CN106280500B - A kind of thermoplastic dynamic vulcanized brombutyl/polypropene composition and preparation method thereof - Google Patents
A kind of thermoplastic dynamic vulcanized brombutyl/polypropene composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of thermoplastic dynamic vulcanized brombutyl/polypropene compositions and preparation method thereof, brombutyl/the polypropene composition is by brombutyl, polypropylene, dialkyl peroxide, peracid ester, N, and penylene bismaleimide, rubber softening oil and antiscorching agent are prepared between N.Preparation method includes the following steps：1）The mixing mixing of brombutyl, polypropylene, rubber softening oil and antiscorching agent；2）Vulcanizing agent is added, is uniformly mixed；3）By step 2）Obtained blend is transferred to single screw extrusion machine, extruding pelletization；4）By step 3）Obtained blend is transferred to parallel equidirectional two-screw extruder, carries out dynamic vulcanization, extruding pelletization.Thermoplastic dynamic vulcanized brombutyl/polypropene composition of the present invention has good hermetic seal and a barrier property, excellent in mechanical performance, can direct injection molding, production process is simple, and production efficiency is high, at low cost, use easy to spread.
Description
Technical field
The present invention relates to a kind of thermoplastic dynamic vulcanized brombutyl/polypropene compositions and preparation method thereof, belong to
In field of compound material.
Background technology
Brombutyl (BIIR) is to manufacture tubeless tyre irreplaceable raw material and druggist rubber sundrier
It must raw material.In early days, the Rubber plug material for hygienic material and pharmaceutical products manufacturing is mainly natural rubber, however, day
T PNR easily reacts with drug there are biological safety defect, and air-tightness is poor, and being directly used in medical packaging can be to the public
Safe medication generates very big threat.State's pencil of Bureau of Drugs Supervision of former country publication in 2000 notes (2000) No. 462 file regulations：Injection
With the antibiotic such as penicillin sodium salt, potassium salt of penicillin, ampicillin, streptomycin sulphate and infusion preparation, oral solution biology system
Product, blood product will stop using natural rubber rubber plug without exception equal to the end of the year 2004, all be changed to butyl rubber (IIR), halogenation fourth
Base rubber or polypropylene (PP), so that natural rubber rubber plug is substituted comprehensively.Butyl rubber plug, halogenated butyl rubber plug or poly- third
Alkene rubber plug has many advantages, such as that bio-safety, chemical stabilization are good, air-tightness is good, easy to clean, has been obtained extensively in Key works Drug packing industry
It uses.
However, conventional thermosetting medicinal butyl rubber, halogenated butyl rubber product generally use die pressing to produce, production
Process include raw rubber plasticate, compounding agent sieving drying, dispensing, mixing, cut-parts, vulcanization, trimming, the processes such as washing, technical process
Complexity, equipment investment is big, and production cost is high.If a kind of thermoplastic processing medicinal materials can be developed, can greatly simplify
Thermoset rubber product producing process can improve production efficiency while reducing pollution.Polypropylene abundance, price is just
Preferably, easily processed into type, product high comprehensive performance has certain compatibility with the brombutyl of low pole, if will
The two combines, and thermoplastic BIIR/PP materials are prepared into using dynamic vulcanization technology, instead of existing thermosetting property IIR and BIIR,
It is technically feasible, and have a vast market foreground.It is issued in March, 2011 in China《Industry restructuring guidance list
(sheet in 2011)》In, it explicitly points out and encourages novel medicinal packaging material and its technological development and production, meanwhile, limitation creates, changes
Build and extend medicinal butyl rubber plug device.
Application No. is 2014108288445 Chinese patents to disclose a kind of medical thermoplasticity brombutyl of soft
And preparation method thereof, but whole preparation process needs five steps to complete, complex process, and used phenolic resin vulcanization system
The easy moisture absorption needs that processing is dried before use, and the brombutyl of preparation before also needs that processing is dried, produce
It is not high with service efficiency, and antiscorching agent is not used in its formula system, brombutyl sulfurate activity is high, exists without using antiscorching agent
Easily incipient scorch in actual production.
