CN109651749A - Resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant and its preparation method and application - Google Patents

Resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant and its preparation method and application Download PDF

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Publication number
CN109651749A
CN109651749A CN201811604769.9A CN201811604769A CN109651749A CN 109651749 A CN109651749 A CN 109651749A CN 201811604769 A CN201811604769 A CN 201811604769A CN 109651749 A CN109651749 A CN 109651749A
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temperature
resistance
parts
cracking
low
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张海洋
李晟
王中林
张春怀
李欣
徐昌竹
张栋玮
钱文轩
陶四平
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TIANJIN KINGFA NEW MATERIALS CO Ltd
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TIANJIN KINGFA NEW MATERIALS CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant

Abstract

The present invention provides resistance to cracking anti-flaming polypropylene materials of a kind of low-temperature impact-resistant and its preparation method and application, wherein, the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking, each component including following parts by weight: 40-75 parts of acrylic resin, 2-20 parts of ethylene-octene copolymer (POE), 0-30 parts of mineral filler, 5-30 parts of brominated flame-retardant, 5-15 parts of synergistic flame retardant, 0.3-3.5 parts of stabilizer, 0.5-2 parts of toner.The low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking of the present invention, it joined brominated flame-retardant and synergistic flame retardant, make material that there is good flame retardant property, and specific acrylic resin copolymer is selected to compound with the ethylene-octene copolymer (POE) as toughener, good low-temperature impact-resistant ability and resistance to cracking are made it have, can be applied in the exterior trimming parts and functor of the oversize vehicles such as truck, engineering truck.

