CN109777025A - A kind of high rigidity, high tenacity, low-shrink polypropylene composite material and preparation method - Google Patents

Abstract

The invention discloses a kind of high rigidity, high tenacity, low-shrink polypropylene composite materials, are made of the raw material of following weight percents: polypropylene 28-63%；Ultra-fine inorganic filler 25-35%；Elastomer flexibilizer 10-20%；Cyclic olefine copolymer 1-10%；Stabilizer 0.1-2%；Other additive 0-5%.The invention has the advantages that 1, characteristic noncrystalline using cyclic olefine copolymer, lower shrinkage, further decreases shrinking percentage on the basis of existing low-shrink polypropylene composite material.2, using cyclic olefine copolymer high rigidity, high-intensitive characteristic, material stiffness is further promoted on the basis of existing high rigidity, low-shrink polypropylene composite material.3, enough mobility and anti-impact grade performance are kept, the scope of application of material is improved while reducing contraction and promoting intensity using cyclic olefine copolymer and ultrafine inorganic powder, the Proper Match of elastomer flexibilizer and synergistic effect.

Description

A kind of high rigidity, high tenacity, low-shrink polypropylene composite material and preparation method

Technical field

The present invention relates to a kind of PP composite material, specially a kind of high rigidity, high tenacity, low-shrink polypropylene are compound Material, with and preparation method thereof；Belong to polymer modification and manufacture field.

Background technique

Automotive light weight technology is research direction most popular in industry in recent years, other than metal parts, for interior exterior trim and The plastic items of partial function part carry out the various methods of loss of weight and thinking is also constantly refreshing.In addition to traditional low-density, It is thinning with other than foam process, is also important lightweight scheme to mould Dai Gang.Due to traditional common or the machine of engineering plastics Tool performance differs farther out with metal, it is necessary to be made up by various modified methods and structure design.It is maximum with interior quantity of plastics Polypropylene material for, other than the difference of mechanical performance, biggish shrinking percentage and thus bring dimensional instability It is also one of the main difficulty of substitution metal.

Domestic and international each modified material manufacturer has studied a variety of methods to reduce the shrinking percentage of polypropylene material for many years, Wherein fiberglass reinforced helps the reduction of polypropylene shrinking percentage maximum, and a large amount of fiber glass reinforced polypropylene materials are applied to all kinds of zero In component, but the disadvantages of such material still has poor appearance, excessive high hardness, is not easily recycled, many components can not It uses.The another kind of scheme being most widely used is that a large amount of talcum powders of addition and elastomer flexibilizer are polyacrylic to reduce Shrinking percentage, while can also reach higher rigidity and toughness, such material are widely used in side skirt, preceding grid, outside tail-gate Plate etc. is in the higher large parts of dimensional stability requirements.But such material property has basically reached bottleneck, continues to mention It rises performance or reduction shrinking percentage is extremely difficult.

Cyclic olefine copolymer refers here particularly to the resulting non-crystalline polymer of the cycloolefin copolymers such as ethylene and double-heptene, tool There is the features such as lower shrinkage, stiffness, high transparency, be chiefly used in promoting the barrier property to liquids and gases in packaging material, Also research is blended for improving flame retardant property, or with acrylic resin to reduce shrinking percentage, but in existing talcum powder/elastomer Continue to add such component on modified low-shrink polypropylene composite material basis to have not been reported with the research further improved performance.

The present invention be existing lower shrinkage, high rigidity, high-toughness polypropylene composite material mature technology on the basis of, utilize The characteristic of cyclic olefine copolymer further increases material stiffness, reduces shrinking percentage, while keeping enough shock resistances, produces It is all kinds of to the higher large parts of dimensional stability requirements that product can be used for being molded production.

Summary of the invention

It is an object of the invention to develop a kind of high rigidity, high tenacity, low-shrink polypropylene composite material and its preparation side Method, for the injection molding in automobile or other industries to the higher large parts of dimensional stability requirements.

Another object of the present invention is to provide the preparation methods of this PP composite material.

The purpose of the present invention can be achieved through the following technical solutions:

A kind of high rigidity, high tenacity, low-shrink polypropylene composite material, are made of the raw material of following weight percents:

Wherein,

The polypropylene is the homopolymerization or co-polypropylene that melt flow rate (MFR) is 5-70g/10min, wherein co-polypropylene Comonomer be ethylene, content 4-10mol%.

The ultra-fine inorganic filler be one or both of talcum powder, mica, whisker, wollastonite, glass fibre with On composition, the talcum powder of preferred average diameter 1um.