The invention discloses a kind of thermoplastic dynamic vulcanized brombutyl/polypropene compositions, using one kind
It is not required to dry pretreated vulcanizing system, can prepare thermoplastic dynamic vulcanized BIIR/PP by a step dynamic vulcanization combines
Object.
Invention content
The purpose of the present invention is to provide a kind of thermoplastic dynamic vulcanized brombutyl/polypropene composition and its systems
Preparation Method.
The technical solution used in the present invention is：
A kind of thermoplastic dynamic vulcanized brombutyl/polypropene composition is prepared by the raw material of following mass parts
It forms：
Brombutyl：100 parts；
Polypropylene：25~55 parts；
Dialkyl peroxide：0.5~1.5 part；
Peracid ester：0.5~1.5 part；
N, N '-penylene bismaleimide：1~3 part；
Rubber softening oil：110~150 parts；
Antiscorching agent：0.5~2 part.
The bromine content of the brombutyl is 1.5wt%~2.5wt%.
The polypropylene be 11~20g/10min of melt index random polypropylene, test condition be 230 DEG C/
2.16kg。
The dialkyl peroxide is di-tert-butyl peroxide.
The peracid ester is peroxidized t-butyl perbenzoate.
The N, grain size≤150 micron of N '-penylene bismaleimide.
The antiscorching agent is at least one of magnesia, calcium oxide, zinc stearate, benzothiazole.
The preparation method of above-mentioned thermoplastic dynamic vulcanized brombutyl/polypropene composition, includes the following steps：
1) mixer is added in brombutyl, polypropylene, rubber softening oil, antiscorching agent, be uniformly mixed；
2) mixer, mixing is added in dialkyl peroxide, peracid ester and N, N '-penylene bismaleimide again
Uniformly；
3) blend that step 2) obtains is transferred to single screw extrusion machine, be granulated；
4) blend that step 3) obtains is transferred to parallel equidirectional two-screw extruder, carries out dynamic vulcanization, extruding pelletization,
Obtain thermoplastic dynamic vulcanized brombutyl/polypropene composition.
The operation temperature of mixer described in step 1) is 160~190 DEG C, and closed-smelting machine rotor rotating speed is 70~120rpm,
Mixing time is 5~20min.
The operation temperature of mixer described in step 2) is 50~100 DEG C, and closed-smelting machine rotor rotating speed is 50~80rpm, close
The refining time is 5~10min.
Each area's temperature of single screw extrusion machine described in step 3) is 20~80 DEG C, and screw speed is 200~300rpm.
The screw speed of double screw extruder described in step 4) is 200~280rpm, and extrusion temperature is 80~200 DEG C.
The screw slenderness ratio of double screw extruder described in step 4) is 48~60.
The beneficial effects of the invention are as follows：Thermoplastic dynamic vulcanized brombutyl/polypropylene (BIIR/PP) of the present invention
Composition can provide BIIR using the peroxide vulcanizing agent that half-life period is different in the leading portion and back segment of dynamic vulcanization
The free radical crosslinked, it is ensured that BIIR is full cross-linked, and the thermoplastic dynamic vulcanized BIIR/PP compositions being prepared were both
Maintain good hermetic seal and the barrier property of BIIR, and show excellent mechanical property, and can direct injection molding, produced
Journey is simple to operation, if being used for medical rubber stopper, is greatly improved rubber plug production efficiency, reduces cost, use easy to spread.
Description of the drawings
Fig. 1 is the production technological process of thermoplastic dynamic vulcanized brombutyl/polypropene composition of the present invention.
Specific implementation mode
A kind of thermoplastic dynamic vulcanized brombutyl/polypropene composition is prepared by the raw material of following mass parts
It forms：
Brombutyl：100 parts；
Polypropylene：25~55 parts；
Dialkyl peroxide：0.5~1.5 part；
Peracid ester：0.5~1.5 part；
N, N '-penylene bismaleimide：1~3 part；
Rubber softening oil：110~150 parts；
Antiscorching agent：0.5~2 part.
Preferably, the bromine content of the brombutyl is 1.5wt%~2.5wt%.
