CN104559205B - A kind of preparation method of in-situ flexible polypropylene alloy - Google Patents
A kind of preparation method of in-situ flexible polypropylene alloy Download PDFInfo
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- CN104559205B CN104559205B CN201510000542.3A CN201510000542A CN104559205B CN 104559205 B CN104559205 B CN 104559205B CN 201510000542 A CN201510000542 A CN 201510000542A CN 104559205 B CN104559205 B CN 104559205B
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Abstract
The invention provides a kind of in-situ flexible polypropylene alloy preparation method.By reactive extrursion method in polypropylene molecular chain situ-formed graft high vinyl polybutadiene, to improve the interface compatibility of polypropylene and high vinyl polybutadiene.Propylene alloy is prepared with reaction melt-blending process has the advantages that compatibility is good, dispersed phase is uniform, toughening effect good.Polypropylene alloy preparation method is simple, environmentally safe for such, be easily achieved large-scale continuous production.Polypropylene alloy prepared by the present invention can be used for the fields such as medicine equipment, packaging for foodstuff and Key works Drug packing, and TPV thermoplastic elastomer (TPE)s can be substituted to a certain extent, reduce production cost.Using the polypropylene alloy of in-situ flexible, product notch impact strength is more than 75kJ/m2, elongation at break is more than 700%, and tensile strength is held essentially constant.
Description
Technical field
The present invention relates to a kind of method for preparing polypropylene alloy, more particularly to a kind of in-situ flexible polypropylene alloy
Preparation method.
Background technology
Polypropylene has that proportion is small, price is low as a kind of thermoplastic having wide range of applications, stable chemical performance,
The features such as fabric filing effect is high.But its fragility is high, notch impact strength is low, is especially particularly acute in low temperature, due to existing
These significant shortcomings, limit the larger range of application of polypropylene（Application study of the building composite in civil engineering,
Information, 2009（11）：50-54）.Therefore, polyacrylic impact property is improved using any approach as polypropylene
One important topic of study on the modification.
Generally, the material available for tenacity-increased profax is a lot, such as traditional rubber or elastomer, thermoplasticity
Plastics, also inorganic rigid particle, nano-particle etc..Wang Wei's will et al. have studied butadiene-styrene rubber tenacity-increased profax（Journal
of engineered fibers and fabrics.2009,4(1):26-33）.Li Haidong et al. have studied PP/EPDM blendings
The toughness of thing（Elastomer, 2005,5:26-28）.Bright sea of Lee et al. have studied polyethylene tenacity-increased profax（Modern plastics processing should
With 2005,5:15-18）.Chen Ming just have studied rare-earth coupling agent to PP/CaCO3The influence of composite ageing properties（Plastics
Industry, 2005,8:60-63）.Zhao Guizhe etc. has done Nano-meter SiO_22The polyacrylic research of activeness and quietness（Jilin University's journal,
2005,2:205-209）.Yang Ning etc. have studied potassium titanate crystal whisker activeness and quietness polypropylene（Chinese Plastics, 2004,1:75-78）.
More than study, there is problems with, first, under low temperature, embrittlement easily occurs for rubber, does not reach improvement polypropylene low temperature
Brittle purpose；Second, elastomer, inorganic rigid particle and nano-particle toughening polypropylene all Presence of an interface are compatible asks
Topic.The present invention uses situ-formed graft technology, and the situ-formed graft high vinyl polybutadiene on polypropylene macromolecular chain can be simultaneously
The shortcoming of elastomer and polyacrylic interface compatibility difference and rubber black brittleness difference is solved, the toughness of polypropylene alloy is improved.
At present, report prepared by in-situ flexible polypropylene alloy is had no.