The elastomer flexibilizer be polybutadiene rubber, Ethylene-Propylene-Diene rubber (EPDM), ethylene-octene without Rule or block copolymer, Ethylene/Butylene be random or the composition of one or more of block copolymer etc., preferably second Alkene-butene block copolymer, (230 DEG C × 2.16kg) of melt flow rate (MFR) are 0.5-20g/10min.

It is the non-crystalline copolymer of ethylene and cycloolefin in the cyclic olefine copolymer, the cycloolefin is cyclopropyl One of alkene, cyclobutane, cyclopentene, cycloheptene, double-heptene, cyclohexene.

The molecular weight of the cyclic olefine copolymer between 3000-60000, the degree of polymerization is between 100-1000.

The stabilizer is that those skilled in the art think required major-minor antioxidant and light stabilizer, wherein primary antioxidant For hindered phenol or sulphur ester antioxidant, auxiliary antioxidant is phosphorite kind antioxidant, and light stabilizer is hindered amines light Stabilizer.

Other additives include colorant, nucleating agent, the foaming agent, surface work that those skilled in the art think required One of property agent, plasticizer, coupling agent, fire retardant, processing aid, antistatic auxiliary, antimicrobial auxiliary agent, lubricant or with On composition.

Above-mentioned high rigidity, high tenacity, the preparation method of low-shrink polypropylene composite material, its step are as follows:

1) raw material is weighed by weight ratio；

2) polypropylene, ultra-fine inorganic filler, elastomer flexibilizer, cyclic olefine copolymer, stabilizer and other auxiliary agents are existed It is 3-15 minutes dry-mixed in super mixer, mixed raw material is added twin-screw extrude, cooling is made after melting extrusion Grain；Wherein temperature in barrel are as follows: 210-220 DEG C of an area, two 210-230 DEG C of areas, three 210-230 DEG C of areas, four 210-230 DEG C of areas, 210-240 DEG C of head, double screw extruder revolving speed is 100-1000 revs/min.

The invention has the advantages that

1, characteristic noncrystalline using cyclic olefine copolymer, lower shrinkage, in the base of existing low-shrink polypropylene composite material Shrinking percentage is further decreased on plinth.

2, using cyclic olefine copolymer high rigidity, high-intensitive characteristic, in existing high rigidity, low-shrink polypropylene composite wood Material stiffness is further promoted on the basis of material.

3, using cyclic olefine copolymer and ultrafine inorganic powder, the Proper Match of elastomer flexibilizer and synergistic effect, While reducing contraction and promote intensity, enough mobility and anti-impact grade performance are kept, the scope of application of material is improved.

Specific embodiment

Below with reference to embodiment, invention is further described in detail.The scope of the present invention is not by these embodiments Limitation, the scope of the present invention propose in detail in the claims.

In the composite-material formula of embodiment and comparative example, polypropylene used be melt flow rate (MFR) (230 DEG C × 2.16kg) the block copolymerization propylene of 30-60/10min, wherein the comonomer of block copolymerization propylene is ethylene, and content is in 4- Within the scope of 10mol%.

Ultra-fine inorganic filler used is the talcum powder of average diameter 1um.

Elastomer used is ethylene-octene block copolymer.

Cyclic olefine copolymer used is the COC5013 of Bao Li company.

Antioxidant agent used is that (chemical name is thio-2 acid stearyl alcohol by the Negonox DSTP of ICE company, Britain Ester), (chemical name is four [β-(3,5- di-t-butyl 4- hydroxy phenyl) propionic acid] Ji Wusi by the Irganox 1010 of Ciba company Alcohol ester) and Ciba company Igrafos168 (chemical name be phosphorous acid three (2,4- di-tert-butyl) ester), use up surely Determine 3808 that agent is Qing Te company.

Embodiment 1

Middle mobility polypropylene 57.5%, superfine talcum powder 30%, elastomer 10%, cycloolefin are weighed by weight percentage Copolymer 2%, Irganox 1010 are 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, mixed in high speed Dry-mixed 5 minutes in clutch, adds melting extrusion in double screw extruder and be granulated, wherein temperature in barrel are as follows: 220 DEG C of an area, Two 230 DEG C of areas, three 230 DEG C of areas, four 230 DEG C of areas, 240 DEG C of head, double screw extruder revolving speed is 400 revs/min.Particle is through drying Sample preparation is injection moulded on injection (mo(u)lding) machine afterwards.

