CN1091122C - Ethylene propylene/polypropene blended thermoplastic elastic body and preparation method - Google Patents
Ethylene propylene/polypropene blended thermoplastic elastic body and preparation method Download PDFInfo
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- CN1091122C CN1091122C CN98121713A CN98121713A CN1091122C CN 1091122 C CN1091122 C CN 1091122C CN 98121713 A CN98121713 A CN 98121713A CN 98121713 A CN98121713 A CN 98121713A CN 1091122 C CN1091122 C CN 1091122C
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Abstract
The present invention relates to a dynamic fully-crosslinked ethylene-propylene rubber/polypropylene cross blend type thermoplastic elastomer and a preparation method thereof. The thermoplastic elastomer is prepared by mixing ethylene propylene terpolymer rubber isotactic polypropylene plastics, a bismaleimide crosslinking system and a compounding agent. The preparation method is carried out by adopting a double-step type double-screw extruding machine, and the product is obtained through drying after material charging through multiple feed openings, ingredient mixing, shearing vulcanization and water fog thermal pelleting. Industrialized continuous production on a large scale can be realized by adopting the present invention. The produced product has the advantages of high strength, high elasticity and favorable fluidity. The produced product can be formed and processed with a processing method of thermoplastic plastics, and the processed product can be widely applied to the fields of automobiles, constructions, electric cables, packaging, household electrical appliances, etc.
Description
Technical field
The present invention relates to a kind of dynamic fully-cross-linked EPT rubber blended thermoplastic elastic body and preparation method thereof.
Background technology
The EPT rubber blended thermoplastic elastic body is under molten state, and rubber phase is crosslinked to carry out simultaneously with the blend of rubber and plastic two-phase, rubber phase with small particles dispersed in the blend of plastics in mutually.This blend available heat thermoplastic plastic working method is processed, and has snappiness in the scope of broad.
(U.S. Pat .4,130,535) such as the Coran of U.S. Monsanto Company as linking agent and be equipped with corresponding promotor etc., prepared EPT rubber blend with dynamic fully-cross-linked method with sulphur.Because the free sulphur in this material prescription has corrosive nature to copper conductor, has limited its application in cable industry.Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences has designed a kind of " ethylene propylene rubber polypropylene thermoplastic elastomer and preparation method thereof " (publication number 85102222A), adopt dicumyl peroxide, diamyl methyne four thiuramsulfides to make linking agent, though it can make rubber phase full cross-linked, again plastics are not had obvious degradation and crosslinked action mutually, metallic substance such as copper there is not corrosive nature, make the product of production can be used for field of cables, but it equally exists with above-mentioned cross-linking system and adds the scent of in man-hour, the product flowability of production and the problem of resilient bias.
The Beijing Chemical Engineering College has designed a kind of " ethylene-propylene rubber/polyolefine thermoplastic elastomer and preparation method " (publication number 1059533A), and adopting ethylidene norbornene is that the 3rd monomeric terpolymer EP rubber and isotatic polypropylene (or high-density and LDPE (Low-density polyethylene plastics)), resol cross-linking system have prepared such elastomerics.Though it is it has overcome the weak point of preceding two kinds of cross-linking systems,, crosslinked with resin alloy again because of its preparation method is to make rubber master batch earlier, must be used alternatingly mill (or Banbury mixer) and forcing machine, make complex process, production process is discontinuous, can not the heavy industrialization continuous production.
Summary of the invention
The objective of the invention is at above-mentioned weak point, aim to provide the EPT rubber thermoplastic elastomer of a kind of good fluidity, good springiness, and energy consumption is low, on a large scale this elastomeric method of continuous industry production.
Implementation of the present invention is,
1, a kind of dynamic fully-cross-linked ethylene propylene/polypropene blended thermoplastic elastic body is by being that the 3rd monomeric terpolymer EP rubber, isotatic polypropylene, cross-linking system, weighting agent, anti-aging agent combine with ethylidene norbornene.The each several part parts by weight are counted for 100 parts by rubber:
Cross-linking system 4-45 weighting agent 10-350
Anti-aging agent 0.5-2.5 acrylic plastering 25-400.
Weighting agent is packing strengthening agent carbon black and extending oil naphthenic oil, and each component umber is:
Carbon black 5-100 naphthenic oil 0-250.
Anti-aging agent is 2,2,4-trimethylammonium-1,2-dihydroquinoline polymkeric substance.
