CN1100087C - Stuffing mother particle for toughening polyolefine and preparation process and usage thereof - Google Patents
Stuffing mother particle for toughening polyolefine and preparation process and usage thereof Download PDFInfo
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- CN1100087C CN1100087C CN98102448A CN98102448A CN1100087C CN 1100087 C CN1100087 C CN 1100087C CN 98102448 A CN98102448 A CN 98102448A CN 98102448 A CN98102448 A CN 98102448A CN 1100087 C CN1100087 C CN 1100087C
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Abstract
The present invention relates to a filling mother particle for toughening polyolefine, a preparation process thereof and a usage thereof, which belongs to the field of polyolefin materials toughened by inorganic particles. The filling mother particle is prepared from an inorganic filler with the particle diameter from 0.5 mum to 40 mum, a surfactant, a functionalized thermoplastic elastomer, functionalized thermoplastic resin, a mixture of the functionalized thermoplastic elastomer and the functionalized thermoplastic resin, and a processing aid; after all the components are uniformly mixed, the mixture is extruded by a double-screw extruder or is mixed by a double-roller mixing roll and then is granulated to obtain the filling mother particle. The filling mother particle for toughening polyolefine in the present invention has the characteristics that the inorganic filler is uniformly dispersed in a carrier for the mother particle, and the filling mother particles can be dispersed in a polyolefin base again in a mode of particles in a 'nuclear-shell' structure using the inorganic filler as a nuclear carrier as a shell when compounded with a polyolefin material; a composite material of the filling mother particle has high rigidity and toughness.
Description
The present invention relates to a kind of filler parent granule that can strengthen the toughening polyolefine material, specially refer to a kind of cheap, polyolefine filler parent granule of increasing rigidity, high toughening type.
Usually, in the plastic working process, the auxiliary agent, compound such as the stablizer that add, fire retardant, pigment etc. are concentrated in and make filler parent granule on the vector resin, it has lot of advantages, good as the plastics stability, be easy to metered charge and blend operation, purify Working environment etc., so the functionalization research of filler parent granule becomes focus as the filler parent granule that development has enhancing, toughening functions.
Xu Shengxiu is in Chinese invention patent " plastic filler parent granule " (notification number 1021857), reported a kind of plastic filler parent granule of high dispersive type, it is based on pearl filler, chelating titanates etc. are the surface treatment agent of filler, petroleum resin, ethylene-propylene rubber(EPR) etc. form for preparing carriers, the characteristics of this filler parent granule are to have good dispersing property in polymeric matrix, and can be under bigger loading level, improve the rigidity of plastics, as add 20% (wt%) this filler parent granule and be used to make the polypropylene strap, the tensile strength of its goods can by departmental standard>160kg/cm
2Be increased to 329kg/cm
2, unit elongation by departmental standard<25% be reduced to 17%, but therefore plastics do not obtain high tenacity.
Sun Shaoxuan is in Chinese invention patent " all purpose plastics packing parent grain and preparation method thereof " (publication number 1061028A), related to the filler parent granule that a kind of general purpose grade plastics are used, it be by through superfine grinding to the filler zeolite of 1-20 μ and white carbon black, molecular weight is that the carrier polyethylene of 1000-6000 and conditioning agent turps and white oil or oneself penta tetrol methyl esters form through mediating granulation, the characteristics of this filler parent granule are applied widely, can be used among most of thermoplasticss, because this master batch is carrier with the low molecular weight polyethylene, so this master batch can not be very remarkable to the enhancing toughening effect of plastics.
People such as Zhang Yun is bright, multitude Paine are in Chinese invention patent " toughening mother particle for polyolefine plastics and manufacture method thereof " (notification number 1124747) and " Supertough master-pellets for polypropylene plastics and manufacture method thereof " (notification number 1131165), reported with multi-functional coupling agent and help coupling agent to come coupling master batch vector resin and mineral filler to prepare the method for plasticizing mother particle and Supertough master-pellets, this filler parent granule has good toughening effect to polyolefin plastics, and optimum toughening effect can make the notched Izod impact strength of polypropylene material by 7.3KJ/m
2Be increased to 70~80KJ/m
2But this method is because being connected mineral filler and coupling agent the two is a chemical bonding between mineral filler and master batch carrier, the two only is the molecular chain physical entanglement and helping coupling agent and carrier, therefore this filler parent granule and polyolefinic matrix material are difficult to obtain high strength, high rigidity, as when above-mentioned master batch filled polypropylene material obtains optimum tenacity, the tensile strength of polypropylene material is reduced to 17~18MPa by 33.2MPa.
