CN100429254C - Composite cross-linked polymer and its prepn process and use - Google Patents
Composite cross-linked polymer and its prepn process and use Download PDFInfo
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- CN100429254C CN100429254C CNB2005100707780A CN200510070778A CN100429254C CN 100429254 C CN100429254 C CN 100429254C CN B2005100707780 A CNB2005100707780 A CN B2005100707780A CN 200510070778 A CN200510070778 A CN 200510070778A CN 100429254 C CN100429254 C CN 100429254C
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Abstract
The present invention relates to a compound cross-linking substance of powder nitrile rubber-low-density polyethylene-metallocene ethylene propylene terpolymer rubber, which is composed of 35 to 45 of weight portions of metallocene ethylene propylene terpolymer rubber grafting substances and 55 to 65 weight portions of powder nitrile rubber-low-density polyethylene cross-linking substances. The graft ratio is between 0.5 and 1.8%, and the cross-linking degree is between 60.5 and 72.3%. In the preparation method, at normal temperature, the metallocene ethylene propylene terpolymer rubber grafting substance components and the powder nitrile rubber-low-density polyethylene cross-linking substance component weighed in proportion are mixed at high speed for 2 to 3 minutes; grafting, cross linking and granulation are completed at one time in a synclastic rotating parallel double-screw extruder. The compound cross linking substance obviously enhances the impact toughness of homopolymerization polypropylene and has small influences on the toughness and the tensile property of homopolymerization polypropylene; the compound cross linking substance can simultaneously obviously improve the oil resistance and the antistatic property of homopolymerization polypropylene; the compound cross linking substance is especially suitable for producing plastic parts of electric refrigerators, has the advantages of reliable simple technology and low cost and is friendly to environment.
Description
Technical field:
The present invention relates to homo-polypropylene modification technology field, particularly a kind of Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer and preparation method thereof.
Technical background:
The homo-polypropylene that with the refinery gas is raw material production is at present still occupied very important ratio in polypropylene market at home.Since have favorable mechanical performance, particularly its tensile strength height, excellent rigidity, good processability, this part polypropylene was mainly used in industries such as packing, non-woven fabrics, polypropylene fiber in the past.Along with the raising of people's living standard, urgent day by day to the demand of environmental protection household electrical appliances, traditional household electric appliances by the monopolization of engineering plastics such as ABS begin to consider to adopt more eco-friendly polypropylene modification product.Has stronger competitive edge as the higher relatively homo-polypropylene of over-all properties.But the low-temperature performance of homo-polypropylene is relatively poor, oil-proofness is poor, static resistance is poor, shrinking percentage is greatly its fatal weakness, be difficult to adapt to household electrical appliances particularly the inner plastic member of refrigerator to the requirement of low-temperature performance, oil-proofness, static resistance.The method of the low-temperature flexibility of raising homo-polypropylene is a lot, method for toughening commonly used is to add rubber components such as terpolymer EP rubber (EPDM) in blending modification system, ethylene-propylene rubber(EPR) (EPR), ethylene-octene copolymer elastomerics (POE), butadiene-styrene thermoplastic elastomer (SBS), hydrogenated butadiene-styrene thermoplastic elastomer (SEBS) etc., but because of need in modified system, adding more rubber or elastomerics, though the toughness of material has obtained remarkable improvement, but other performances of material have but lost balance, and especially its rigidity and loss of tensile strength are bigger.The POE/ high density polyethylene(HDPE) toughened master batch that patent CN01114932.9 introduces can improve polyacrylic toughness to greatest extent with minimum addition, and simultaneously unlikely again undue other performances that influence material are rigidity particularly.Patent CN200510002251.4 has introduced the preparation method and the purposes of Cisdene-low density polyethylene cross-linked material, but its objective is the low-temperature flexibility that is intended to improve homo-polypropylene, and the rigidity and the toughness of balance matrix material to a certain extent.Though but these toughening modifying methods can obviously improve the toughness of homo-polypropylene, but seem weak aspect its static resistance and the oil-proofness improving.Though adopt graft polypropylene such as maleic anhydride can improve the polarity of homo-polypropylene