It is characterized in that cross-linking system is the bismaleimides cross-linking system, its composition umber is:
4,4 '-methylene phenylbenzene bismaleimides 1-10
Dibenzothiazyl disulfide 0.25-5
ZnO 2-10 stearic acid 1-20
2, a kind of preparation method of dynamic fully-cross-linked ethylene propylene/polypropene blended thermoplastic elastic body, with ethylene-propylene rubber(EPR), polypropylene, cross-linking system and Synergist S-421 95 through batch mixes, shearing, sulfuration, water smoke hot cut pellet, dry product.The present invention adopts the production of two steps type twin screw extruder, and the first rank twin screw extruder is provided with a plurality of dog-houses, adds ethylene-propylene rubber(EPR), polypropylene, cross-linking system and Synergist S-421 95 respectively.Screw design is that feeding section, mixing section are alternately formed, and the feeding section is selected the dark single thread element of screw channel for use, and mixing section is then selected two screwing elements for use.The screw design multiselect of the second rank twin screw extruder is with three strong screwing elements of shearing action.Material adopts the pelletizing of water smoke hot cut pellet mode after mixing fully, shear, vulcanizing, get product again after water pre-separation, drying.
It is the 3rd monomeric terpolymer EP rubber that rubber of the present invention adopts ethylidene norbornene, and its ethylene content (weight ratio %) is 60-80%, mooney viscosity (ML
120 ℃) be 65-85.Plastics adopt isotactic polyprophlene, and melting index (MI) is 1.5-3.0, and degree of isotacticity is 92-98%.Rubber/mould weight ratio is 80/20-20/80.
Cross-linking system is the bismaleimides cross-linking system, adopt 4,4 '-methylene phenylbenzene bismaleimides (BMI) makes vulcanizing agent, and dibenzothiazyl disulfide (DM) is done promotor, and zinc oxide, stearic acid are made promoting agent.Adopt this cross-linking system curing time short, odorlessness during process for processing can suppress the high temperature phenomenon of reverting, the elastomerics good fluidity of production well.
Employing 2,2,4-trimethylammonium-1,2-dihydroquinoline polymkeric substance (anti-aging agent RD) are made anti-aging agent, and carbon black is made packing strengthening agent, and naphthenic oil is done to fill and improved property, can adjust hardness, the intensity of thermoplastic elastomer in a big way.
The main physical properties of this ethylene propylene/polypropene blended thermoplastic elastic body is as follows:
Tensile strength 12-30MPa hardness (Shao Shi) 45A-68D
100% tensile modulus 3-11MPa tear strength 20-120KN/m
Elongation 300-1000% tension set 20-80% is separated in fracture
Life-time service temperature-35-140 ℃ of aging coefficient 0.9-1.02
(100 ℃ of 168h) similar thermoplastic elastomer with other is compared, intensity height, good springiness, good fluidity, the no high temperature phenomenon of reverting.
The present invention adopts two rank twin screw extruder method to prepare thermoplastic elastomer.The first rank twin screw extruder adopts many material mouth feed way as shown in Figure 1, mainly plays batching, blended effect.The screw design of the second rank twin screw extruder is selected the strong triple thread element of shearing action for use morely, to guarantee curing time and shearing resistance.The screw arrangement figure of twin screw extruder sees Fig. 2.
Rubber also can add a part at single order twin screw extruder top charging opening, rest part adds at second order twin screw extruder top charging opening, when guaranteeing that rubber content is high, material can mix, rubber phase can form littler uniform particles be scattered in plastics mutually in, make material in that to add man-hour mobile better simultaneously.
The present invention adopts twin screw extruder to produce that the thermoplastic elastomer energy consumption is low, efficient is high, can adapt on a large scale continuously, suitability for industrialized production stably, and the product of production can be widely used in fields such as automobile, building, cable, packing, household electrical appliance.
With reference to the accompanying drawings present device is further specified.
Fig. 1 technical process of the present invention and equipment synoptic diagram
Fig. 2 twin screw extruder screw combinations synoptic diagram
Fig. 3 two start screw component structure synoptic diagram
Fig. 4 triple thread component structure synoptic diagram
Among Fig. 1,2,1 be the heavy feeder of major ingredient meter, the heavy feeder of 2 auxiliary material meters, the heavy feeder of 3 solid-state meters, 4 liquid flux feeders, 5 vulcanizing agent feeders, the heavy feeder of 6 major ingredient meters, 7 devolatilizations, 8 water smoke hot cut pellets, 9 water preseparators, 10 pellet dryers.
Embodiment
Enumerate the embodiment of the invention below:
Each Example formulations is as shown in table 1, and the product performance of preparing see Table 2.