In order to overcome the shortcoming that can not obtain the composite polyolefine material of high rigidity, high tenacity in the above-mentioned prior art simultaneously, the invention provides and adopting mineral filler is main body, the easy dispersion that thermoplastic elastomer, thermoplastic resin, polymer emulsion and composition thereof form for preparing carriers, enhancing, high toughening type filler parent granule, this filler parent granule and polyolefine material carry out compound tense, can obtain cheap, have mineral filler for nuclear carrier be the high rigidity of " nuclear-shell " structured particles of shell, the composite polyolefine material of high tenacity.
It is based on mineral filler that the technology of a kind of stuffing mother particle for toughening polyolefine of the present invention constitutes, coupling agent, organic monomer are the surface treatment agent of mineral filler, thermoplastic elastomer, thermoplastic resin, polymer emulsion and composition thereof are carrier, and low-molecular(weight)polymer, low branch seed oil, fatty acid ester, lipid acid and salt thereof are processing aid.Filler parent granule comprises following component and content (weight percentage):
Mineral filler 47.5-84.5
Surface treatment agent 0.5-2.5
Carrier 10-30
Processing aid 5-18
Oxidation inhibitor 0-2
Above-mentioned mineral filler is talcum powder, kaolin, lime carbonate, wollastonite, mica, silicon-dioxide, aluminum oxide, aluminium hydroxide, titanium dioxide, agalmatolite, wilkinite, and its particle dia is at 0.5 μ m-40 μ m, and particle dia is 1.5 μ m-5 μ m preferably.Above-mentioned surface treatment agent is silane coupling agent such as γ-An Jibingjisanyiyangjiguiwan, γ-propyl methacrylate base Trimethoxy silane, γ-Racemic glycidol oxygen propyl trimethoxy silicane, titanate coupling agent such as sec.-propyl three different stearoyl titanic acid ester, positively charged ion, negatively charged ion, nonionic surface active agent, vinyl monomer and esters of gallic acid monomer (containing initiator) are as the mixture of vinylbenzene and maleic anhydride (containing initiator DTBP).Above-mentioned carrier is a natural rubber, cis-1,4-polybutadiene rubber, isoprene-isobutylene rubber; styrene-butadiene rubber(SBR); paracril; chloroprene rubber; polyisoprene rubber; EPDM; EVA; SBS; ethene-alpha-olefin copolymer; polyester; urethane; polyolefine such as hydroxy-terminated polybutadienes; polypropylene; high density polyethylene(HDPE); new LDPE (film grade) and maleic anhydride thereof; bismaleimides; acrylate; the ethylene-propylene-diene copolymer of vinyl monomer grafting or copolymerized grafting modification thermoplastic elastomer and thermoplastic resin such as bismaleimides graft modification; the ethylene-propylene-diene copolymer of trimethoxy propane triacrylate modification; the ethylene-propylene rubber(EPR) of modified by maleic acid anhydride graft, its melt flow rate (MFR) are 0.5g/10min-50g/10min.Above-mentioned processing aid is petroleum resin, Poly Propylene Wax, polyethylene wax, solid paraffin, whiteruss, naphthenic oil, laurate, oleic acid ester, oleic acid, stearate, stearic acid and salt thereof such as calcium stearate.Above-mentioned oxidation inhibitor is homemade phenolic antioxidant, amine antioxidants.
The preparation method of a kind of stuffing mother particle for toughening polyolefine of the present invention follows these steps to order carry out:
(1) percentage ratio by weight adds thinner with above-mentioned surface treatment agent 0.5-2.5 and in super mixer the surface of mineral filler 47.5-84.5 is handled,
(2) with mineral filler 48.0-87.0, the carrier 10-30, processing aid 5-18, the oxidation inhibitor 0-2 that handle well, in super mixer, to mediate evenly, the kneading time is 5-30 minute, mediating temperature is 10 ℃-100 ℃,
(3) kneaded material is extruded and granulation forms so that 140 ℃-200 ℃ processing temperature is compound in twin screw extruder.
Another preparation method of a kind of stuffing mother particle for toughening polyolefine of the present invention follows these steps to order carry out:
(1) percentage ratio by weight adds thinner with above-mentioned surface treatment agent 0.5-2.5 and in super mixer the surface of mineral filler 47.5-84.5 is handled,
(2) with mineral filler 48.0-87.0, the carrier 10-30, processing aid 5-18, the oxidation inhibitor 0-2 that handle well, in super mixer, to mediate evenly, the kneading time is 5-30 minute, mediating temperature is 10 ℃-100 ℃,
(3) with kneaded material in mixing roll, mixing with 120 ℃-150 ℃ temperature, in flakes, pelletizing forms.