matrix material to a certain extent as modified component, the percentage of grafting of this class grafts is generally lower, is difficult to significantly improve the oil-proofness of matrix material.Consider the vinyl cyanide group that contains higher proportion in a large amount of ABS molecular structures that adopt of traditional home appliance, just give ABS good oil resistance, we plan to adopt paracril to improve the oil-proofness of homo-polypropylene as blend components.As everyone knows, the solubility parameter of non-polar polyolefinic and paracril differs greatly, and is the complete incompatible polymers of two classes.In order to improve the consistency of non-polar polyolefinic and paracril, the related personnel has done a large amount of work.ZL98117005.6 adopts dynamic vulcanization process to prepare polypropylene/paracril thermoplastic elastomer blend.Used expanding material is the reaction product of acrylic monomer graft polypropylene and diamine compounds; Vulcanizing agent is a tert butyl phenolic resin.Other components also comprise vulcanization activator, tenderizer, filler etc.US4355139 has proposed polypropylene (PP)/maleic anhydride inoculated polypropylene (the MAPP)/end capped paracril of amido (ATBN)/paracril co-mixing system, and MAPP and ATBN have generated the expanding material of PP and NBR on the spot in twin screw extruder.It is " Geolast " oil-resisting type dynamic vulcanization thermoplastic elastomer that Monsabto company adopted special capacity increasing technique to develop the trade mark in 1985, and its main component is polypropylene and paracril, and the physical and mechanical properties of intermingling material significantly improves.It is the Powdered acrylonitrile-butadiene rubber with crosslinking structure, polypropylene, maleic anhydride inoculated polypropylene, the blend of crosslinking coagent diethylene glycol diacrylate of 0.02～0.5 μ m with median size that ZL01110732.4 adopts the method for melt blending, then with blend cross-linking radiation under nitrogen atmosphere or vacuum, it is little to have prepared rubber size, tensile strength and elongation at break height, outward appearance is good, the thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer that processing characteristics is good.The thermoplastic elastomer that CN1365376A introduces and the composition of polar polymer are the reactive blending products of polyacrylic rubber and paracril, nonpolar crystalline olefin polymers and polyolefin elastomer.Product has favorable mechanical performance and antistatic property, can be used for making multi-layer sheet and film.As seen adopt maleic anhydride or acrylic monomer graft polypropylene can significantly improve the consistency of polyolefine and paracril as compatilizer.But these patents relate to all is the preparation Thermoplastic Elastomer, Olefinic, irrelevant with the modification of homo-polypropylene, and its production technique needs multistep to carry out, and is unfavorable for that heavy industrialization uses.In addition in order further to improve the toughness of matrix material, and, can consider to adopt the terpolymer EP rubber grafts, even realize terpolymer EP rubber grafts and paracril co-crosslinking as compatilizer in conjunction with the consistency that improves polyolefine and paracril.Patent CN1465614A adopts two-pack vulcanizing agent resol/superoxide and two-pack carboxylation polyolefine has solved paracril and ethylene-propylene rubber(EPR) is difficult to problems such as covulcanization and the two consistency difference, products obtained therefrom physicals excellence, particularly compression set performance significantly improves.Patent ZL00131707.5 has selected relative higher terpolymer EP rubber of vulcanization rate and paracril covulcanization for use with ZL96105334.8 when preparing ethylene/alpha-alkene/non-conjugated polyene trimerization rubber combination, the weathering resistance and the ozone resistance of paracril have significantly been improved, and the intensity height of products therefrom, oil-proofness is good, can be used for making automobile weather strip, brake facing etc.Though ethylene-propylene rubber(EPR) has participated in sulfidation in these patents, it more relates to how to improve the vulcanization rate of ethylene-propylene rubber(EPR), and technological process also needs multistep to finish.
Summary of the invention:
The objective of the invention is to address the above problem, a kind of Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer and preparation method thereof is provided, this composite cross-linked polymer significantly improves the impelling strength of homo-polypropylene, rigidity, tensile property influence to homo-polypropylene are less, can significantly improve simultaneously the oil-proofness and the static resistance of homo-polypropylene, be particularly useful for producing the refrigerator plastic components, production technique is simple and reliable, cost is lower, environmental friendliness.