The prescription of table 1, each embodiment (parts by weight)
| Prescription number composition | I | II | III | IV | V |
| EPDM | 80 | 70 | 60 | 40 | 20 |
| PP | 20 | 30 | 40 | 60 | 80 |
| BMI | 2.4 | 1.8 | 1.8 | 1.5 | 1.5 |
| DM | 0.6 | 0.5 | 0.5 | 0.5 | 0.5 |
| ZnO | 2.4 | 2 | 2 | 1.8 | 1.8 |
| Stearic acid | 1.3 | 6 | 4.5 | 3.2 | 3 |
| Carbon black | 5 | 60 | 40 | 30 | 20 |
| Naphthenic oil | 5 | 40 | 80 | 50 | |
| Anti-aging agent | 0.8 | 0.7 | 0.5 | 0.4 | 0.4 |
Table 2, each embodiment product performance
| Prescription number composition | I | II | III | IV | V |
| Hardness (Shao Shi) | 76A | 88A | 45D | 50D | 56D |
| 100% tensile modulus (MPa) | 3.61 | 6.33 | 12.20 | 15.31 | 17.26 |
| Tensile strength (MPa) | 19.2 | 16.1 | 19.6 | 21.3 | 24.8 |
| Elongation at break (%) | 960 | 440 | 530 | 320 | 370 |
| Tear strength (KN/m) | 57.9 | 71.4 | 109.6 | 113.2 | 119.6 |
| Tension set (%) | 9 | 17 | 33 | 45 | 68 |
| The hot air aging coefficient (100 ℃, 168h) | 0.87 | 0.91 | 0.95 | 0.93 | 0.96 |
Example 1:
Ethylene-propylene rubber(EPR), polypropylene, cross-linking system and Synergist S-421 95 are pressed the formula I composition of table 1, are added by many charging openings automatic gauge, and wherein ethylene-propylene rubber(EPR) only adds half of total amount, and second half charging opening by the second rank twin screw extruder adds.The temperature of each section of twin screw extruder is controlled to be 175 ℃-190 ℃.Material is the water smoke hot cut pellet after mixing, vulcanizing, and again through the water preseparator, gets product after the drying, and its performance sees Table 2I.
Example 2:
Press the composition of the formula I I of table 1, ethylene-propylene rubber(EPR), polypropylene and cross-linking system, Synergist S-421 95 add from many charging openings, and ethylene-propylene rubber(EPR) all adds at the first rank dual-screw-stem machine, and other operating process and processing condition are identical with embodiment 1, and the products obtained therefrom performance sees Table 2II.
Example 3:
Press the composition of the formula I II of table 1, operating process and control are with embodiment 2, and the products obtained therefrom performance sees Table 2III.
Example 4: press the composition of the formula I I of table 1, operating process and control are with embodiment 2, and the products obtained therefrom performance sees Table 2IV.
Example 5: press the composition of the prescription V of table 1, operating process and control are with embodiment 2, and the products obtained therefrom performance sees Table 2V.
Claims (3)
1, ethylene propylene/polypropene blended thermoplastic elastic body, by being that the 3rd monomeric terpolymer EP rubber, isotatic polypropylene, cross-linking system, weighting agent, anti-aging agent combine with ethylidene norbornene, the each several part parts by weight are counted for 100 parts by rubber:
Cross-linking system 4-45 weighting agent 10-350
Anti-aging agent 0.5-2.5 acrylic plastering 25-400
Weighting agent is packing strengthening agent carbon black and extending oil naphthenic oil, and each component umber is:
Carbon black 5-100 naphthenic oil 0-250
Anti-aging agent is 2,2,4-trimethylammonium-1,2-dihydroquinoline polymkeric substance.
It is characterized in that cross-linking system is the bismaleimides cross-linking system, its composition umber is:
4,4 '-methylene phenylbenzene bismaleimides 1-10
Dibenzothiazyl disulfide 0.25-5
ZnO 2-10 stearic acid 1-20
2, the preparation method of the ethylene propylene/polypropene blended thermoplastic elastic body of claim 1, with ethylene-propylene rubber(EPR), polypropylene, cross-linking system and Synergist S-421 95 are through batch mixes, shear, sulfuration, the water smoke hot cut pellet, the dry product that gets, it is characterized in that adopting the production of two steps type twin screw extruder, the first rank twin screw extruder is provided with a plurality of dog-houses, add ethylene-propylene rubber(EPR) respectively, polypropylene, cross-linking system and Synergist S-421 95, screw design is the feeding section, mixing section is alternately formed, the feeding section is selected the dark single thread element of screw channel for use, mixing section is then selected two screwing elements for use, the screw design multiselect of the second rank twin screw extruder is with three strong screwing elements of shearing action, material is through mixing fully, shear, after the sulfuration, adopt the pelletizing of water smoke hot cut pellet mode, again through the water pre-separation, get product after the drying.