Preferably, the polypropylene is the random polypropylene of 11~20g/10min of melt index, test condition 230
℃/2.16kg。
It is further preferred that the melt index that the polypropylene is platform modeling (Ningbo) limited liability company is 15g/
The random polypropylene of 10min, test condition are 230 DEG C/2.16kg.
Preferably, the dialkyl peroxide is di-tert-butyl peroxide (DBP).
It is further preferred that the dialkyl peroxide is the Trigonox B of Akzo Nobel N.V..
Preferably, the peracid ester is peroxidized t-butyl perbenzoate (TBPB).
It is further preferred that the peracid ester is the Trigonox C of Akzo Nobel N.V..
Preferably, the N, grain size≤150 micron of N '-penylene bismaleimide.
It is further preferred that the N, N '-penylene bismaleimide is Xi'an span new material Co., Ltd
HVA-2。
Preferably, the antiscorching agent is at least one of magnesia, calcium oxide, zinc stearate, benzothiazole.
The preparation method of above-mentioned thermoplastic dynamic vulcanized brombutyl/polypropene composition, includes the following steps：
1) mixer is added in brombutyl, polypropylene, rubber softening oil, antiscorching agent, be uniformly mixed；
2) mixer, mixing is added in dialkyl peroxide, peracid ester and N, N '-penylene bismaleimide again
Uniformly；
3) blend that step 2) obtains is transferred to single screw extrusion machine, be granulated；
4) blend that step 3) obtains is transferred to parallel equidirectional two-screw extruder, carries out dynamic vulcanization, extruding pelletization,
Obtain thermoplastic dynamic vulcanized brombutyl/polypropene composition.
Preferably, the operation temperature of the mixer described in step 1) be 160~190 DEG C, closed-smelting machine rotor rotating speed be 70~
120rpm, mixing time are 5~20min.
Preferably, the operation temperature of the mixer described in step 2) be 50~100 DEG C, closed-smelting machine rotor rotating speed be 50~
80rpm, mixing time are 5~10min.
Preferably, each area's temperature of single screw extrusion machine described in step 3) is 20~80 DEG C, screw speed is 200~
300rpm。
Preferably, the screw speed of the double screw extruder described in step 4) be 200~280rpm, extrusion temperature be 80~
200℃。
Preferably, the screw slenderness ratio of the double screw extruder described in step 4) is 48~60.
Preferably, the screw configuration of the double screw extruder described in step 4) is single thread, and there are five screw rods above
Gear block area, there are two above left-hand thread areas for screw rod.
The present invention is made further explanation and description with reference to specific embodiment.
Fig. 1 is the production technological process of thermoplastic dynamic vulcanized brombutyl/polypropene composition of the present invention,
Examples 1 to 6 is carried out according to the technological process.
Embodiment 1：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：55 parts；
Di-tert-butyl peroxide (Trigonox B)：0.5 part；
Peroxidized t-butyl perbenzoate (Trigonox C)：0.5 part；
N, N '-penylene bismaleimide (HVA-2)：1 part；
Rubber softening oil：150 parts；
MgO：0.5 part.
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 190 DEG C of mixer temperature, mixer
Rotor speed 120rpm, mixing time 5min；
2) mixer is added in DBP, TBPB and HVA-2 again, be uniformly mixed, mixer temperature 50 C, closed-smelting machine rotor turns
Fast 80rpm, mixing time 5min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 200rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
48, screw rod has 6 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Embodiment 2：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 2.0wt%, sinopec Yanshan Petrochemical company)：100 parts；
PP：40 parts；
Di-tert-butyl peroxide (Trigonox B)：1 part；
Peroxidized t-butyl perbenzoate (Trigonox C)：1 part；
N, N '-penylene bismaleimide (HVA-2)：2 parts；
Rubber softening oil：130 parts；
MgO：1 part.