For achieving the above object, the technical solution adopted in the present invention is: a kind of Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, and it is made up of following component: ratio of quality and the number of copies is 35～45 metallocene tribasic ethylene propylene rubber grafts component; Ratio of quality and the number of copies is 55～65 Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component;
Wherein said metallocene tribasic ethylene propylene rubber grafts component is obtained by following one-tenth component reaction: ratio of quality and the number of copies is 75～85 metallocene tribasic ethylene propylene rubber; Ratio of quality and the number of copies is the acrylic ester monomer between 1～3; Ratio of quality and the number of copies is 1～4 styrene monomer; Ratio of quality and the number of copies is 0.1～0.5 initiator; Ratio of quality and the number of copies is 8～15 inorganic rigid particle white carbon black; The GMA percentage of grafting of described metallocene tribasic ethylene propylene rubber grafts component is between 0.5～1.8%;
The mooney viscosity ML of described metallocene tribasic ethylene propylene rubber
125 ℃ 1+4Between 20～70;
Described methyl acrylic ester monomer is the methacrylic acid glyceryl ester (GMA) that contracts;
Described styrene monomer is a vinylbenzene;
The inorganic rigid particle white carbon black is a fumed silica, and particle diameter is between 7～12nm;
Wherein said Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component is obtained by following component reaction: ratio of quality and the number of copies is 65～85 Powdered acrylonitrile-butadiene rubber; Ratio of quality and the number of copies is 15～35 new LDPE (film grade); The initiator of ratio of quality and the number of copies 0.1-1; Its degree of crosslinking is between 60.5～72.3%;
Described initiator is an organo-peroxide;
Described organo-peroxide is dicumyl peroxide (DCP), di-t-butyl peroxide (DTBP), 2,5-2 (two " 2,5 " vulcanizing agent), preferred two " 2,5 " vulcanizing agents;
The acrylonitrile content of described Powdered acrylonitrile-butadiene rubber between 33～40%, mooney viscosity ML
100 ℃ 1+4Between 40～70;
The long-branch-chain polyethylene that described new LDPE (film grade) is produced for the high pressure vapor method, density is at 0.919～0.923g/cm
3Between, melting index MI is between 1.8～3.2g/10min;
The preparation method of a kind of Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer:
(1) raw material takes by weighing:
The metallocene tribasic ethylene propylene rubber grafts prepares feed composition: ratio of quality and the number of copies is 75～85 metallocene tribasic ethylene propylene rubber; Ratio of quality and the number of copies is 1～3 acrylic ester monomer; Ratio of quality and the number of copies is 1～4 styrene monomer; Ratio of quality and the number of copies is 0.1～0.5 initiator; Ratio of quality and the number of copies is 8～15 thermal silica.
Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density prepares feed composition: ratio of quality and the number of copies is 65～85 Powdered acrylonitrile-butadiene rubber; Ratio of quality and the number of copies is 15～35 new LDPE (film grade); The initiator of ratio of quality and the number of copies 0.1-1;
(2) mix: earlier independent mixed metallocene terpolymer EP rubber grafts component, independent again mixed powder paracril-polyethylene crosslinking substance in low density component.Mixing condition is under the normal temperature high-speed mixing 2-3 minute;
(3) grafting and crosslinked: the preceding opening for feed and the back opening for feed that the metallocene tribasic ethylene propylene rubber grafts component that mixes respectively in (2) and Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component are added the homodromy parallel twin screw extruder according to the front and back order respectively, granulation, regulate feed screw speed, guarantee that metallocene tribasic ethylene propylene rubber grafts component and Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density constituent mass portion rate is 35～45 and 55～65; Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer preparation process is made up of metallocene tribasic ethylene propylene rubber grafting process and paracril-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber co-crosslinking two-step reaction, and two-step reaction order on same twin screw extruder is finished; The granulation process condition is that (a) each section temperature is between 180～200 ℃; (b) screw speed is between 150-250 rev/min; The fervent pelletizing of water ring die face.
Described Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer is used for the modification of homo-polypropylene, both improved the impelling strength of homo-polypropylene, significantly improved its oil-proofness, static resistance again, the ratio that it added is 12% of a homo-polypropylene quality.
The crosslinking degree of Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) provided by the invention-metallocene tribasic ethylene propylene rubber composite cross-linked polymer represents with degree of crosslinking, i.e. the per-cent of gel content and material resin total amount.Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) provided by the invention-metallocene tribasic ethylene propylene rubber composite cross-linked polymer is used for the toughening modifying of homo-polypropylene, and its principle is: GMA grafting metallocene tribasic ethylene propylene rubber carries out the co-crosslinking reaction with paracril and new LDPE (film grade).The terpolymer EP rubber after the grafting and the consistency of paracril increase, and chemical reaction can take place, and its final product has perfect relatively cross-linked network.The inorganic rigid particle that is etched away by chromic acid is evenly distributed in the cross-linking system, form typical " nuclear-shell " structure, the existence of inorganic rigid particle is on the one hand as liquid organo-peroxide two " 2; 5 " the carrier of vulcanizing agent, help two " 2; 5 " the dispersion of vulcanizing agent, the while also can further be reduced the shearing resistance of cross-linking agent, helps shearing being dispersed into fine and homogeneous rubber grain more.The toughness reinforcing component of using as the homo-polypropylene toughening modifying, with compound uses of other auxiliary agents such as block copolymerization polypropylene expanding material and oxidation inhibitor, under the effect of shear-stress, this toughened master batch can be scattered in the homo-polypropylene matrix resin with littler more uniform fine micelle, absorb the impact energy that puts on matrix material effectively, thereby obtain significant toughening effect with less consumption.Simultaneously owing to contain a large amount of itrile group groups on the co-crosslinking thing macromolecular main chain, and micelle is uniformly dispersed tricklely, demonstrated the performance characteristics of vinyl cyanide component to a certain extent, significantly improved the oil-proofness and the static resistance of matrix material.