Embodiment 2

Middle mobility polypropylene 57.5%, superfine talcum powder 25%, elastomer 15%, cycloolefin are weighed by weight percentage Copolymer 2%, Irganox 1010 are 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, mixed in high speed Dry-mixed 5 minutes in clutch, adds melting extrusion in double screw extruder and be granulated, wherein temperature in barrel are as follows: 220 DEG C of an area, Two 230 DEG C of areas, three 230 DEG C of areas, four 230 DEG C of areas, 240 DEG C of head, double screw extruder revolving speed is 400 revs/min.Particle is through drying Sample preparation is injection moulded on injection (mo(u)lding) machine afterwards.

Embodiment 3

Middle mobility polypropylene 42.5%, superfine talcum powder 35%, elastomer 20%, cycloolefin are weighed by weight percentage Copolymer 2%, Irganox 1010 are 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, mixed in high speed Dry-mixed 5 minutes in clutch, adds melting extrusion in double screw extruder and be granulated, wherein temperature in barrel are as follows: 220 DEG C of an area, Two 230 DEG C of areas, three 230 DEG C of areas, four 230 DEG C of areas, 240 DEG C of head, double screw extruder revolving speed is 400 revs/min.Particle is through drying Sample preparation is injection moulded on injection (mo(u)lding) machine afterwards.

Embodiment 4

Middle mobility polypropylene 52.5%, superfine talcum powder 30%, elastomer 15%, cycloolefin are weighed by weight percentage Copolymer 2%, Irganox 1010 are 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, mixed in high speed Dry-mixed 5 minutes in clutch, adds melting extrusion in double screw extruder and be granulated, wherein temperature in barrel are as follows: 220 DEG C of an area, Two 230 DEG C of areas, three 230 DEG C of areas, four 230 DEG C of areas, 240 DEG C of head, double screw extruder revolving speed is 400 revs/min.Particle is through drying Sample preparation is injection moulded on injection (mo(u)lding) machine afterwards.

Embodiment 5

Middle mobility polypropylene 49.5%, superfine talcum powder 30%, elastomer 15%, cycloolefin are weighed by weight percentage Copolymer 5%, Irganox 1010 are 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, mixed in high speed Dry-mixed 5 minutes in clutch, adds melting extrusion in double screw extruder and be granulated, wherein temperature in barrel are as follows: 220 DEG C of an area, Two 230 DEG C of areas, three 230 DEG C of areas, four 230 DEG C of areas, 240 DEG C of head, double screw extruder revolving speed is 400 revs/min.Particle is through drying Sample preparation is injection moulded on injection (mo(u)lding) machine afterwards.

Embodiment 6

Middle mobility polypropylene 46.5%, superfine talcum powder 30%, elastomer 15%, cycloolefin are weighed by weight percentage Copolymer 8%, Irganox 1010 are 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, mixed in high speed Dry-mixed 5 minutes in clutch, adds melting extrusion in double screw extruder and be granulated, wherein temperature in barrel are as follows: 220 DEG C of an area, Two 230 DEG C of areas, three 230 DEG C of areas, four 230 DEG C of areas, 240 DEG C of head, double screw extruder revolving speed is 400 revs/min.Particle is through drying Sample preparation is injection moulded on injection (mo(u)lding) machine afterwards.

Comparative example

Weigh by weight percentage middle mobility polypropylene 59.5%, superfine talcum powder 30%, elastomer 10%, Irganox 1010 is 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, dry-mixed in super mixer It 5 minutes, adds melting extrusion in double screw extruder and is granulated, wherein temperature in barrel are as follows: 220 DEG C of an area, two 230 DEG C of areas, Three 230 DEG C of areas, four 230 DEG C of areas, 240 DEG C of head, double screw extruder revolving speed is 400 revs/min.Particle is being injected into after drying Sample preparation is injection moulded on type machine.

Performance evaluation mode:

Sample rate test is carried out by ISO1183-1 standard；Melt flow rate (MFR) is carried out by ISO1133-1 standard, test Condition is 230 DEG C × 2.16kg；Bending modulus test is carried out by 178 standard of ISO, and specimen size is 80 × 10 × 4mm, speed 2mm/min；Notch impact strength test is carried out by ISO179 standard, and specimen size is 80 × 10 × 4mm, and notch depth is sample The one third of thickness；Shrinking percentage test is carried out with the smooth plates having a size of 150 × 100 × 3mm, constant temperature and humidity item after injection molding It places 48 hours, measures flow direction template length (side 150mm), and according to change in size shrinkage from mold dimensions under part.