Description

Resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant and its preparation method and application
Technical field
The invention belongs to modified plastics field, more particularly, to a kind of resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant and Preparation method and application, the specifically application in automobile exterior and functor.
Background technique
Polypropylene (PP) is current application range in the world most one of wide, the maximum general-purpose plastics of yield, because it is with close The features such as small, good mechanical performance, mobility are high, resistant to chemical etching, electrical insulating property is good, molding easy to process is spent, in automobile work Industry, household electrical appliance, electronics, wire and cable, packaging and building materials etc. are widely used.But due to molecular structure, gather The limit oxygen index of propylene only has 17.5, and charring rate is almost 0, therefore its chance fire easily burns, and calorific value is high, burning velocity Fastly, easily melting is dripped.Once fire occurs, great threat can be caused to the security of the lives and property.
Compared to small passenger car, certain privileged sites products of some oversize vehicles such as truck, engineering truck, in addition to requiring Except basic flame retardant property, it is necessary to there is good intensity and toughness, guarantee that it can be subjected to welding process and be likely to occur Cracking and long run during vibration.Since polypropylene is crystalline polymer, brittleness is poor under low temperature, therefore its The low-temperature impact-resistant performance of product is also poor, limits its use at low ambient temperatures.
Patent CN107286479A does not add any toughener and improves impact resistance ability, system by reducing Dispersed Phase Size For a kind of cold-resistant highly effective flame-retardant polypropene composition of lightweight HI high impact, but its intensity is lower, is unfavorable for welding.Patent The notch impact strength of material is increased to 15.0KJ/m by addition composite toughing agent by CN103724806A2, but it is -30 Notch impact strength under the conditions of DEG C is lower, and low-temperature impact property is poor.Patent CN101974195A discloses a kind of fire-retardant Low temperature resistant polypropylene material and its preparation method and application, but its notch impact strength is insufficient, and low temperature impact properties are poor.
Summary of the invention
In view of this, the present invention is directed to propose a kind of low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking, existing to overcome The defect of technology has good flame retardant property, low-temperature impact-resistant ability and resistance to cracking.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking, each component including following parts by weight: acrylic resin 40-75 parts, 2-20 parts of ethylene-octene copolymer (POE), 0-30 parts of mineral filler, 5-30 parts of brominated flame-retardant, synergistic flame retardant 5-15 parts, 0.3-3.5 parts of stabilizer, 0.5-2 parts of toner.
Preferably, the acrylic resin be two kinds of ethylene block copolymerization polypropylenes mixture, the mixture it is each Its melt flow rate (MFR) of component is 0.5-15g/10min under the conditions of 230 DEG C of test temperature, test counterweight weight 2.16kg, Notch impact strength is 10-50KJ/m2
Ethylene-octene copolymer (hereinafter referred to as POE) can play the role of coordination plasticizing with acrylic resin copolymer.
Preferably, the mineral filler is the mixture of one or more of talcum powder, calcium carbonate and mica powder.
Preferably, the brominated flame-retardant is one of deca-BDE, decabromodiphenylethane and eight bromo ether;The association Effect fire retardant is stibium trioxide.
Preferably, the stabilizer includes that Hinered phenols antioxidant, phosphite ester antioxidant and hindered amines light are stablized Agent, and the weight ratio of three is 1:1:2.
Another object of the present invention is to propose a kind of preparation method of resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant, To prepare the above-mentioned low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of the resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant, comprising the following steps:
(1) polypropylene, POE, mineral filler, brominated flame-retardant, synergistic flame retardant, stabilizer and the color of formula ratio are weighed Powder, and by it in high mixer mixed at high speed 1-3min, be uniformly mixed, obtain premix;
(2) premix is added to the main spout of double screw extruder, carries out melting extrusion, granulating and drying obtains described The low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking.
Preferably, the melting extrusion condition of the double screw extruder are as follows: 80-120 DEG C of area's temperature, two area temperature 190- 210 DEG C, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five 210-230 DEG C of area's temperature, six area temperature 210-230 DEG C, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, nine 210-230 DEG C of area's temperature, 250-600 revs/min of engine speed Clock;The draw ratio of the double screw extruder is 40:1.
The invention further relates to the resistance to cracking anti-flaming polypropylene materials of above-mentioned low-temperature impact-resistant in auto industry exterior trim and functor The application in field, the especially application in the oversize vehicles industry exterior trim and functor field such as truck, engineering truck.
Compared with the existing technology, the resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant of the present invention has following excellent Gesture:
(1) brominated flame-retardant and synergistic flame retardant are selected, makes material that there is good flame retardant property, vertical burn test is full Sufficient UL94V-0 flame retardant rating.
(2) by selecting acrylic resin copolymer and adding POE as toughener, the toughness of material greatly improved, make It is with good low-temperature impact-resistant ability, and notch impact strength is up to 4KJ/m under the conditions of -30 DEG C2More than.
(3) eutectic with higher molecular weight has been selected to refer to that acrylic resin copolymer system, high molecular weight mean high poly- Object has longer segment, and strand is more difficult to be destroyed when by external force, while eutectic refers to the dispersion of resin Yu elastomer POE Property is more preferable, to make toughening effect more preferably, the above two o'clock significant increase resistance to cracking energy of material, at -30 DEG C of low temperature into Row ball falling impact tests flawless.
(4) it is big to can be applied to truck, engineering truck etc. for the resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant of the present invention In the exterior trimming parts and functor of type vehicle.
The preparation method and the resistance to cracking of above-mentioned low-temperature impact-resistant of the resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant hinder Firing polypropylene material, possessed advantage is identical compared with the existing technology, and details are not described herein.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent;It is described Experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