From above-mentioned principle of work as can be seen, the present invention compared with prior art, composite cross-linked polymer of the present invention can significantly improve the impelling strength of homo-polypropylene, and is less to rigidity, the tensile property influence of homo-polypropylene, significantly improved the oil-proofness and the static resistance of homo-polypropylene simultaneously.Under same proportioning, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer is compared with independent use metallocene tribasic ethylene propylene rubber, and the normal temperature shock strength of homo-polypropylene matrix material improves more than 3 times; Compare with POE/ high density polyethylene(HDPE) toughened master batch ,-20 ℃ shock strength of homo-polypropylene matrix material is suitable.In addition, compare with other cross-linking agent toughened systems, the required compatilizer block copolymerization polypropylene consumption of Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) of the present invention-metallocene tribasic ethylene propylene rubber composite cross-linked polymer still less more helps reducing cost.The more important thing is paracril as one of main ingredient of homo-polypropylene matrix material, with the surface resistivity of homo-polypropylene by 10
-16Ω
-1Level is reduced to 10
-12Ω
-1Level has improved the static resistance of homo-polypropylene; The surface contact angle of homo-polypropylene is reduced to 62.0 ° by 73.5 °, significantly improved homo-polypropylene polarity, and then improved the oil-proofness of homo-polypropylene.
Embodiment 1:
Taking by weighing model is that 125 ℃ of NORDEL IP 3745P, mooney viscosity ML (1+4) are 45 metallocene tribasic ethylene propylene rubber 1500g; GMA60g; Vinylbenzene 80g; DTBP10g; Model is that A-380, granularity are that the moral of 7 μ m is fixed the sand (Degussa) fumed silica 300g.In high-speed mixer, mix 3min under the normal temperature, obtain the Preblend of metallocene tribasic ethylene propylene rubber grafts component.Taking by weighing model subsequently is that ChemigumP615-D, acrylonitrile content are 33%, mooney viscosity ML
100 ℃ 1+4Be 50 paracril 2342g; (density is 0.923g/cm to the new LDPE (film grade) that the high pressure vapor method is produced
3, melting index MI is 3.2g/10min) and 1261g; DTBP 18g.In high-speed mixer, mix 3min under the normal temperature, obtain Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend.Earlier metallocene tribasic ethylene propylene rubber grafts component Preblend the past opening for feed is added the twin screw extruder that runs well, behind the 15s Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend is added the back opening for feed, in same cocurrent and parallel twin screw extruder, realize grafting-crosslinked-granulation process.Extruder temperature is distributed as, 180 ℃ of district's temperature, 185 ℃ of two district's temperature, 190 ℃ of three district's temperature, 190 ℃ of four district's temperature, 195 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 200 ℃ of eight district's temperature.200 rev/mins of screw speeds, preceding opening for feed feeding machine and back opening for feed feeding machine rotating ratio are 35: 65; The water ring die face cutting, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, the GMA percentage of grafting is 1.6%, degree of crosslinking 63.2%.
This cross-linking agent 85g, adding model is the homo-polypropylene 710g of B200, model is the Co-polypropylene 200g of K8303, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains toughness reinforcing rigid polypropylene blend, its tensile strength: 30.6MPa; Elongation at break: 297%; Flexural strength: 32.0MPa; Modulus in flexure: 1427MPa; Notched Izod impact strength: 557..2J/m during 23 ℃ of IZOD; Notched Izod impact strength in the time of IZOD-20 ℃: 61.9J/m; Surface resistivity is 2.5 * 10
-12Ω
-168.3 ° of surface contact angles.
Embodiment 2:
Most of with embodiment 1, difference is that organic peroxide evocating agent is two " 2,5 " vulcanizing agents.This Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, GMA percentage of grafting are 1.7%, degree of crosslinking 67.8%.
This cross-linking agent 85g, adding model is the homo-polypropylene 710g of B200, model is the Co-polypropylene 200g of K8303, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains toughness reinforcing rigid polypropylene blend, its tensile strength: 31.1MPa; Elongation at break: 285%; Flexural strength: 33.5MPa; Modulus in flexure: 1456MPa; Notched Izod impact strength: 563.7J/m during 23 ℃ of IZOD; Notched Izod impact strength in the time of IZOD-20 ℃: 66.4J/m; Surface resistivity is 7.1 * 10
-12Ω
-166.8 ° of surface contact angles.