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 170 DEG C of mixer temperature, mixer
Rotor speed 100rpm, mixing time 10min；
2) mixer is added in DBP, TBPB and HVA-2 again, be uniformly mixed, 80 DEG C of mixer temperature, closed-smelting machine rotor turns
Fast 60rpm, mixing time 8min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 300rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Embodiment 3：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 2.4wt%, Exxon Mobil company)：100 parts；
PP：25 parts；
Di-tert-butyl peroxide (Trigonox B)：1.5 part；
Peroxidized t-butyl perbenzoate (Trigonox C)：1.5 part；
N, N '-penylene bismaleimide (HVA-2)：3 parts；
Rubber softening oil：110 parts；
MgO：2 parts.
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 160 DEG C of mixer temperature, mixer
Rotor speed 70rpm, mixing time 20min；
2) mixer is added in DBP, TBPB and HVA-2 again, be uniformly mixed, 100 DEG C of mixer temperature, closed-smelting machine rotor turns
Fast 50rpm, mixing time 10min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 200rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
60, screw rod has 7 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Embodiment 4：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：55 parts；
Di-tert-butyl peroxide (Trigonox B)：0.5 part；
Peroxidized t-butyl perbenzoate (Trigonox C)：1 part；
N, N '-penylene bismaleimide (HVA-2)：1 part；
Rubber softening oil：150 parts；
MgO：0.5 part.
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 190 DEG C of mixer temperature, mixer
Rotor speed 70rpm, mixing time 20min；
2) mixer is added in DBP, TBPB and HVA-2 again, be uniformly mixed, 100 DEG C of mixer temperature, closed-smelting machine rotor turns
Fast 50rpm, mixing time 10min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 300rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Embodiment 5：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：55 parts；
Di-tert-butyl peroxide (Trigonox B)：1 part；
Peroxidized t-butyl perbenzoate (Trigonox C)：1 part；
N, N '-penylene bismaleimide (HVA-2)：1 part；
Rubber softening oil：150 parts；
MgO：0.5 part.
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 180 DEG C of mixer temperature, mixer
Rotor speed 70rpm, mixing time 20min；
2) mixer is added in DBP, TBPB and HVA-2 again, be uniformly mixed, 100 DEG C of mixer temperature, closed-smelting machine rotor turns
Fast 50rpm, mixing time 10min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 300rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Embodiment 6：
A kind of thermoplastic dynamic vulcanized BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：55 parts；
Di-tert-butyl peroxide (Trigonox B)：1 part；
Peroxidized t-butyl perbenzoate (Trigonox C)：1 part；
N, N '-penylene bismaleimide (HVA-2)：2 parts；
Rubber softening oil：150 parts；
CaO：0.5 part.
The preparation method of above-mentioned thermoplastic dynamic vulcanized BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 180 DEG C of mixer temperature, mixer
Rotor speed 70rpm, mixing time 20min；
2) mixer is added in DBP, TBPB and HVA-2 again, be uniformly mixed, 100 DEG C of mixer temperature, closed-smelting machine rotor turns
Fast 50rpm, mixing time 10min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 300rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains thermoplastic dynamic vulcanized BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Comparative example 1：
A kind of BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：55 parts；
Di-tert-butyl peroxide (Trigonox B)：0.5 part；
Peroxidized t-butyl perbenzoate (Trigonox C)：0.5 part；
N, N '-penylene bismaleimide (HVA-2)：1 part；
Rubber softening oil：150 parts；
MgO：0.5 part.
The preparation method of above-mentioned BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 190 DEG C of mixer temperature, mixer
Rotor speed 120rpm, mixing time 5min；
2) mixer is added in DBP, TBPB and HVA-2 again, be uniformly mixed, mixer temperature 50 C, closed-smelting machine rotor turns
Fast 80rpm, mixing time 5min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 200rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is double thread, and the ratio between spiro rod length L and diameter D are
30, screw rod has 1 gear block area, screw rod not to have left-hand thread area；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Comparative example 2：
A kind of BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 1.8wt%, German Lanxess Corporation)：100 parts；
PP：55 parts；
Rubber softening oil：150 parts；
MgO：0.5 part.