One, the raw material sources of embodiment 1-4 and comparative example 1,2
1, the raw material of embodiment 1-4
Acrylic resin: acrylic resin used is the mixture of two kinds of high molecular weight copolymer polypropylene, the respectively Yanshan Mountain Petrochemical industry K8303 and Lanzhou Petrochemical SP179, the weight ratio of the former with the latter are 2:1.
POE uses the Engage 7467 of the Dow Chemical Company's production.
Mineral filler: embodiment 2 uses 3000 mesh talcum powder, and embodiment 4 uses 3000 mesh calcium carbonate.
Brominated flame-retardant: decabromodiphenylethane is used.
Synergistic flame retardant: stibium trioxide is used.
Stabilizer: using primary antioxidant 1010, auxiliary anti-oxidant 168, light stabilizer LA-402AF 1:1:2 in mass ratio it is mixed Close object.
2, the raw material of comparative example
Acrylic resin used in comparative example 1 is identical as embodiment 1-4, and acrylic resin used in comparative example 2 is molecular weight phase To lower Yanshan Petrochemical K9829H, melt flow rate (MFR) is under the conditions of 230 °C of test temperature, test counterweight weight 2.16kg ≥25g/10min;Remaining ingredient in comparative example 1 and 2 is identical with embodiment 1-3.
Two, the formula composition and preparation method of embodiment 1-4 and the polypropylene material of comparative example 1,2
Embodiment 1
A kind of low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking, each component including following parts by weight: acrylic resin 71.2 parts, POE7 parts, 15 parts of decabromodiphenylethane, 5 parts of stibium trioxide, 0.8 part of stabilizer, 1 part of toner.
The above-mentioned resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant mixes the preparation method comprises the following steps: each component is respectively placed in high speed It is sufficiently stirred to obtain premix in conjunction machine, premix is added to the main spout of double screw extruder, carry out melting extrusion, be granulated It is dry, obtain the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking.
Wherein, the melting extrusion temperature of double screw extruder are as follows: 100-120 DEG C of area's temperature, two area temperature 190-210 DEG C, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five 210-230 DEG C of area's temperature, six 210-230 DEG C of area's temperature, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, nine 210-230 DEG C of area's temperature, 250-600 revs/min of engine speed;It is double The draw ratio of screw extruder is 40:1.
Embodiment 2
A kind of low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking, each component including following parts by weight: acrylic resin 61.2 parts, POE7 parts, 10 parts of talcum powder, 15 parts of decabromodiphenylethane, 5 parts of stibium trioxide, 0.8 part of stabilizer, 1 part of toner.
The above-mentioned resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant mixes the preparation method comprises the following steps: each component is respectively placed in high speed It is sufficiently stirred to obtain premix in conjunction machine, premix is added to the main spout of double screw extruder, carry out melting extrusion, be granulated It is dry, obtain the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking.
Wherein, the melting extrusion temperature of double screw extruder are as follows: 100-120 DEG C of area's temperature, two area temperature 190-210 DEG C, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five 210-230 DEG C of area's temperature, six 210-230 DEG C of area's temperature, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, nine 210-230 DEG C of area's temperature, 250-600 revs/min of engine speed;It is double The draw ratio of screw extruder is 40:1.
Embodiment 3
A kind of low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking, each component including following parts by weight: acrylic resin 60.2 parts, POE10 parts, 21 parts of decabromodiphenylethane, 7 parts of stibium trioxide, 0.8 part of stabilizer, 1 part of toner.
The above-mentioned resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant mixes the preparation method comprises the following steps: each component is respectively placed in high speed It is sufficiently stirred to obtain premix in conjunction machine, premix is added to the main spout of double screw extruder, carry out melting extrusion, be granulated It is dry, obtain the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking.
Wherein, the melting extrusion temperature of double screw extruder are as follows: 100-120 DEG C of area's temperature, two area temperature 190-210 DEG C, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five 210-230 DEG C of area's temperature, six 210-230 DEG C of area's temperature, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, nine 210-230 DEG C of area's temperature, 250-600 revs/min of engine speed;It is double The draw ratio of screw extruder is 40:1.
Embodiment 4
A kind of low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking, each component including following parts by weight: acrylic resin 56.2 parts, POE7 parts, 7 parts of calcium carbonate, 21 parts of decabromodiphenylethane, 7 parts of stibium trioxide, 0.8 part of stabilizer, 1 part of toner.
The above-mentioned resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant mixes the preparation method comprises the following steps: each component is respectively placed in high speed It is sufficiently stirred to obtain premix in conjunction machine, premix is added to the main spout of double screw extruder, carry out melting extrusion, be granulated It is dry, obtain the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking.
Wherein, the melting extrusion temperature of double screw extruder are as follows: 100-120 DEG C of area's temperature, two area temperature 190-210 DEG C, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five 210-230 DEG C of area's temperature, six 210-230 DEG C of area's temperature, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, nine 210-230 DEG C of area's temperature, 250-600 revs/min of engine speed;It is double The draw ratio of screw extruder is 40:1.
Comparative example 1
A kind of polypropylene material, each component including following parts by weight: 71.2 parts of acrylic resin, POE7 parts, talcum powder 20 parts, 0.8 part of stabilizer, 1 part of toner.
Above-mentioned polypropylene material the preparation method comprises the following steps: each component is respectively placed in high-speed mixer be sufficiently stirred to obtain it is pre- The main spout of double screw extruder is added in premix by mixing, carries out melting extrusion, and granulating and drying obtains polypropylene material.
Wherein, the melting extrusion temperature of double screw extruder are as follows: 100-120 DEG C of area's temperature, two area temperature 190-210 DEG C, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five 210-230 DEG C of area's temperature, six 210-230 DEG C of area's temperature, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, nine 210-230 DEG C of area's temperature, 250-600 revs/min of engine speed;It is double The draw ratio of screw extruder is 40:1.