Embodiment 3:
Taking by weighing model is that 125 ℃ of NORDEL IP 3745P, mooney viscosity ML (1+4) are 45 metallocene tribasic ethylene propylene rubber 1640g; GMA60g; Vinylbenzene 20g; Two " 2,5 " vulcanizing agent 6g; Model is that A-380, granularity are that the moral of 7 μ m is fixed the sand (Degussa) fumed silica 240g.In high-speed mixer, mix 3min under the normal temperature, obtain metallocene tribasic ethylene propylene rubber grafts component (A) Preblend.Taking by weighing model subsequently is that Chemigum P615-D, acrylonitrile content are 33%, mooney viscosity ML
100 ℃ 1+4Be 50 paracril 1669g; (density is 0.923g/cm to the new LDPE (film grade) that the high pressure vapor method is produced
3, melting index MI is 3.2g/10min) and 715g; " 2,5 " vulcanizing agent 19g.In high-speed mixer, mix 3min under the normal temperature, obtain Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend.Earlier metallocene tribasic ethylene propylene rubber grafts component Preblend the past opening for feed is added the twin screw extruder that runs well, behind the 15s Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend is added the back opening for feed, in same cocurrent and parallel twin screw extruder, realize grafting-crosslinked-granulation process.Extruder temperature is distributed as, 180 ℃ of district's temperature, 185 ℃ of two district's temperature, 190 ℃ of three district's temperature, 190 ℃ of four district's temperature, 195 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 200 ℃ of eight district's temperature.200 rev/mins of screw speeds, preceding opening for feed feeding machine and back opening for feed feeding machine rotating ratio are 45: 55; The water ring die face cutting, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, the GMA percentage of grafting is 1.5%, degree of crosslinking 70.6%.
This cross-linking agent 85g, adding model is the homo-polypropylene 710g of B200, model is the Co-polypropylene 200g of K8303, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains toughness reinforcing rigid polypropylene blend, its tensile strength: 32.7MPa; Elongation at break: 274%; Flexural strength: 34.1MPa; Modulus in flexure: 1504MPa; Notched Izod impact strength: 587.5J/m during 23 ℃ of IZOD; Notched Izod impact strength in the time of IZOD-20 ℃: 68.1J/m; Surface resistivity is 2.3 * 10
-12Ω
-163.5 ° of surface contact angles.
Embodiment 4:
Taking by weighing model is that 125 ℃ of NORDEL IP 3745P, mooney viscosity ML (1+4) are 45 metallocene tribasic ethylene propylene rubber 1700g; GMA20g; Vinylbenzene 60g; Two " 2,5 " vulcanizing agent 2g; Model is that A-380, granularity are that the moral of 7 μ m is fixed the sand (Degussa) fumed silica 180g.In high-speed mixer, mix 3min under the normal temperature, obtain metallocene tribasic ethylene propylene rubber grafts component (A) Preblend.Taking by weighing model subsequently is that Chemigum P615-D, acrylonitrile content are 33%, mooney viscosity ML
100 ℃ 1+4Be 50 paracril 2012g; (density is 0.923g/cm to the new LDPE (film grade) that the high pressure vapor method is produced
3, melting index MI is 3.2g/10min) and 671g; " 2,5 " vulcanizing agent 27g.In high-speed mixer, mix 3min under the normal temperature, obtain Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend.Earlier metallocene tribasic ethylene propylene rubber grafts component Preblend the past opening for feed is added the twin screw extruder that runs well, behind the 15s Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend is added the back opening for feed, in same cocurrent and parallel twin screw extruder, realize grafting-crosslinked-granulation process.Extruder temperature is distributed as, 180 ℃ of district's temperature, 185 ℃ of two district's temperature, 190 ℃ of three district's temperature, 190 ℃ of four district's temperature, 195 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 200 ℃ of eight district's temperature.200 rev/mins of screw speeds, preceding opening for feed feeding machine and back opening for feed feeding machine rotating ratio are 42: 58; The water ring die face cutting, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, the GMA percentage of grafting is 0.5%, degree of crosslinking 72.3%.
This cross-linking agent 85g, adding model is the homo-polypropylene 710g of B200, model is the Co-polypropylene 200g of K8303, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains toughness reinforcing rigid polypropylene blend, its tensile strength: 32.3MPa; Elongation at break: 255%; Flexural strength: 33.2MPa; Modulus in flexure: 1462MPa; Notched Izod impact strength: 530.6J/m during 23 ℃ of IZOD; Notched Izod impact strength in the time of IZOD-20 ℃: 60.7J/m; Surface resistivity is 5.2 * 10
-12Ω
-165.4 ° of surface contact angles.