The preparation method of above-mentioned BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 190 DEG C of mixer temperature, mixer
Rotor speed 120rpm, mixing time 5min；
2) rubber blend made from step 1) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 200rpm；
3) by rubber blend made from step 2) in parallel equidirectional two-screw extruder extruding pelletization, obtain BIIR/
PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
48, screw rod has 6 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Comparative example 3：
A kind of BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 1.03wt%, Exxon Mobil company)：100 parts；
PP：55 parts；
Di-tert-butyl peroxide (Trigonox B)：0.5 part；
Peroxidized t-butyl perbenzoate (Trigonox C)：0.5 part；
N, N '-penylene bismaleimide (HVA-2)：1 part；
Rubber softening oil：150 parts；
MgO：0.5 part.
The preparation method of above-mentioned BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil and MgO, be uniformly mixed, 190 DEG C of mixer temperature, mixer
Rotor speed 120rpm, mixing time 5min；
2) mixer is added in DBP, TBPB and HVA-2 again, be uniformly mixed, mixer temperature 50 C, closed-smelting machine rotor turns
Fast 80rpm, mixing time 5min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 200rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
Comparative example 4：
A kind of BIIR/PP compositions, raw material composition are following (mass parts)：
BIIR (bromine content 2.0wt%, sinopec Yanshan Petrochemical company)：100 parts；
PP：40 parts；
Di-tert-butyl peroxide (Trigonox B)：1 part；
N, N '-penylene bismaleimide (HVA-2)：2 parts；
Rubber softening oil：130 parts；
MgO：1 part.
The preparation method of above-mentioned BIIR/PP compositions, includes the following steps：
1) mixer is added in BIIR, PP, rubber softening oil, MgO, be uniformly mixed, 190 DEG C of mixer temperature, mixer
Rotor speed 120rpm, mixing time 5min；
2) mixer is added in DBP and HVA-2 again, be uniformly mixed, mixer temperature 50 C, closed-smelting machine rotor rotating speed
80rpm, mixing time 5min；
3) rubber blend made from step 2) is granulated in single screw extrusion machine, setting each area's temperature of single screw rod is 20
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, screw speed 200rpm；
4) rubber blend made from step 3) is subjected to dynamic vulcanization in parallel equidirectional two-screw extruder, extrusion is made
Grain, obtains BIIR/PP compositions.
The screw configuration of the parallel equidirectional two-screw extruder is single thread, and the ratio between spiro rod length L and diameter D are
52, screw rod has 7 gear block areas, screw rod to have 3 left-hand thread areas；The screw speed of the parallel equidirectional two-screw extruder is
280rpm；Screw zones and head temperature 80,150,160,170,180,190,200,200,200,200,200,200,200/
195℃。
The raw material of Examples 1 to 6 and comparative example 1~4 composition is as shown in table 1.
The raw material of 1 Examples 1 to 6 of table and comparative example 1~4 forms (mass parts)
Test case：
The BIIR/PP compositions prepared to Examples 1 to 6 and comparative example 1~4 are tested for the property, test result such as table 2
It is shown.
The performance test data of the BIIR/PP compositions of 2 Examples 1 to 6 of table and comparative example 1~4
Testing standard and method：
Shore A hardness：By ASTM-D2240 standard testings；
Tensile strength and elongation at break：By ASTM-D412 standard testings, rate of extension 500mm/min；
Melt index：By ASTM D1238 standard testings, 230 DEG C of test temperature, load 5kg.