Each embodiment and comparative formulation and the performance test results see below Lie Gebiao:

1 embodiment 1-6 of table and comparative example material prescription (weight %)

2 embodiment 1-6 of table and comparative example the performance test results

Comparative example is existing common low-shrinkage PP composite material, strong and unyielding property and lower shrinkage characteristic had reached compared with High level, but continue to lift up substantially without space；A small amount of cyclic olefine copolymer is added in embodiment 1 on the basis of comparative example, It can be seen that shrinking percentage has further decline, so that toughness is declined slightly, rigidity is mentioned for the addition of cyclic olefine copolymer It rises；Embodiment 2-4 has adjusted the ratio of talcum powder and elastomer on that basis of example 1, and wherein 2 rigidity of embodiment is inclined Low, 3 mobility of embodiment is relatively low, limited by practical, and the strong and unyielding property of embodiment 4 more balances；Embodiment 5-6 is on 4 basis of embodiment On continue growing the content of cyclic olefine copolymer, under shrinking percentage is able to continue to decline, rigidly continues to improve, but toughness is also corresponding Drop, wherein the whole strong and unyielding property of embodiment 5 is ideal, and shrinking percentage has compared with than comparative example to be substantially reduced, and can be used for big absolutely Injection molding of the part to the higher components of dimensional stability requirements；For embodiment 6 other than toughness is slightly lower, cost is also relatively high, But shrinking percentage is lower, also can be applied in most of components slightly lower to toughness reguirements.

Claims (10)

1. a kind of high rigidity, high tenacity, low-shrink polypropylene composite material, it is characterised in that: by the original of following weight percents Material composition:

2. a kind of high rigidity according to claim 1, high tenacity, low-shrink polypropylene composite material, it is characterised in that: institute The polypropylene stated is the homopolymerization or co-polypropylene that melt flow rate (MFR) is 5-70g/10min, wherein the comonomer of co-polypropylene For ethylene, content 4-10mol%.

3. a kind of high rigidity according to claim 1, high tenacity, low-shrink polypropylene composite material, it is characterised in that: institute The ultra-fine inorganic filler stated is the composition of one or more of talcum powder, mica, whisker, wollastonite, glass fibre.

4. a kind of high rigidity according to claim 3, high tenacity, low-shrink polypropylene composite material, it is characterised in that: institute The ultra-fine inorganic filler stated is the talcum powder of average diameter 1um.

5. a kind of high rigidity according to claim 1, high tenacity, low-shrink polypropylene composite material, it is characterised in that: institute The elastomer flexibilizer stated is polybutadiene rubber, Ethylene-Propylene-Diene rubber (EPDM), ethylene-octene is random or block is total Polymers, Ethylene/Butylene be random or the composition of one or more of block copolymer etc., optimal ethylene-butylene blocks Copolymer, (230 DEG C × 2.16kg) of melt flow rate (MFR) are 0.5-20g/10min.

6. a kind of high rigidity according to claim 1, high tenacity, low-shrink polypropylene composite material, it is characterised in that: institute It is the non-crystalline copolymer of ethylene and cycloolefin in the cyclic olefine copolymer stated, the cycloolefin is cyclopropylene, cyclobutane, ring One of amylene, cycloheptene, double-heptene, cyclohexene.

7. a kind of high rigidity according to claim 6, high tenacity, low-shrink polypropylene composite material, it is characterised in that: institute The molecular weight for the cyclic olefine copolymer stated between 3000-60000, the degree of polymerization is between 100-1000.

8. a kind of high rigidity according to claim 1, high tenacity, low-shrink polypropylene composite material, it is characterised in that: institute State stabilizer be those skilled in the art think required major-minor antioxidant and light stabilizer, wherein primary antioxidant be hindered phenol or Sulphur ester antioxidant, auxiliary antioxidant are phosphorite kind antioxidant, and light stabilizer is hindered amine light stabilizer.

9. a kind of high rigidity according to claim 1, high tenacity, low-shrink polypropylene composite material, it is characterised in that: institute Stating other additives includes colorant, nucleating agent, foaming agent, the surfactant, plasticising that those skilled in the art think required One of agent, coupling agent, fire retardant, processing aid, antistatic auxiliary, antimicrobial auxiliary agent, lubricant or above combination Object.

10. the preparation method of high rigidity, high tenacity described in claim 1, low-shrink polypropylene composite material, it is characterised in that: Its step are as follows:

1) raw material is weighed by weight ratio；

2) by polypropylene, ultra-fine inorganic filler, elastomer flexibilizer, cyclic olefine copolymer, stabilizer and other auxiliary agents in high speed It is 3-15 minutes dry-mixed in mixer, mixed raw material is added twin-screw extrude, the cooling granulation after melting extrusion；Its Temperature in middle barrel are as follows: 210-220 DEG C of an area, two 210-230 DEG C of areas, three 210-230 DEG C of areas, four 210-230 DEG C of areas, head 210-240 DEG C, double screw extruder revolving speed is 100-1000 revs/min.