Comparative example 2
A kind of polypropylene material, each component including following parts by weight: 71.2 parts of acrylic resin, POE7 parts, ten bromines two 15 parts of vinylbenzene, 5 parts of stibium trioxide, 0.8 part of stabilizer, 1 part of toner.
Above-mentioned polypropylene material the preparation method comprises the following steps: each component is respectively placed in high-speed mixer be sufficiently stirred to obtain it is pre- The main spout of double screw extruder is added in premix by mixing, carries out melting extrusion, and granulating and drying obtains polypropylene material.
Wherein, the melting extrusion temperature of double screw extruder are as follows: 100-120 DEG C of area's temperature, two area temperature 190-210 DEG C, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five 210-230 DEG C of area's temperature, six 210-230 DEG C of area's temperature, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, nine 210-230 DEG C of area's temperature, 250-600 revs/min of engine speed;It is double The draw ratio of screw extruder is 40:1.
The polypropylene material each group distribution ratio of embodiment 1-4 and comparative example 1,2 is shown in Table 1.
1 embodiment 1-4 of table and comparative example 1-2 formula composition (unit of feed components is parts by weight)
Raw material Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1 Comparative example 2
Acrylic resin 71.2 61.2 60.2 56.2 71.2 71.2
POE 7 7 10 7 7 7
Mineral filler \ 10 \ 7 20 \
Brominated flame-retardant 15 15 21 21 \ 15
Synergistic flame retardant 5 5 7 7 \ 5
Stabilizer 0.8 0.8 0.8 0.8 0.8 0.8
Toner 1 1 1 1 1 1
Three, the performance test of embodiment 1-4 and the polypropylene material of comparative example 1,2
1, test method
(1) tensile property is executed by ISO527;
(2) bending property is executed by ISO178;
(3) impact property is executed by ISO179;
(4) low-temperature impact-resistant performance is characterized by low temperature notched impact strength;
(5) resistance to cracking can be characterized by -30 DEG C of low temperature ball falling impacts;
(6) flame retardant property is classified according to UL94 combustion testing standard.
2, the performance test results of embodiment 1-4 and the polypropylene material of comparative example 1,2
According to above-mentioned test method, reality is tested for the property to the obtained polypropylene material of embodiment 1-4 and comparative example 1-2 It tests, test result is shown in Table 2.
2 embodiment 1-4 of table and comparative example 1-2 the performance test results
It can be seen from the performance comparison of each embodiment and comparative example in table 2 brominated flame-retardant and synergistic flame retardant with After certain proportion addition, material has good flame retardant property, and vertical combustion grade can achieve V-0 grades.Pass through copolymerization poly- third Olefine resin is used in compounding with toughener POE's, and the low-temperature impact-resistant performance and resistance to cracking of material are significantly improved, and low temperature lacks Mouth impact strength >=4KJ/m2, low temperature ball falling impact flawless.Comparative example 1 and comparative example 2 are it is also found that in other groups When dividing identical, the biggish eutectic of molecular weight is selected to refer to acrylic resin copolymer, high fluidity more relatively small than molecular weight Acrylic resin copolymer is more advantageous to the resistance to cracking energy for improving material.Above-mentioned performance can effectively avoid the certain special of automobile The long run that components crack in welding and assembling process, and are amenable under low temperature environment.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking, it is characterised in that: each component including following parts by weight: poly- 40-75 parts of allyl resin, 2-20 parts of ethylene-octene copolymer, 0-30 parts of mineral filler, 5-30 parts of brominated flame-retardant, synergistic resistance Agent 5-15 parts, 0.3-3.5 parts of stabilizer, 0.5-2 parts of toner of combustion.
2. the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking according to claim 1, it is characterised in that: the polypropylene Resin is the mixture of two kinds of ethylene block copolymerization polypropylenes, its melt flow rate (MFR) of each component of the mixture is in test temperature It is 0.5-15g/10min, notch impact strength 10-50KJ/m under the conditions of 230 DEG C of degree, test counterweight weight 2.16kg2
3. the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking according to claim 1, it is characterised in that: the mineral are filled out Material is the mixture of one or more of talcum powder, calcium carbonate and mica powder.
4. the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking according to claim 1, it is characterised in that: the brominated resistance Combustion agent is one of deca-BDE, decabromodiphenylethane and eight bromo ether;The synergistic flame retardant is stibium trioxide.
5. the low-temperature impact-resistant anti-flaming polypropylene material of resistance to cracking according to claim 1, it is characterised in that: the stabilizer Including Hinered phenols antioxidant, phosphite ester antioxidant and hindered amine light stabilizer, and the weight ratio of three is 1:1:2.
6. a kind of side of the resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant prepared as described in claim 1 to 5 any one Method, it is characterised in that: the following steps are included:
(1) polypropylene, ethylene-octene copolymer, mineral filler, brominated flame-retardant, the synergistic flame retardant, stabilization of formula ratio are weighed Agent and toner, and by it in high mixer mixed at high speed 1-3min, be uniformly mixed, obtain premix;
(2) premix is added to the main spout of double screw extruder, carries out melting extrusion, granulating and drying obtains described resistance to low The temperature impact anti-flaming polypropylene material of resistance to cracking.
7. the preparation method of the resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant according to claim 6, it is characterised in that: The melting extrusion condition of the double screw extruder are as follows: 80-120 DEG C of area's temperature, two 190-210 DEG C of area's temperature, three Qu Wendu 210-230 DEG C, four 210-230 DEG C of area's temperature, five 210-230 DEG C of area's temperature, six 210-230 DEG C of area's temperature, seven area temperature 210- 230 DEG C, eight 210-230 DEG C of area's temperature, nine 210-230 DEG C of area's temperature, 250-600 revs/min of engine speed;The twin-screw squeezes The draw ratio of machine is 40:1 out.
8. the resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant described in claim 1 to 5 any one is in auto industry exterior trim With the application in functor field.
CN201811604769.9A 2018-12-26 2018-12-26 Resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant and its preparation method and application Pending CN109651749A (en)

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