The purposes of a kind of stuffing mother particle for toughening polyolefine of the present invention is the preparation composite polyolefine material.Above-mentioned polyolefine is homo-polypropylene, Co-polypropylene, high density polyethylene(HDPE), new LDPE (film grade), linear low density polyethylene, ethylene copolymer.
The purpose that inorganic filler surface is handled is to introduce reactive group or unsaturated link(age) on its surface, when above-mentioned mineral filler and have can with the carrier or the modified support of the functional group of filling surface reactive group generation chemical reaction, or have can with the carrier of filling surface unsaturated link(age) generation copolymerization or modified support mediate, in the extrusion, cause by heat or initiator, the two surperficial reactive group of mineral filler and carrier partly contacts concurrent biochemical reaction, the two is linked up with certain linking intensity and is present in the filler parent granule of preparation.Filler parent granule and polyolefine compound tense when preparation, filler and master batch carrier can be that the nuclear carrier is that " hard core-soft core " structured particles form of shell is dispersed in the polyolefin substrate with the mineral filler in the filler parent granule, replace simple rubber elastomer toughening polyolefine material.
Stuffing mother particle for toughening polyolefine of the present invention has mineral filler and can be dispersed in the filler parent granule carrier, and is evenly distributed on the characteristics in the polyolefin substrate with mineral filler-master batch carrier " hard core-soft core " structure formation.When the filler parent granule addition is 30-40wt%, can make the modulus of composite polyolefine material improve 0.5-1 doubly, notched Izod impact strength improves 1-4 doubly, and easy to process, and cost is low.
Embodiment 1
To handle through γ-propyl methacrylate base Trimethoxy silane 115g, granularity is the talcum powder 774.5g of 5 μ m, the ethylene-propylene-diene copolymer 91.2g of bismaleimides graft modification, its melt flow rate is 2.5g/10min, polypropylene 60.8g, its melt flow rate is 30g/10min, Poly Propylene Wax 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, after in homogenizer, mediating 20min under the room temperature, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 150-160-190-200-190 ℃ from the import to the outlet, and the water-cooled pelletizing forms.
With this talcum powder filler parent granule with the ethylene-propylene copolymer acrylic resin mixes 3-5min in 10: 90 ratio (weight percentage) in super mixer after, compound in twin screw extruder, the extruder barrel temperature is followed successively by 195-205-205-220-195 ℃ from the import to the outlet, its composite materials property test result sees Table 1.
Embodiment 2:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 20: 80.
Embodiment 3:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 30: 70.
Embodiment 4:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 40: 60.After table 1 talcum powder filler parent granule and copolymerization acrylic resin were compound, the mechanical property mixture of its material was implemented
Example 1 example 2 examples 3 examples 4 notched izod are impacted 218.0 267.0 308.0 525.0 intensity, (J/m) tensile strength, (MPa) 28.5 27.8 26.1 24.7 elongation at breaks, (%) 1044.8 1020.0 979.2 997.8 flexural strengths, (MPa) 27.4 26.1 25.0 23.2 modulus in flexurees, (GPa) 0.7 0.8 0.8 0.9
Embodiment 5 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 10: 90 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.
Embodiment 6 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 20: 80 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.
Embodiment 7 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 30: 70 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.
Embodiment 8 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 40: 60 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.The mechanical property mixture of table 2 talcum powder and copolymerization polypropylene composite material is implemented
Example 5 examples 6 examples 7 examples 8 notched izod are dashed 181.0 178.0 160.5 129.0 hit intensities, (J/m) tensile strength, (MPa) 29.8 30.5 30.2 29.8 elongation at breaks, (%) 1021.2 1122.4 659.8 389.2 flexural strengths, (MPa) 34.1 37.9 38.5 40.2 modulus in flexurees, (GPa) 1.0 1.1 1.2 1.2
Embodiment 9:
To handle through sec.-propyl three different stearoyl titanic acid ester 11.5g, granularity is the talcum powder 704.5g of 5 μ m, titanium dioxide 70g, ethene-alpha-olefin copolymer 91.2g, its melt flow rate is 0.5g/10min, polypropylene 60.8g, its melt flow rate is 50g/10min, naphthenic oil 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, in homogenizer, mediate 30min with 40 ℃-50 ℃ kneading temperature after, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 160-180-190-200-170 ℃ from the import to the outlet, the water-cooled pelletizing forms.
