CN102719021A - Vehicular low-emission polypropylene composition and preparation method thereof - Google Patents
Vehicular low-emission polypropylene composition and preparation method thereof Download PDFInfo
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- CN102719021A CN102719021A CN2012102309970A CN201210230997A CN102719021A CN 102719021 A CN102719021 A CN 102719021A CN 2012102309970 A CN2012102309970 A CN 2012102309970A CN 201210230997 A CN201210230997 A CN 201210230997A CN 102719021 A CN102719021 A CN 102719021A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a vehicular low-emission polypropylene composition and a preparation method thereof. The vehicular low-emission polypropylene composition comprises the following components in weight percentage: 40-94% of polypropylene A, 2-20% of polypropylene B, 2-20% of elastomer, 1-2% of liquid extractant, 0-30% of talcum powder and 1-3% of auxiliary agent. The preparation method comprises the following steps: firstly, mixing the polypropylene A, the polypropylene B, the elastomer, the liquid extractant and the auxiliary agent for 1-2 minutes in a high-speed mixer; secondly, adding the talcum powder and mixing for 3-5 minutes to obtain a premix; and finally, melting and extruding the premix by a twin-screw extruder, and performing two-stage vacuum granulation to obtain a finished product. Emission of free organic matters in the vehicular polypropylene can be reduced by introducing the polypropylene with a high melt strength and the liquid extractant; two-stage vacuum devolatilization can prolong the effective acting time of the time in the system, so that the prepared composition has a lower emission characteristic; and the preparation method is simple in process, low in equipment requirement and high in product yield.
Description
Technical field
The present invention relates to a kind of polypropene composition, particularly a kind of automobile-used low polypropene composition and preparation method thereof that distributes.
Background technology
Automobile bodies is owing to often be in closure state, and interior products such as its skin chair cover or cloth chair cover can produce sporadic organic cpds such as free formaldehyde, alkane, benzene, toluene, thereby human body is produced detrimentally affect.For reducing the content of sporadic material in the material; Need control from aspects such as starting material source, complete processing, additives; Or add the material that can react with these small molecules volatile matter; It is bigger to generate molecular weight, not volatile can the stable existence material in and the compound that is difficult for evaporating, thereby reach the purpose that reduces sporadic material.
Main both at home and abroad at present employing prepared in one of two ways is hanged down and is distributed automobile-used polypropene composition: 1. the sporadic material that reduces material through the chemical physics adsorption; Patent WO2007052074-A2 discloses a kind of palladium doped molecular sieve and has adsorbed VOC gas; This molecular sieve is adsorb volatile gas long-term effectively; In wet environment, be a kind of effective VOC remover particularly; Chinese patent CN1727390A discloses PP composite material of a kind of low smell and preparation method thereof; Its method is in system, to add alkali metal aluminosilicate powder smell remover (sodium type molecular sieve); Bad smell in the absorption system is prepared the PP composite material that hangs down smell.
Yet the method that reduces sporadic material through chemical reaction often only is directed against a factor, can not solve the sporadic problem that various factors produces simultaneously; Physical adsorption does not possess particular selecting property; Can the small molecules of all generations be adsorbed; But add molecular sieve and prepare low two shortcomings of polypropylene material existence of distributing: the one, can not add oily substance in the system, in actual production process, generally to obtain the uniform compsn of performance; Need to add a certain amount of white oil or MO and stick to resin material grain surface, add behind the molecular sieve easily the absorption oily substance and make the adsorption effect variation by filler; The 2nd, the material of molecular sieve adsorption still exists in the system, under secular thermal ageing, photoaging effect, the risk that discharges is again arranged.
2. polymkeric substance devolatilization, the main devolatilization equipment and the technology of special use of adopting is carried out devolatilization in Vestolen PP 7052 polymerization or modifying process, in polymerization process, carry out the high restriction of devolatilization required equipment cost and be difficult for extensively adopting; Patent CN200810023327.5 discloses a kind of low molecule organic matter remover that in modifying process, adds and has adopted three grades of low methods of distributing the automotive trim PP Pipe Compound of vacuum preparation again; Yet the remover that this method is added stably is dispersed in the polymer melt than difficulty, and three grades of vacuum make remover exist reduce the effective acting time of system, and devolatilization efficient is not high.
