橡胶（同实施例 15 )与聚对苯二甲 酸丁二醇酯（ BASF, 牌号 4500， 特性粘度 1.02 )及硬脂酸钙（北 京长阳化工厂， 化学纯）、 超细滑石粉（河北鹿泉市建筑材料厂， 1250目）均勾混合， 具体组成以重量份数计为： 全硫化粉末丙烯 酸丁酯橡胶 0.5份， 聚对苯二甲酸丁二醇酯 100份， 硬脂酸钙为 0.3份， 超细滑石粉 0.3份。 采用德国 WP公司的 ZSK - 25双螺 杆挤出机共混造粒， 挤出机各段温度分别为： 220" 、 240 °C、 240 V、 240V , 245 X和 240°C (机头温度） 。 粒料烘干后经注塑法 制成标准样条， 进行各项力学性能测试。 测试标准及性能结果如 表 7所示。
实施例 20
将实施例 19中的组分配比改为：全硫化粉末丙烯酸丁酯橡胶 1份， 聚对笨二甲酸丁二醇酯 100份，其余条件与实施例 19相同， 粒料经注塑法制成标准样条， 进行各项力学性能测试， 力学测试 结果列于表 7。
实施例 21
将实施例 19中的組分配比改为：全硫化粉末丙烯酸丁酯橡胶 2份， 聚对笨二甲酸丁二醇酯 100份，其余条件与实施例 19相同， 粒料经注塑法制成标准样条， 进行各项力学性能测试， 力学测试 结果列于表 7。
实施例 22
将实施例 19中的組分配比改为：全硫化粉末丙烯酸丁酯橡胶 5份， 聚对苯二甲酸丁二醇酯 100份，其佘条件与实施例 19相同， 粒料经注塑法制成标准样条， 进行各项力学性能测试， 力学测试 结果列于表 7。
对比例 13
将聚对苯二甲酸丁二醇酯（同实施例 19 )经注塑法制成标准 样条， 进行各项力学性能测试， 力学测试结果列于表 7。
表 7
拉伸强度 拉伸断裂 悬臂梁缺 弯曲强度 弯曲模量 热变形 伸长率 口冲击强度 温度 单位 MPa % J/m MPa GPa "C 实施例 19 63.7 22 48.7 80.9 2.39 67.2 实施例 20 67.6 32 59.8 83.6 2.46 69.5 实施例 21 66.8 34 63.1 81.2 2.41 68.7 实施例 22 61.5 37 56.7 78.3 2.21 66.9 对比例 13 55.2 9 31.5 74.3 2.18 62.8 测试标准 ASTM ASTM ASTM ASTM ASTM ASTM
D638 D638 D256 D790 D790 D648