With above-mentioned filler parent granule and ethylene-propylene copolymer acrylic resin ratio in 40: 60 (weight percentage), obtain filling the Co-polypropylene matrix material with the working method identical with embodiment 1, its mechanical property sees Table 3.
Embodiment 10:
To handle through the 11.5g γ-An Jibingjisanyiyangjiguiwan, granularity is the talcum powder 774.5g of 5 μ m, the ethylene-propylene-diene copolymer 152g of trimethoxy propane triacrylate modification, its melt flow rate is 5g/10min, Poly Propylene Wax 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, under the working method and processing conditions identical, be prepared into filler parent granule and be combined into filled composite materials in the ratio of 40: 60 (weight percentage) with the copolymerization acrylic resin with embodiment 1.
Embodiment 11 (comparative example):
Ethylene-propylene copolymer acrylic resin, the trade mark are PP1330, and chemical industry two factories of Beijing Yanshan Petro-Chemical Industry Corporation produce, pellet, and processing conditions and embodiment 9 are together.
Embodiment 12 (comparative example):
When Co-polypropylene and ethylene-propylene-diene elastomer are pressed the master batch filled polyolefin matrix material of embodiment 9 preparations, wherein the Co-polypropylene matrix is with after the two identical ratio (weight percentage) of ethylene-propylene-diene elastomer as the master batch carrier mixes, composite molding, condition of molding and embodiment 9 are together.Table 3 embodiment 9, embodiment 10 implement with embodiment 8, embodiment 11, embodiment 12 results' comparison mixture
Strong 22.0 24.7 29.8 27.8 21.9 degree (MPa) fractures of outstanding 343.8 429.5 129.0 239.0 615.0 arm beam impact strengths (J/m) stretching of example 9 examples 10 examples 8 examples 11 examples 12 breach are stretched 511.4 752.8 389.2 592.0 530.2 long rates (%) crooked strong 34.7 25.3 40.2 30.7 24.9 and are spent (MPa) bending dies 1.5 1.0 1.2 0.8 0.7 amounts (GPa)
Embodiment 13:
To adsorb initiator DTBP0.1g, styrene monomer 8.0g, maleic anhydride 1.6g, granularity is the lime carbonate 750.8g of 1.5 μ m, and propylene-alpha-olefin copolymers 158.0g, its melt flow rate are 0.5g/10min, hydroxy-terminated polybutadienes 39.6g, laurate 7.9g, polyethylene wax 42.1g is at room temperature after homogenizer is mediated 10min, mixing on double roll mill, in flakes, pelletizing forms, and melting temperature is 120-150 ℃.
With above-mentioned filler parent granule and acrylic resin prescription by 40: 60 (weight percentage), the filling polypropylene composite material that obtains with the working method identical with embodiment 1.
Embodiment 14 (comparative example):
With lime carbonate and the polypropylene matrix proportioning by 40: 60 (weight percentage), the mechanical property of the filling polypropylene composite material that obtains with working method identical with embodiment 13 and processing conditions also sees Table 4.
Embodiment 15 (comparative example):
Homo-polypropylene, the trade mark are PP2401, and chemical industry two factories of Beijing Yanshan Petro-Chemical Industry Corporation produce, pellet, and the processing conditions processing identical with embodiment 13 also is injection molded into national testing standard sample.It is crooked that table 4 embodiment 13 and embodiment 14, the result of embodiment 15 contrast the outstanding tension fracture of mixture breach
The arm beam is towards intensity elongation strengths modulus
Hit intensity (MPa) rate (%) is (GPa) (MPa)
(J/m) embodiment 13 166.3 29.2 156.0 48.5 2.0 embodiment 14 47.5 35.0 212.6 52.1 1.7 embodiment 15 22.5 37.3 381.7 50.3 1.4
Embodiment 16:
2.5 μ m kaolin 679.5g with 7.5g γ-Racemic glycidol oxygen propyl trimethoxy silicane processing, 2.5 μ m aluminium hydroxide 75.5g, high density polyethylene(HDPE) 47.3g, its melt flow rate is 5g/10min, new LDPE (film grade) 47.3g, its melt flow rate is 50g/min, the ethylene-propylene rubber(EPR) 94.6g of maleic anhydride graft, its melt flow rate is 3g/min, whiteruss 37.8g, calcium stearate 8g, four [β-(and 3,5-di-tert-butyl-4-hydroxy phenyl propionic acid] pentaerythritol ester 4g, the two ten diester 6g of thio-2 acid mediate 20min with room temperature in homogenizer after, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 140-160-180-200-190 ℃ from the import to the outlet, and the water-cooled pelletizing forms.