The content of the invention
In order to improve polyacrylic low-temperature flexibility, the problems such as interface compatibility is poor is overcome.It is an object of the invention to provide
A kind of method for preparing in-situ flexible polypropylene alloy, by reactive extrursion in polypropylene molecular chain situ-formed graft high-vinyl
Polybutadiene, then prepares polypropylene alloy by it with polypropylene fusion blending.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method prepared by in-situ flexible polypropylene alloy, it is characterised in that prepared as steps described below with condition：
The first step：The preparation of functionalization high vinyl polybutadiene
Component A and component B is added in reaction bulb, dissolved in magnetic agitation at 65 DEG C to component A, is added into reaction bulb
Component C and D, are stirred, and quantitative component E is added into system, in reacting a period of time under constant temperature, are reacted after terminating,
Product is poured out, adding absolute ethyl alcohol separates out solid, sedimentation a period of time, suction filtration, with sodium bicarbonate solution and distillation moisture
Other washed product solid several times, are put into 60 DEG C of vacuum drying 12h of baking oven, obtain product.
Wherein described component A is high vinyl polybutadiene, and using lithium alkylide catalyst system and catalyzing, ionic polymerization, number is divided equally
Son amount Mn is 1200000, and crystallinity 20%, contents of ethylene is more than 95%.
Wherein described component B is lower paraffin hydrocarbon or cycloalkane, such as hexamethylene.
Wherein described component C is a kind of carboxylic acid, such as formic acid, acetic acid etc..
Wherein described component D is a kind of phase transfer catalyst, such as polyethylene glycol.
Wherein described component E is a kind of oxidant, such as hydrogen peroxide.
Wherein described component A mass concentration is that 8g/dL, component C and component A mass concentration ratio are Mc/Ma=21.5%,
Component C and component E mol ratio is：C/E=1:1.
Second step：The pre-irradiation of acrylic resin
Pre-irradiation processing is carried out to acrylic resin using electron accelerator or cobalt source, irradiation dose is 5-30kGy, is prepared
Pre-irradiation polypropylene with polymeric peroxide；
Described acrylic resin is COPP, melt flow rate (MFR) 0.5-20g/10min；
3rd step：The preparation of the acrylic resin of situ-formed graft functionalization high vinyl polybutadiene
The polypropylene, functionalization high vinyl polybutadiene, pre-irradiation polypropylene for weighing formula consumption carry out mechanical mixture
Afterwards, reactive extrusion, the acrylic resin of situ-formed graft functionalization high vinyl polybutadiene in double screw extruder are added；
Described polypropylene is COPP, ethylene-propylene random copolymer or their mixture, and wherein copolymerization gathers
Ethylene contents are 1-15wt% in the melt flow rate (MFR) 0.5-20g/10min of propylene, ethylene-propylene random copolymer；
Described functionalization high vinyl polybutadiene consumption is the 1-10% of polypropylene weight, and pre-irradiation is polyacrylic to be used
Measure the 5-30% for polypropylene weight；
Described double screw extruder is hing surface in the same direction, and draw ratio is 40-48, and machine barrel is equipped with multiple
Independent heating unit and multiple steam vents, energy independent control react the temperature in each stage；
170-220 DEG C described of reactive extrusion temperature, screw speed 10-200rpm, 3-8 points of residence time of material
Clock；
Beneficial effects of the present invention：
By reactive extrursion method in polypropylene molecular chain situ-formed graft functionalization high vinyl polybutadiene, with improve
The interface compatibility of its alloy, so as to improve its low-temperature flexibility.Functionalization high vinyl polybutadiene is prepared with reactive grafting method
Situ-formed graft polypropylene alloy has the advantages that dispersed phase is uniformly dispersed, interface compatibility is good, low temperature performance excellent.This birdss of the same feather flock together third
Alkene alloy preparation method is simple, environmentally safe, be easily achieved large-scale continuous production.Polypropylene alloy prepared by the present invention
Available for fields such as medicine equipment, packaging for foodstuff and Key works Drug packings, TPV thermoplastic elastomer (TPE)s can be substituted to a certain extent,
Reduce production cost.When functionalization high vinyl polybutadiene content is less than 10%, the elongation at break of product can exceed
700%, normal temperature notch impact strength is not less than 75KJ/m2.Therefore such polypropylene alloy has good resistance to low temperature.