Summary of the invention
The purpose of this invention is to provide a kind of automobile-used hanging down and distribute polypropene composition, can significantly reduce the discharging of organic cpds, thereby reduce the interior gas contamination of car of its generation.
Automobile-used hanging down according to the invention distributed polypropene composition, and its compositions in weight percentage comprises:
Vestolen PP 7052 A 40 ~ 94%
Vestolen PP 7052 B 2 ~ 20%
Elastomerics 2 ~ 20%
Liquid extractant 1 ~ 2%
Talcum powder 0 ~ 30%
Auxiliary agent 1 ~ 3%
Said Vestolen PP 7052 A is a COPP; Under 230 ℃, load 2.16KG condition, the melt flow rate(MFR) of COPP (MFR) is 5-60g/10min by GB GB/T 3682-2000; Measure its socle girder notched Izod impact strength＞5 KJ/m according to GB GB/T 1843-1996
2(23 ℃), breach type are the A type, and COPP is random or segmented copolymer, and cationic coordinate polymerization, Ziegler-Natta negative ion coordination polymerization or synthetic with metallocene catalyst.
Vestolen PP 7052 B is the Vestolen PP 7052 of high fondant-strength; The melt strength of high melt strength, propylene is 8-30cN, and melt flow rate(MFR) is 0.2-10g/10min.Wherein, the melt strength test condition is: under 190 ℃ test temperature, use the capillary die of length-to-diameter ratio as 10:1, mouthful mould is 24cm to the distance of roller, and the plunger lowering speed is 0.10mm/s, and the acceleration stresses of traction rollers is 5mm/s
2Its melt flow rate(MFR) is measured under 230 ℃, load 2.16KG condition by GB GB/T 3682-2000.
Described elastomerics is one or more a mixture of ethylene-propylene copolymer, ethene-hexene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, and its density is 0.850-0.900g/cm
3
Said talcous median size size (D50) is 2 ~ 20 μ m, and D97 is 10 ~ 45 μ m, and talcous particle diameter D50 commonly used and D97 represent; D50 representes that particle diameter accounts for 50% greater than its particle, also accounts for 50% less than its particle, i.e. median size, and D97 representes that particle diameter accounts for 97% less than its particle.
Liquid extractant normal temperature is liquid, and boiling point or volatilization temperature are 90 ~ 180 ℃ under the normal pressure, and colorless and odorless.Liquid extractant is selected from water, SWS-F 221, hexamethyldisilane, triethyl silicane, triethyl silanol, octamethylcyclotetrasiloxane or octamethyltrisiloxane.
Said auxiliary agent is one or more the mixture in oxidation inhibitor, photostabilizer, lubricant or the toner; Described oxidation inhibitor is Hinered phenols and phosphorous acid esters, and one or both that comprise four [(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethanes and tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester are composite; Said photostabilizer is the low molecular weight hindered amine and the benzoic ether compound 3808 that is obstructed; Said lubricant is calcium stearate or Zinic stearas; Said toner is pigment dyestuff and mineral dye, because the present invention is used for the injection molded automobile product, in order to reach needs attractive in appearance; The normal different colours of making; So also include micro-pigment dyestuff and mineral dye in the present composition, pigment dyestuff has permanent bordeaux, permanent yellow, phthalocyanine blue, phthalocyanine green, inorganic have titanium oxide, carbon black, red iron oxide, iron oxide black, a ultramarine; These pigment can require to use separately according to the moulding color, also can compoundly use.
Automobile-used hanging down according to the invention distributed polypropene composition, and its preparation method comprises the steps:
Take by weighing component Vestolen PP 7052 A, Vestolen PP 7052 B, elastomerics, liquid extractant and auxiliary agent by weight percentage, in high-speed mixer, mixed 1-2 minute earlier, and then add talcum powder mixing 3-5 minute, obtain Preblend; Preblend through twin screw extruder melt extrude, the secondary vacuum granulation makes finished product.
Polypropene composition of the present invention can be used for preparing the automotive plastic product, and automotive plastic workpieces is meant automotive upholstery, comprises test board, auxiliary fasia console, column, glove box, door-plate, trunk plate, threshold.