Embodiment 5:
Taking by weighing model is that 125 ℃ of NORDEL IP 3745P, mooney viscosity ML (1+4) are 45 metallocene tribasic ethylene propylene rubber 1700g; GMA60g; Vinylbenzene 80g; Two " 2,5 " vulcanizing agent 10g; Model is that A-380, granularity are that the moral of 7 μ m is fixed the sand (Degussa) fumed silica 160g.In high-speed mixer, mix 3min under the normal temperature, obtain the Preblend of metallocene tribasic ethylene propylene rubber grafts component.Taking by weighing model subsequently is that Chemigum P615-D, acrylonitrile content are 33%, mooney viscosity ML
100 ℃ 1+4Be 50 paracril 2664g; (density is 0.923g/cm to the new LDPE (film grade) that the high pressure vapor method is produced
3, melting index MI is 3.2g/10min) and 470g; " 2,5 " vulcanizing agent 9.4g.In high-speed mixer, mix 3min under the normal temperature, obtain Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend.Earlier metallocene tribasic ethylene propylene rubber grafts component Preblend the past opening for feed is added the twin screw extruder that runs well, behind the 15s Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend is added back opening for feed charging opening, in same cocurrent and parallel twin screw extruder, realize grafting-crosslinked-granulation process.Extruder temperature is distributed as, 180 ℃ of district's temperature, 185 ℃ of two district's temperature, 190 ℃ of three district's temperature, 190 ℃ of four district's temperature, 195 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 200 ℃ of eight district's temperature.200 rev/mins of screw speeds, preceding opening for feed feeding machine and back opening for feed feeding machine rotating ratio are 39: 61; The water ring die face cutting, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, the GMA percentage of grafting is 1.8%, degree of crosslinking 60.5%.
This cross-linking agent 85g, adding model is the homo-polypropylene 710g of B200, model is the Co-polypropylene 200g of K8303, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains toughness reinforcing rigid polypropylene blend, its tensile strength: 30.8MPa; Elongation at break: 298%; Flexural strength: 32.2MPa; Modulus in flexure: 1421MPa; Notched Izod impact strength: 471.4J/m during 23 ℃ of IZOD; Notched Izod impact strength in the time of IZOD-20 ℃: 57.5J/m; Surface resistivity is 1.7 * 10
-12Ω
-162.0 ° of surface contact angles.
Embodiment 6:
Taking by weighing model is that 125 ℃ of NORDEL IP 3745P, mooney viscosity ML (1+4) are 45 metallocene tribasic ethylene propylene rubber 1956g; GMA60g; Vinylbenzene 60g; Two " 2,5 " vulcanizing agent 10g; Model is that A-380, granularity are that the moral of 7 μ m is fixed the sand (Degussa) fumed silica 240g.In high-speed mixer, mix 3min under the normal temperature, obtain the Preblend of metallocene tribasic ethylene propylene rubber grafts component.Taking by weighing model subsequently is that Chemigum P615-D, acrylonitrile content are 33%, mooney viscosity ML
100 ℃ 1+4Be 50 paracril 1956g; (density is 0.923g/cm to the new LDPE (film grade) that the high pressure vapor method is produced
3, melting index MI is 3.2g/10min) and 489g; " 2,5 " vulcanizing agent 12g.In high-speed mixer, mix 3min under the normal temperature, obtain Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend.Earlier metallocene tribasic ethylene propylene rubber grafts component Preblend the past opening for feed is added the twin screw extruder that runs well, behind the 15s Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component Preblend is added the back opening for feed, in same cocurrent and parallel twin screw extruder, realize grafting-crosslinked-granulation process.Extruder temperature is distributed as, 180 ℃ of district's temperature, 185 ℃ of two district's temperature, 190 ℃ of three district's temperature, 190 ℃ of four district's temperature, 195 ℃ of five district's temperature, 200 ℃ of six district's temperature, 200 ℃ of seven district's temperature, 200 ℃ of eight district's temperature.200 rev/mins of screw speeds, preceding opening for feed feeding machine and back opening for feed feeding machine rotating ratio are 45: 55; The water ring die face cutting, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, the GMA percentage of grafting is 1.3%, degree of crosslinking 71.5%.
This cross-linking agent 85g, adding model is the homo-polypropylene 710g of B200, model is the Co-polypropylene 200g of K8303, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains toughness reinforcing rigid polypropylene blend, its tensile strength: 32.5MPa; Elongation at break: 263%; Flexural strength: 34.6MPa; Modulus in flexure: 1523MPa; Notched Izod impact strength: 595.1J/m during 23 ℃ of IZOD; Notched Izod impact strength in the time of IZOD-20 ℃: 70.8J/m; Surface resistivity is 1.9 * 10
-12Ω
-162.5 ° of surface contact angles.
Contrast application examples 1
Do not adopt cross-linking agent to make toughner, and adopt metallocene tribasic ethylene propylene rubber NORDEL IP 3745P 85g, adding model is the homo-polypropylene 910g of B200, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains the toughening modifying polypropylene blend, its tensile strength: 27.7MPa; Elongation at break: 343%; Flexural strength: 29.4MPa; Modulus in flexure: 1431MPa; Notched Izod impact strength: 152.5J/m during 23 ℃ of IZOD; Notched Izod impact strength in the time of IZOD-20 ℃: 53.7J/m; Surface resistivity is 3.5 * 10
-16Ω
-173.5 ° of surface contact angles.