Embodiment
Embodiment 1
By 15g polybutadiene, 200ml hexamethylenes are put into 500ml there-necked flasks, at 65 DEG C, treat high-vinyl polybutadiene
Alkene is completely dissolved, and is slowly added into system after 3.2g formic acid, 0.6g polyethylene glycol, completion of dropping, is reacted 0.5 hour, will
3.2g hydrogen peroxide is interior in 20min to be slowly dropped in system, in continuing to react 2 hours under constant temperature, after reaction terminates, will be produced
Thing is poured out, and adding absolute ethyl alcohol separates out solid, and sedimentation a period of time, suction filtration is washed respectively with sodium bicarbonate solution and distilled water
Wash product solid for several times, be put into 60 DEG C of vacuum drying 12h of baking oven, obtain white toughness product.
Embodiment 2
By 15g polybutadiene, 200ml hexamethylenes are put into 500ml there-necked flasks, at 65 DEG C, treat high-vinyl polybutadiene
Alkene is completely dissolved, and is slowly added into system after 1.8 formic acid, 0.3g polyethylene glycol, completion of dropping, is reacted 0.5 hour, by 1.8g
Hydrogen peroxide is interior in 20min to be slowly dropped in system, and in continuing to react 2 hours under constant temperature, after reaction terminates, product is fallen
Go out, adding absolute ethyl alcohol separates out solid, sedimentation a period of time, suction filtration washs production respectively with sodium bicarbonate solution and distilled water
Thing solid several times, are put into 60 DEG C of vacuum drying 12h of baking oven, obtain white toughness product.
Embodiment 3-6
Pre-irradiation processing is carried out to COPP using electron accelerator, irradiation dose is listed in Table 1 below, and is prepared with big
The pre-irradiation polypropylene of molecule peroxide.
By COPP, ethylene-propylene random copolymer（CPP）Or their blend carries out pre-irradiation, prepares band
There is the pre-irradiation polypropylene of polymeric peroxide.Reactive extrusion temperature is 200 DEG C, and screw speed is 80rpm, and material stops
It is 3min to stay the time.Pre-irradiation polypropylene material proportioning is shown in Table 1.COPP melt flow rate (MFR) used is 2.0g/
10min, CPP melt flow rate (MFR)s used are 3.0g/10min.
Embodiment 7-10
Embodiment 7,8,9 and 10 is that will correspond to the pre-irradiation acrylic resin and work(prepared in embodiment 3,4,5 and 6 respectively
High vinyl polybutadiene can be changed and polypropylene carries out reactive extrusion, the polypropylene alloy of melting toughness reinforcing in situ is prepared.
Reactive extrusion temperature is 200 DEG C, and screw speed is 80rpm, and residence time of material is 3min.It is high in polypropylene alloy material
The content of vinyl polybutadiene is shown in Table 2.COPP melt flow rate (MFR) used is 2.0g/10min, CPP used
Melt flow rate (MFR) is 3.0g/10min, its elongation at break, notch impact strength, is listed in Table 2 below.