Through test, the trolley part of polypropylene material preparation of the present invention, its various performances all reach request for utilization, have low distribution performance, satisfy automobile and use standard and standard.
Compared with prior art, according to the inventionly automobile-usedly low distribute polypropene composition and have following beneficial effect:
1. in COPP, introducing Vestolen PP 7052 B is the Vestolen PP 7052 and the liquid extractant of high fondant-strength, can reduce the sporadic of automobile-used polypropylene modified material, thereby reduces distributing of free matter;
2. use the devolatilization of secondary vacuum, can increase the effective acting time of liquid extractant in system, prepared compsn has lower emission characteristics;
3. preparation technology is simple, and equipment requirements is low, and the product good article rate is high, can be widely used in the production of various emission rate automotive interior materials.
Embodiment
The A of Vestolen PP 7052 described in the embodiment is a COPP, and under 230 ℃, load 2.16KG condition, the melt flow rate(MFR) of said COPP (MFR) is 5-60g/10min by GB GB/T 3682-2000; Measure its socle girder notched Izod impact strength＞5 KJ/m according to GB GB/T 1843-1996
2(23 ℃), breach type are the A type, and COPP is random or segmented copolymer, and cationic coordinate polymerization, Ziegler-Natta negative ion coordination polymerization or synthetic with metallocene catalyst.
The B of Vestolen PP 7052 described in the embodiment is the Vestolen PP 7052 of high fondant-strength, and the melt strength of said high melt strength, propylene is 8-30cN, and melt flow rate(MFR) is 0.2-10g/10min.Wherein, the melt strength test condition is: under 190 ℃ test temperature, use the capillary die of length-to-diameter ratio as 10:1, mouthful mould is 24cm to the distance of roller, and the plunger lowering speed is 0.10mm/s, and the acceleration stresses of traction rollers is 5mm/s
2Its melt flow rate(MFR) is measured under 230 ℃, load 2.16KG condition by GB GB/T 3682-2000.
Provide embodiment below so that the present invention is carried out concrete description, but be not limited thereto.
Embodiment one
Take by weighing the component shown in the table 1 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 5 g/10min, and its socle girder notched Izod impact strength is 6KJ/m
2, the melt strength of Vestolen PP 7052 B is 30cN, melt flow rate(MFR) is 0.2g/10min.In high-speed mixer, mixed 1 minute, obtain Preblend; Preblend through twin screw extruder melt extrude, the secondary vacuum granulation makes finished product, and measures its over-all properties, concrete numerical value is listed in table 1.
Embodiment two
Take by weighing the component shown in the table 1 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 30 g/10min, and its socle girder notched Izod impact strength is 8KJ/m
2, the melt strength of Vestolen PP 7052 B is 8cN, melt flow rate(MFR) is 10g/10min.Earlier Vestolen PP 7052 A, Vestolen PP 7052 B, elastomerics, liquid extractant and auxiliary agent were mixed in high-speed mixer 1 minute, and then add talcum powder mixing 3 minutes, obtain Preblend; Preblend through twin screw extruder melt extrude, the secondary vacuum granulation makes finished product, and measures its over-all properties, concrete numerical value is listed in table 1.
Embodiment three
Take by weighing the component shown in the table 1 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 60g/10min, and its socle girder notched Izod impact strength is 15 KJ/m
2, the melt strength of Vestolen PP 7052 B is 15cN, melt flow rate(MFR) is 5g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 1.
Embodiment four
Take by weighing the component shown in the table 1 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 20g/10min, and its socle girder notched Izod impact strength is 12 KJ/m
2, the melt strength of Vestolen PP 7052 B is 25cN, melt flow rate(MFR) is 1g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 1.
Embodiment five
Take by weighing the component shown in the table 1 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 40g/10min, and its socle girder notched Izod impact strength is 10 KJ/m
2, the melt strength of Vestolen PP 7052 B is 12cN, melt flow rate(MFR) is 6g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 1.
Embodiment six
Take by weighing the component shown in the table 1 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 50g/10min, and its socle girder notched Izod impact strength is 20 KJ/m
2, the melt strength of Vestolen PP 7052 B is 18cN, melt flow rate(MFR) is 3g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 1.