Claims

权 利 要 求
1. 一种高韧性塑料， 包含以下组分： 高分子链缠结密度 Ve> ~ 0.15mmol/mK 特征比 C∞< ~ 7.5 的韧性塑料和平均粒径为 20 ~ 200nm 的橡胶粒子， 其中橡胶粒子和塑料的重量比为 0.5:99.5 ~ 70:30。
2. 根据权利要求 1 所迷的高韧性塑料， 其特征在于所述韧性 塑料包括聚丙烯、 聚乙烯、 聚酰胺、 聚甲醛、 聚碳酸酯、 聚酯、 聚苯醚或聚氨酯。
3. 根据权利要求 1 所述的高韧性塑料， 其特征在于所述橡胶 粒子的平均粒径范围为 50 ~ 150nm。
4. 根据权利要求 1 所述的高韧性塑料， 其特征在于所述橡胶 粒子与塑料的重量比为 5:95 - 50:50。
5. 根据权利要求 1-4 中任一项所述的高韧性塑料， 其特征在 于所述橡胶粒子为均相结构的橡胶粒子。
6. 根据权利要求 5所述的高韧性塑料， 其特征在于所述橡胶 粒子为凝胶含量不小于 60 %重量的交联橡胶粒子。
7. 根据权利要求 6所述的高韧性塑料， 其特征在于所述橡胶 粒子为全疏化粉末橡胶。
8. 根据权利要求 7所述的高韧性塑料， 其特征在于所述全硫 化粉末橡胶包括以下物盾中的至少一种： 全硫化粉末天然橡胶、 全硫化粉末丁苯橡胶、 全硫化粉末羧基丁苯橡胶、 全硫化粉末丁 腈橡胶、 全硫化粉末羧基丁腈橡胶、 全硫化粉末氯丁橡胶、 全硫 化粉末聚丁二烯橡胶、 全硫化粉末硅橡胶或全硫化粉末丙烯酸酯 橡胶。
9. 一种制备^ I利要求 1 - 8 中任一项所述的高韧性塑料的方 法， 包括将高分子链缠结密度 Ve> ~ 0.15mmol/ml、特征比 C»< ~
7.5的韧性塑料和平均粒径 20 ~ 200nm的橡胶粒子共混， 其中橡 胶粒子和塑料重量比为 0.5:99.5 ~ 70:30。
10. 根据权利要求 9所迷的方法， 其特征在于所述橡胶粒子为 全硫化粉末橡胶。
11. 根据权利要求 10所述的方法， 其特征在于所述的全硫化 粉末橡胶以干燥的交联粉末形态或干燥的交联乳液形态加入。
12. 一种高刚高韧性塑料， 包含以下组分： 结晶型塑料和平均 粒径为 20 ~ 500nm的橡胶粒子， 其中橡胶粒子在塑料基质中的添 加量基于 100重量份塑料为 0.3 ~ 5份。
13. 根据权利要求 12所迷的高刚高韧性塑料， 其特征在于所 述结晶型塑料包括： 聚丙烯、 聚乙烯、 聚酰胺、 聚甲醛、 聚对苯 二甲酸丁二醇酯或聚对苯二甲酸 二醇酯。
14. 根据权利要求 12所述的高刚高韧性塑料， 其特征在于所 述橡胶粒子的平均粒径范围为 50 ~ 300mn。
15. 根据权利要求 12所迷的高刚高韧性塑料， 其特征在于橡 胶粒子在塑料基质中的添加量基于 100重量份塑料为 0.5 ~ 2份。
16. 根据权利要求 12-15中任一项所述的高刚高韧性塑料， 其 特征在于所述橡胶粒子为均相结构的橡胶粒子。
17. 根据权利要求 16所述的高刚高韧性塑料， 其特征在于所 述橡胶粒子为凝胶含量不小于 60 %重量的交联橡胶粒子。
18. 根据权利要求 17所述的高刚高韧性塑料， 其特征在于所 述橡胶粒子为全硫化粉末橡胶。
19. 根据权利要求 18所述的高刚高韧性塑料， 其特征在于所 迷全硫化粉末橡胶包括以下物质中的至少一种： 全硫化粉末天然 橡胶、 全硫化粉末丁笨橡胶、 全硫化粉末羧基丁苯橡胶、 全硫化 粉末丁腈橡胶、 全硫化粉末羧基丁腈橡胶、 全硫化粉末氯丁橡胶、 全硫化粉末聚丁二烯橡胶、 全硫化粉末硅橡胶或全硫化粉末丙烯 酸酯橡胶。
20. —种制备权利要求 12-19 中任一项所述的高刚高韧性塑 料的方法， 包括将结晶型塑料和平均粒径为 20~500nm的橡胶粒 子共混， 其中橡胶粒子在塑料基质中的添加量基于 100重量份塑 料基质为 0.3~5重量份。
21. 根据权利要求 20所述的方法， 其特征在于所迷橡胶粒子 为全硫化粉末橡胶。
22. 根据权利要求 21 所述的方法， 其特征在于所述的全硫化 粉末橡胶以干燥的交联粉末形态或干燥的交联乳液形态加入。
PCT/CN2001/001265 2000-08-22 2001-08-22 Matiere plastique malleable et son procede de fabrication Ceased WO2002026869A1 (fr)

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AU2002213767A AU2002213767A1 (en) 2000-08-22 2001-08-22 Tenacity plastic and its preparation method
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