Contrast application examples 2
Do not adopt cross-linking agent to make toughner, and employing metallocene tribasic ethylene propylene rubber NORDEL IP 3745P 85g, adding model is the homo-polypropylene 660g of B200, model is the Co-polypropylene 250g of K8303, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains the toughening modifying polypropylene blend, its tensile strength: 26.5MPa; Elongation at break: 356%; Flexural strength: 28.5MPa; Modulus in flexure: 1229MPa; Notched Izod impact strength in the time of IZOD23 ℃: 270.2J/m; Notched Izod impact strength in the time of IZOD-20 ℃: 56.9J/m; Surface resistivity is 3.3 * 10
-16Ω
-173.2 ° of surface contact angles.
Contrast application examples 3
Do not adopt cross-linking agent to make toughner, and the described POE/HDPE cross-linking agent of employing patent CN01114932.9 85g, adding model is the homo-polypropylene 710g of B200, model is the Co-polypropylene 200g of K8303, antioxidant 1010 2g, oxidation inhibitor 168 is used 3g, obtains the toughening modifying polypropylene blend, its tensile strength: 30.2MPa; Elongation at break: 367%; Flexural strength: 31.7MPa; Modulus in flexure: 1475MPa; Notched Izod impact strength in the time of IZOD23 ℃: 831.8J/m; Notched Izod impact strength in the time of IZOD-20 ℃: 58.1J/m; Surface resistivity is 2.7 * 10
-16Ω
-173.0 ° of surface contact angles.
In sum, the modification that is used for homo-polypropylene provided by the invention had both improved the impelling strength of homo-polypropylene, had significantly improved its oil-proofness, static resistance again.Its principle is: GMA grafting metallocene tribasic ethylene propylene rubber carries out the co-crosslinking reaction with paracril and new LDPE (film grade).The terpolymer EP rubber after the grafting and the consistency of paracril increase, and chemical reaction can take place, and its final product has perfect relatively cross-linked network.The inorganic rigid particle that is etched away by chromic acid is evenly distributed in the cross-linking system, form typical " nuclear-shell " structure, the existence of inorganic rigid particle is on the one hand as liquid organo-peroxide two " 2; 5 " the carrier of vulcanizing agent, help two " 2; 5 " the dispersion of vulcanizing agent, the while also can further be reduced the shearing resistance of cross-linking agent, helps shearing being dispersed into fine and homogeneous rubber grain more.The toughness reinforcing component of using as the homo-polypropylene toughening modifying, with compound uses of other auxiliary agents such as block copolymerization polypropylene expanding material and oxidation inhibitor, under the effect of shear-stress, this toughened master batch can be scattered in the homo-polypropylene matrix resin with littler more uniform fine micelle, absorb the impact energy that puts on matrix material effectively, thereby obtain significant toughening effect with less consumption.Simultaneously owing to contain a large amount of itrile group groups on the co-crosslinking thing macromolecular main chain, and micelle is uniformly dispersed tricklely, demonstrated the performance characteristics of vinyl cyanide component to a certain extent, significantly improved the oil-proofness and the static resistance of matrix material.
The present invention compared with prior art, composite cross-linked polymer of the present invention can significantly be carried The impact flexibility of high HOPP is to rigidity, the tensile property impact of HOPP Littler, the while has significantly been improved oil resistivity and the antistatic behaviour of HOPP. Equally Under the proportioning, PNBR-low density polyethylene (LDPE)-metallocene tribasic ethylene propylene rubber is multiple Close cross-linking agent and compare with independent use metallocene tribasic ethylene propylene rubber, HOPP is compound The normal temperature impact strength of material improves 3.1～3.9 times; Toughness reinforcing with the POE/ high density polyethylene (HDPE) Masterbatch is compared, and-20 ℃ impact strength of HOPP composite is suitable. In addition, Compare with other cross-linking agent toughened systems, PNBR-low-density of the present invention is poly-The compatilizer block copolymerization that ethene-metallocene tribasic ethylene propylene rubber composite cross-linked polymer is required The polypropylene consumption still less more is conducive to reduce cost. The more important thing is the acrylonitrile-butadiene rubber conduct One of key component of HOPP composite is with the sheet resistance of HOPP Rate is by 1016The order of magnitude is reduced to 1012The order of magnitude has improved the antistatic of HOPP The property; The surface contact angle of HOPP is reduced to 62.0 ° by 73.5 °, significantly carries The high polarity of HOPP, and then improved the oil resistivity of HOPP.