Embodiment seven
Take by weighing the component shown in the table 2 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 12g/10min, and its socle girder notched Izod impact strength is 35 KJ/m
2, the melt strength of Vestolen PP 7052 B is 10cN, melt flow rate(MFR) is 8g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 2.
Embodiment eight
Take by weighing the component shown in the table 2 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 28g/10min, and its socle girder notched Izod impact strength is 15 KJ/m
2, the melt strength of Vestolen PP 7052 B is 16cN, melt flow rate(MFR) is 4g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 2.
Embodiment nine
Take by weighing the component shown in the table 2 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 10g/10min, and its socle girder notched Izod impact strength is 15 KJ/m
2, the melt strength of Vestolen PP 7052 B is 22cN, melt flow rate(MFR) is 2g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 2.
Embodiment ten
Take by weighing the component shown in the table 2 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 55g/10min, and its socle girder notched Izod impact strength is 25 KJ/m
2, the melt strength of Vestolen PP 7052 B is 29cN, melt flow rate(MFR) is 0.6g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 2.
Embodiment 11
Take by weighing the component shown in the table 2 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 36g/10min, and its socle girder notched Izod impact strength is 15 KJ/m
2, the melt strength of Vestolen PP 7052 B is 18cN, melt flow rate(MFR) is 3g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 2.
Embodiment 12
Take by weighing the component shown in the table 2 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 23g/10min, and its socle girder notched Izod impact strength is 36KJ/m
2, the melt strength of Vestolen PP 7052 B is 10cN, melt flow rate(MFR) is 8g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 2.
Comparative Examples one
Take by weighing the component shown in the table 3 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 62g/10min, and its socle girder notched Izod impact strength is 2 KJ/m
2, the melt strength of Vestolen PP 7052 B is 40cN, melt flow rate(MFR) is 0.1g/10min.The preparation method is with embodiment one, and measures its over-all properties, and concrete numerical value is listed in table 3.
Comparative Examples two
Take by weighing the component shown in the table 3 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 4g/10min, and its socle girder notched Izod impact strength is 3 KJ/m
2, the melt strength of Vestolen PP 7052 B is 6cN, melt flow rate(MFR) is 12g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 3.
Comparative Examples three
Take by weighing the component shown in the table 3 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 4g/10min, and its socle girder notched Izod impact strength is 3 KJ/m
2, the melt strength of Vestolen PP 7052 B is 36cN, melt flow rate(MFR) is 0.15g/10min.The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 3.
Comparative Examples four
Take by weighing the component shown in the table 3 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 4g/10min, and its socle girder notched Izod impact strength is 3 KJ/m
2, the melt strength of Vestolen PP 7052 B is 2cN, melt flow rate(MFR) is 20g/10min.
The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 3.
Comparative Examples five
Take by weighing the component shown in the table 3 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 4g/10min, and its socle girder notched Izod impact strength is 3 KJ/m
2, the melt strength of Vestolen PP 7052 B is 4cN, melt flow rate(MFR) is 15g/10min.
The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 3.
Comparative Examples six
Take by weighing the component shown in the table 3 by weight percentage, wherein the melt flow rate(MFR) of Vestolen PP 7052 A (MFR) is 65g/10min, and its socle girder notched Izod impact strength is 4 KJ/m
2, the melt strength of Vestolen PP 7052 B is 35cN, melt flow rate(MFR) is 0.16g/10min.
The preparation method is with embodiment two, and measures its over-all properties, and concrete numerical value is listed in table 3.
Table 1 polypropene composition is formed and distribution performance
Table 2 polypropene composition is formed and distribution performance
Table 3 polypropene composition is formed and the distribution performance Comparative Examples
Performance evaluation mode and implementation standard
The organic cpds emissions measurement (TVOC) of polypropene composition detects according to TS-INT-002.
Distribution performance test result by each embodiment and Comparative Examples can be found out; After the present invention adopts Vestolen PP 7052 B and liquid extractant; The polypropene composition that obtains has lower TVOC value, and promptly the distribution performance of compsn is greatly improved, and satisfies the use standard of automotive upholstery.
Embodiment according to the invention only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, content still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes to the person skilled in the art in this field according to the present invention.