Above-mentioned filler parent granule and high-density polyethylene resin are pressed the prescription of 20: 80 (weight percentage), after simple the mixing, in injector, directly be injection molded into national testing standard sample, injection temperature is 200 ℃, injection pressure is 13.5MPa, and its composite materials property test result sees Table 5.
Embodiment 17:
High-density polyethylene resin, the trade mark are HDPE DMD7006, and plastic molding and processing plant of Qilu Petrochemical company produces, pellet, and processing conditions and embodiment 16 are together.
Embodiment 18:
Will with the kaolin of embodiment 16 identical proportionings and aluminium hydroxide mixed fillers and high-density polyethylene resin prescription by 20: 80 (weight percentage), with the filling high-density polyethylene matrix material that working method identical with embodiment 16 and processing conditions obtain, its Mechanics Performance Testing result also can see Table 5.Table 5 embodiment 16 and embodiment 17, embodiment 18 results' contrast mixture breach cantilever tension fracture is crooked
Beam impacts intensity elongation strengths modulus
Degree (J/m) is (MPa) (GPa) embodiment 16 56.0 22.7 72.0 39.8 1.5 comparative examples 17 34.1 25.9 150.0 33.8 0.8 comparative examples 18 37.6 26.3 136.0 37.6 1.3 of rate (%) (MPa)
Claims (8)
1. the preparation method of a stuffing mother particle for toughening polyolefine is characterized in that following these steps to order and carries out:
(1) percentage ratio by weight, with the surface of surface treatment agent 0.5-2.5 treatment inorganic filling material 47.5-84.5 in super mixer,
(2) mineral filler 48.0-87.0 and carrier 10-30, processing aid 5-18, the oxidation inhibitor 0-2 that handles well mediated in super mixer evenly, the kneading time is 20-30 minute, and mediating temperature is 25 ℃-50 ℃,
(3) above-mentioned kneaded material is extruded through twin screw extruder is compound under 140 ℃-200 ℃, granulation is made.
2. the preparation method of a stuffing mother particle for toughening polyolefine is characterized in that following these steps to order and carries out:
(1) percentage ratio by weight, with the surface of surface treatment agent 0.5-2.5 treatment inorganic filling material 47.5-84.5 in super mixer,
(2) with the mineral filler 48.0-87.0 that handles well and carrier 10-30, processing aid 5-18, oxidation inhibitor 0-2, in super mixer, mediate evenly,
(3) with above-mentioned kneaded material in 120 ℃ of-150 ℃ of mixing rolls, through mixing, in flakes, pelletizing forms.
3. the preparation method of a kind of stuffing mother particle for toughening polyolefine according to claim 1 and 2 is characterized in that described mineral filler is talcum powder, kaolin, lime carbonate, titanium dioxide or aluminium hydroxide.
4. the preparation method of a kind of stuffing mother particle for toughening polyolefine according to claim 1 and 2, the particle dia that it is characterized in that described mineral filler is 1.5 μ m-5 μ m.
5. the preparation method of a kind of stuffing mother particle for toughening polyolefine according to claim 1 and 2 is characterized in that described surface treatment agent is γ-propyl methacrylate base Trimethoxy silane, γ-An Jibingjisanyiyangjiguiwan, γ-Racemic glycidol oxygen propyl trimethoxy silicane, sec.-propyl three different stearoyl titanic acid ester or is 5: 1 vinylbenzene and maleic anhydride mixture by weight.
6. the preparation method of a kind of stuffing mother particle for toughening polyolefine according to claim 1 and 2 is characterized in that described carrier is the ethylene-propylene-diene copolymer of bismaleimides graft modification, the ethylene-propylene-diene copolymer of trimethoxy propane triacrylate graft modification, ethylene-propylene rubber(EPR), ethene-alpha-olefin copolymer, polypropylene, new LDPE (film grade), high density polyethylene(HDPE) or the hydroxy-terminated polybutadienes of maleic anhydride graft.
7. the preparation method of a kind of stuffing mother particle for toughening polyolefine according to claim 6, the melt flow rate that it is characterized in that described carrier is 0.5g/10min-50g/10min.
8. the preparation method of a kind of stuffing mother particle for toughening polyolefine according to claim 1 and 2 is characterized in that described processing aid is Poly Propylene Wax, polyethylene wax, laurate, calcium stearate, whiteruss or naphthenic oil.
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