3, preparation method according to claim 2 is characterized in that rubber can add a part earlier on single order twin screw extruder top, and rest part adds on second order twin screw extruder top.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN98121713A CN1091122C (en) | 1998-12-17 | 1998-12-17 | Ethylene propylene/polypropene blended thermoplastic elastic body and preparation method |
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| CN98121713A CN1091122C (en) | 1998-12-17 | 1998-12-17 | Ethylene propylene/polypropene blended thermoplastic elastic body and preparation method |
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| CN1225931A CN1225931A (en) | 1999-08-18 |
| CN1091122C true CN1091122C (en) | 2002-09-18 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155652C (en) * | 2000-11-03 | 2004-06-30 | 中国石油化工股份有限公司 | Toughened plastics and its preparing process |
| ITTO20020578A1 (en) * | 2002-07-03 | 2004-01-05 | Maris Spa Flli | CONTINUOUS PRODUCTION PROCESS OF A COMPOSITION INCLUDING HYDROCARBONIC AND SOLVENT RESIN RUBBER |
| US6890990B2 (en) * | 2003-05-30 | 2005-05-10 | Solvay Engineered Polymers, Inc. | Co-agents for the preparation of thermoplastic elastomeric blends of rubber and polyolefins |
| JP4595488B2 (en) * | 2003-12-09 | 2010-12-08 | 東海ゴム工業株式会社 | Anti-vibration rubber composition |
| JP4622619B2 (en) * | 2005-03-28 | 2011-02-02 | 東海ゴム工業株式会社 | Anti-vibration rubber composition |
| CN102532724A (en) * | 2010-12-30 | 2012-07-04 | 四川晨光科新塑胶有限责任公司 | Method for preparing thermoplastic dynamic vulcanized rubber by one-step method |
| CN103524895B (en) * | 2013-09-30 | 2016-01-27 | 芜湖航天特种电缆厂 | A kind of Halogen-free flame-retardant polypropylene cable material with high temperature resistance and preparation method thereof |
| CN103524901A (en) * | 2013-10-25 | 2014-01-22 | 安徽文峰电子科技集团有限公司 | Toughness-enhanced ethylene propylene diene rubber cable material |
| CN103978582B (en) * | 2014-05-12 | 2016-08-24 | 扬州华声电子实业有限公司 | A kind of EP rubbers elastomeric compound fully automatic integral streamline and processing technique |
| CN108586945A (en) * | 2018-03-29 | 2018-09-28 | 苏州耐思特塑胶有限公司 | A kind of preparation method and applications of corrosion resistance rubber composite material |
| CN108687997A (en) * | 2018-05-28 | 2018-10-23 | 泗阳宝源塑胶材料有限公司 | Dual-band twin-screw extruder |
| CN109130138B (en) * | 2018-07-31 | 2021-02-02 | 南京科森挤出装备有限公司 | Method for combining all single-head thread sleeves of parallel double-screw extruder |
| CN110394962A (en) * | 2019-08-20 | 2019-11-01 | 仙居县创新机械设备有限公司 | A kind of rubber strip production whole line equipment of Dual-conveying tall co-extrusion |
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| US4130535A (en) * | 1975-07-21 | 1978-12-19 | Monsanto Company | Thermoplastic vulcanizates of olefin rubber and polyolefin resin |
| CN85102222A (en) * | 1985-04-01 | 1986-08-06 | 中国科学院长春应用化学研究所 | Ethylene propylene rubber polypropylene thermoplastic elastomer and preparation method |
| CN1059533A (en) * | 1991-10-30 | 1992-03-18 | 北京化工学院 | Thermoplastic ethylene-propylene rubber/polyolefine elastomer and preparation method |
| CA2095504A1 (en) * | 1992-05-06 | 1993-11-07 | Joseph K. Valaitis | Mineral filled epdm/epr compositions for white sidewall compounds |
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1998
- 1998-12-17 CN CN98121713A patent/CN1091122C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4130535A (en) * | 1975-07-21 | 1978-12-19 | Monsanto Company | Thermoplastic vulcanizates of olefin rubber and polyolefin resin |
| CN85102222A (en) * | 1985-04-01 | 1986-08-06 | 中国科学院长春应用化学研究所 | Ethylene propylene rubber polypropylene thermoplastic elastomer and preparation method |
| CN1059533A (en) * | 1991-10-30 | 1992-03-18 | 北京化工学院 | Thermoplastic ethylene-propylene rubber/polyolefine elastomer and preparation method |
| CA2095504A1 (en) * | 1992-05-06 | 1993-11-07 | Joseph K. Valaitis | Mineral filled epdm/epr compositions for white sidewall compounds |
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