Claims (8)
1, a kind of Powdered acrylonitrile-butadiene rubber-new LDPE (film grade)-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, it is characterized in that: it is made up of following component: ratio of quality and the number of copies is 35～45 metallocene tribasic ethylene propylene rubber grafts component; Ratio of quality and the number of copies is Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component of 55～65; Described metallocene tribasic ethylene propylene rubber grafts component is obtained by following component reaction: ratio of quality and the number of copies is 75～85 metallocene tribasic ethylene propylene rubber; Ratio of quality and the number of copies is the methyl acrylic ester monomer between 1～3; Ratio of quality and the number of copies is 1～4 styrene monomer; Ratio of quality and the number of copies is 0.1～0.5 initiator; Ratio of quality and the number of copies is 8～15 inorganic rigid particle white carbon black; The percentage of grafting of described metallocene tribasic ethylene propylene rubber grafts component is between 0.5～1.8%; Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component is obtained by following component reaction: ratio of quality and the number of copies is 65～85 Powdered acrylonitrile-butadiene rubber; Ratio of quality and the number of copies is 15～35 new LDPE (film grade); The initiator of ratio of quality and the number of copies 0.1-1; Its degree of crosslinking is between 60.5～72.3%.
2, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) according to claim 1-metallocene tribasic ethylene propylene rubber composite cross-linked polymer is characterized in that: 125 ℃ of the mooney viscosity ML (1+4) of metallocene tribasic ethylene propylene rubber are between 20～70 in the described metallocene tribasic ethylene propylene rubber grafts component; Described methyl acrylic ester monomer is the methacrylic acid glyceryl ester that contracts; Described styrene monomer is a vinylbenzene; Described inorganic rigid particle white carbon black is a fumed silica, and particle diameter is between 7～12nm.
3, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) according to claim 1-metallocene tribasic ethylene propylene rubber composite cross-linked polymer is characterized in that: described initiator is an organo-peroxide.
4, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) according to claim 3-metallocene tribasic ethylene propylene rubber composite cross-linked polymer is characterized in that: described organo-peroxide is 2,5-dimethyl-2,5-two hexanes.
5, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) according to claim 1-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, it is characterized in that: in described Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component, acrylonitrile content is between 33～40% in the Powdered acrylonitrile-butadiene rubber, and 125 ℃ of mooney viscosity ML (1+4) are between 40～70.
6, Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) according to claim 5-metallocene tribasic ethylene propylene rubber composite cross-linked polymer, it is characterized in that: in described Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component, the long-branch-chain polyethylene that new LDPE (film grade) is produced for the high pressure vapor method, density is at 0.919～0.923g/cm
3Between, melting index MI is between 1.8～3.2g/10min.
7, the preparation method of a kind of Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) as claimed in claim 1-metallocene tribasic ethylene propylene rubber composite cross-linked polymer the steps include:
(1) raw material takes by weighing:
The metallocene tribasic ethylene propylene rubber grafts prepares feed composition: ratio of quality and the number of copies is 75～85 metallocene tribasic ethylene propylene rubber; Ratio of quality and the number of copies is 1～3 acrylic ester monomer; Ratio of quality and the number of copies is 1～4 styrene monomer; Ratio of quality and the number of copies is 0.1～0.5 initiator; Ratio of quality and the number of copies is 8～15 inorganic rigid particle white carbon black;
Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density prepares feed composition: ratio of quality and the number of copies is 65～85 Powdered acrylonitrile-butadiene rubber; Ratio of quality and the number of copies is 15～35 new LDPE (film grade); The initiator of ratio of quality and the number of copies 0.1-1;
(2) mix:
Earlier independent mixed metallocene terpolymer EP rubber grafts component, independent again mixed powder paracril-polyethylene crosslinking substance in low density component; Mixing condition is under the normal temperature high-speed mixing 2-3 minute;
(3) grafting and crosslinked: the preceding opening for feed and the back opening for feed that the metallocene tribasic ethylene propylene rubber grafts component that mixes respectively in (2) and Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density component are added the homodromy parallel twin screw extruder according to the front and back order respectively, granulation, regulate feed screw speed, guarantee that metallocene tribasic ethylene propylene rubber grafts component and Powdered acrylonitrile-butadiene rubber-polyethylene crosslinking substance in low density constituent mass portion rate is 35～45 and 55～65; The granulation process condition is that (a) each section temperature is between 180～200 ℃; (b) screw speed is between 150-250 rev/min; The fervent pelletizing of water ring die face.
8, the described Powdered acrylonitrile-butadiene rubber-new LDPE (film grade) of claim 1-metallocene tribasic ethylene propylene rubber composite cross-linked polymer is in the impelling strength that improves homo-polypropylene, improve the purposes in its oil-proofness, static resistance field, it is characterized in that: the ratio that it added is 12% of a homo-polypropylene quality.
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