From Tables 1 and 2：
1) different with double screw extruder used by Examples 1 to 6 due to comparative example 1, BIIR/ prepared by comparative example 1
Tensile strength, elongation at break and the melt index of PP compositions are significantly lower than BIIR/PP compositions prepared by Examples 1 to 6,
Its mechanical property and processing performance are poor；
2) due to being not added with vulcanizing agent in comparative example 2, the combination of DBP, TBPB and HVA-2 are added in Examples 1 to 6
Vulcanizing agent, tensile strength, elongation at break and the melt index of BIIR/PP compositions prepared by comparative example 2 will be significantly lower than in fact
The BIIR/PP compositions of the preparation of example 1~6 are applied, comprehensive performance is poor；
3) since the bromine content of the BIIR employed in comparative example 3 is only 1.03wt%, hence it is evident that less than in Examples 1 to 6
1.5wt%~2.5wt%, the hardness of BIIR/PP compositions, tensile strength and elongation at break prepared by comparative example 3 be low
In BIIR/PP compositions prepared by Examples 1 to 6, comprehensive performance is poor；
4) due to being not added with vulcanizing agent TBPB in comparative example 4, the melt index of BIIR/PP compositions prepared by comparative example 4,
Tensile strength and elongation at break are below the BIIR/PP compositions of Examples 1 to 6 preparation, and comprehensive performance is poor；
5) as PP and rubber softening oil additive amount increase in Examples 1 to 6, the BIIR/PP compositions being prepared
Increased trend is presented in tensile strength and melt index；By embodiment 1 and embodiment 4,5,6 as can be seen that with high temperature sulphur
The increase of agent TBPB contents, the tensile strength for the BIIR/PP compositions being prepared are gradually increased, but melting can be caused to refer to
The faint decline of number and elongation at break.Wherein, the comprehensive performance of the thermoplastic dynamic vulcanized BIIR/PP compositions of embodiment 4
It is best.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (5)
1. a kind of thermoplastic dynamic vulcanized brombutyl/polypropene composition, it is characterised in that：It is by following mass parts
Raw material is prepared：
Brombutyl：100 parts；
Polypropylene：25~55 parts；
Dialkyl peroxide：0.5~1.5 part；
Peracid ester：0.5~1.5 part；
N, N '-penylene bismaleimide：1~3 part；
Rubber softening oil：110~150 parts；
Antiscorching agent：0.5~2 part；
The bromine content of the brombutyl is 1.5wt%~2.5wt%；
The dialkyl peroxide is di-tert-butyl peroxide；
The peracid ester is peroxidized t-butyl perbenzoate；
Thermoplastic dynamic vulcanized brombutyl/the polypropene composition is prepared by the following method to obtain：1) by bromine
Change butyl rubber, polypropylene, rubber softening oil, antiscorching agent and mixer is added, is uniformly mixed；2) again by dialkyl peroxide,
Mixer is added in peracid ester and N, N '-penylene bismaleimide, is uniformly mixed；3) blend for obtaining step 2) turns
Enter single screw extrusion machine, is granulated；4) blend that step 3) obtains is transferred to parallel equidirectional two-screw extruder, into Mobile state sulphur
Change, extruding pelletization obtains thermoplastic dynamic vulcanized brombutyl/polypropene composition；
The screw slenderness ratio of double screw extruder described in step 4) is 48~60.
2. thermoplastic dynamic vulcanized brombutyl/polypropene composition according to claim 1, it is characterised in that：
The polypropylene is the random polypropylene of 11~20g/10min of melt index, and test condition is 230 DEG C/2.16kg.
3. thermoplastic dynamic vulcanized brombutyl/polypropene composition according to claim 1, it is characterised in that：
Grain size≤150 micron of the N, N ＇-penylene bismaleimide.
4. thermoplastic dynamic vulcanized brombutyl/polypropene composition according to claim 1, it is characterised in that：
The antiscorching agent is at least one of magnesia, calcium oxide, zinc stearate, benzothiazole.
5. thermoplastic dynamic vulcanized brombutyl/polypropene composition according to claim 1, it is characterised in that：
The operation temperature of mixer described in step 1) is 160~190 DEG C, and closed-smelting machine rotor rotating speed is 70~120rpm, mixing time
For 5~20min；The operation temperature of mixer described in step 2) is 50~100 DEG C, and closed-smelting machine rotor rotating speed is 50~80rpm,
Mixing time is 5~10min；Each area's temperature of single screw extrusion machine described in step 3) is 20~80 DEG C, screw speed is 200~
300rpm；The screw speed of double screw extruder described in step 4) is 200~280rpm, and extrusion temperature is 80~200 DEG C.
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| CN102585319A (en) * | 2012-01-11 | 2012-07-18 | 华东理工大学 | Vulcanizing system of brominated butyl rubber/ polypropylene thermoplastic elastomer sealing material and preparation method for sealing material |
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