Claims (9)
1. automobile-used hanging down distributed polypropene composition, and its compositions in weight percentage comprises:
Vestolen PP 7052 A 40 ~ 94%
Vestolen PP 7052 B 2-20%
Elastomerics 2 ~ 20%
Liquid extractant 1 ~ 2%
Talcum powder 0 ~ 30%
Auxiliary agent 1 ~ 3%
Said Vestolen PP 7052 A is a COPP; The melt flow rate(MFR) of COPP is 5-60g/10min under 230 ℃, load 2.16KG condition; , its socle girder notched Izod impact strength under 23 ℃ greater than 5KJ/m
2
Said Vestolen PP 7052 B is the Vestolen PP 7052 of high fondant-strength, and its melt strength is 8-30cN, and melt flow rate(MFR) is 0.2-10 g/10min under 230 ℃, load 2.16KG condition;
Said melt flow rate(MFR) is to measure by GB GB/T 3682-2000, and the socle girder notched Izod impact strength is to measure according to GB GB/T 1843-1996.
2. the automobile-used low polypropene composition that distributes according to claim 1; It is characterized in that; The test condition of described melt strength is: under 190 ℃ test temperature, use the capillary die of length-to-diameter ratio as 10:1, mouthful mould is 24cm to the distance of roller; The plunger lowering speed is 0.10mm/s, and the acceleration stresses of traction rollers is 5mm/s
2
3. the automobile-used low polypropene composition that distributes according to claim 1; It is characterized in that; Described elastomerics is one or more a mixture of ethylene-propylene copolymer, ethene-hexene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, and its density is 0.850-0.900g/cm
3
4. a kind of automobile-used hanging down according to claim 1 distributed polypropene composition, it is characterized in that described talcous median size dimension D 50 is 2 ~ 20 μ m, and D97 is 10 ~ 45 μ m.
5. automobile-used hanging down according to claim 1 distributed polypropene composition, it is characterized in that described liquid extractant normal temperature is liquid, and boiling point or volatilization temperature are 90 ~ 180 ℃ under the normal pressure, and colorless and odorless.
6. the automobile-used low polypropene composition that distributes according to claim 5; It is characterized in that described liquid extractant is water, SWS-F 221, hexamethyldisilane, triethyl silicane, triethyl silanol, octamethylcyclotetrasiloxane or octamethyltrisiloxane.
7. according to claim 1ly automobile-usedly low distribute polypropene composition, it is characterized in that, described auxiliary agent is one or more the mixture in oxidation inhibitor, photostabilizer, lubricant or the toner.
8. prepare each said automobile-used low method of distributing polypropene composition of claim 1-7, comprise the steps:
Take by weighing component Vestolen PP 7052 A, Vestolen PP 7052 B, elastomerics, liquid extractant and auxiliary agent by weight percentage, in high-speed mixer, mixed 1-2 minute earlier, and then add talcum powder mixing 3-5 minute, obtain Preblend; Preblend through twin screw extruder melt extrude, the secondary vacuum granulation makes finished product.
9. said each the automobile-used low polypropene composition that distributes of claim 1 ~ 7 is used in the preparation automotive part.
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| CN102276926A (en) * | 2011-07-22 | 2011-12-14 | 金发科技股份有限公司 | Polypropylene composition for vehicle and preparation method thereof |
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| CN104262783A (en) * | 2014-09-17 | 2015-01-07 | 上海日之升新技术发展有限公司 | Low-odor mineral reinforced polypropylene composite material and preparation method thereof |
| CN104262783B (en) * | 2014-09-17 | 2016-08-17 | 上海日之升新技术发展有限公司 | A kind of low abnormal smells from the patient mineral-reinforced polypropylene composite material and preparation method thereof |
| CN105037867A (en) * | 2015-05-06 | 2015-11-11 | 合肥创新轻质材料有限公司 | TPV material being low in odor and TVOC content and preparation method thereof |
| CN105602184A (en) * | 2015-12-30 | 2016-05-25 | 上海金发科技发展有限公司 | Low-diffusion, ultrahigh-shading and high-reflective styryl composition and preparation method thereof |
| CN107652532A (en) * | 2016-07-25 | 2018-02-02 | 中国石油化工股份有限公司 | A kind of low VOC preparation method of acrylic resin and its acrylic resin of preparation |
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|---|---|
| CN102276926A (en) | 2011-12-14 |
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