Table 1
Table 2
Claims (7)
1. a kind of method prepared by in-situ flexible polypropylene alloy, it is characterised in that prepared as steps described below with condition：
The first step：The preparation of functionalization high vinyl polybutadiene
Component A and component B is added in reaction bulb, is dissolved in magnetic agitation at 65 DEG C to component A, component is added into reaction bulb
C and D, is stirred, and quantitative component E is added into system, in being reacted under constant temperature a period of time, after reaction terminates, will be produced
Thing is poured out, and adding absolute ethyl alcohol separates out solid, and sedimentation a period of time, suction filtration is washed respectively with sodium bicarbonate solution and distilled water
Wash product solid for several times, be put into 60 DEG C of vacuum drying 12h of baking oven, obtain product；
Second step：The pre-irradiation of acrylic resin
Pre-irradiation processing is carried out to acrylic resin using electron accelerator or cobalt source, irradiation dose is 5-30kGy, and preparation is carried
The pre-irradiation polypropylene of polymeric peroxide；
3rd step：The preparation of the acrylic resin of situ-formed graft functionalization high vinyl polybutadiene
The polypropylene, functionalization high vinyl polybutadiene, pre-irradiation polypropylene for weighing formula consumption are carried out after mechanical mixture, plus
Enter reactive extrusion in double screw extruder, the acrylic resin of situ-formed graft functionalization high vinyl polybutadiene.
2. method prepared by a kind of in-situ flexible polypropylene alloy according to claim 1, it is characterised in that the component
A is high vinyl polybutadiene, and using lithium alkylide catalyst system and catalyzing, ionic polymerization, number-average molecular weight Mn is 1200000, crystallinity
20%, contents of ethylene is more than 95%；
Described component B is lower paraffin hydrocarbon or cycloalkane；
Described component C is a kind of carboxylic acid；
Described component D is a kind of phase transfer catalyst；
Described component E is a kind of oxidant；
The mass concentration of the component A is that 8g/dL, component C and component A mass concentration ratio are Mc/Ma=21.5%, component C and
Component E mol ratio is：C/E=1:1.
3. method prepared by a kind of in-situ flexible polypropylene alloy according to claim 1, it is characterised in that described is poly-
Allyl resin is COPP, melt flow rate (MFR) 0.5-20g/10min.
4. method prepared by a kind of in-situ flexible polypropylene alloy according to claim 1, it is characterised in that described is poly-
Propylene is the melt flows speed of COPP, ethylene-propylene random copolymer or their mixture, wherein COPP
Ethylene contents are 1-15wt% in rate 0.5-20g/10min, ethylene-propylene random copolymer.
5. method prepared by a kind of in-situ flexible polypropylene alloy according to claim 1, it is characterised in that described work(
The 1-10% that high vinyl polybutadiene consumption is polypropylene weight can be changed, the polyacrylic consumption of pre-irradiation is polypropylene weight
5-30%。
6. method prepared by a kind of in-situ flexible polypropylene alloy according to claim 1, it is characterised in that described pair of spiral shell
Bar extruder is hing surface in the same direction, and draw ratio is 40-48, and machine barrel is furnished with multiple independent heating units and multiple
Steam vent, energy independent control reacts the temperature in each stage.
7. method prepared by a kind of in-situ flexible polypropylene alloy according to claim 1, it is characterised in that described is anti-
Answer 170-220 DEG C of extruding graft temperature, screw speed 10-200rpm, residence time of material 3-8 minutes.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747557A (en) * | 2008-12-17 | 2010-06-23 | 黑龙江省科学院技术物理研究所 | Polybutadiene Nano powder rubber toughening polypropylene composite and preparation method thereof |
| CN102516655A (en) * | 2011-11-29 | 2012-06-27 | 金发科技股份有限公司 | Strengthening and toughening polypropylene composite and preparation method thereof |
| CN102898591A (en) * | 2012-11-05 | 2013-01-30 | 华东理工大学 | Method for preparing styrene/isoprene in-situ toughened polypropylene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747557A (en) * | 2008-12-17 | 2010-06-23 | 黑龙江省科学院技术物理研究所 | Polybutadiene Nano powder rubber toughening polypropylene composite and preparation method thereof |
| CN102516655A (en) * | 2011-11-29 | 2012-06-27 | 金发科技股份有限公司 | Strengthening and toughening polypropylene composite and preparation method thereof |
| CN102898591A (en) * | 2012-11-05 | 2013-01-30 | 华东理工大学 | Method for preparing styrene/isoprene in-situ toughened polypropylene |
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