CN1730534A - Method for making little odor polypropylene material using odor agglomerate - Google Patents
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Abstract
The invention relates to a method for making little odor polypropylene material using odor agglomerate, wherein the content of the flavor agglomerate is 20-70 wt% of the matrix resin, the content of flavor depressant is 30-80%, the matrix resin has good compatibility with polypropene material, which includes polypropylene or the copolymer of ethylene-octene, the liquation flow speed (230 deg C X 2.16kg) of the polypropene is 5-50g/10min, the density of the copolymer of ethylene-octene (POE) is 0.88-0.90g/cm3, the melting index is 1-50g/10min, the flavour depressant is physical adsorption material comprising one of molecular screen material or pore silica gel material or their combination, the molecular sieve material is a alkali metal aluminosilicate powder with sodium type crystal structure.
Description
Technical field
The present invention relates to a kind of method of using the smell master batch to prepare the low odor polypropylene material, more specifically relate to the smell master batch that smell inhibitor by effectively suppressing bad smell in the polypropylene composite material and matrix resin are made high density earlier, sealing then, when the polypropylene material moulding, mix moulding with polypropylene material more at last, thereby prepare the method for the polypropylene material of low smell.
Background technology
In recent years, because the fast development of polypropylene material through engineering approaches modification technology, therefore, it in the application of automotive field more and more widely.Yet, as the important component part of through engineering approaches polypropylene material in automotive field, the various automotive trim products of making by the through engineering approaches polypropylene material, though all can meet corresponding requirements on its use properties in every respect, but, therefore be subjected to the human consumer and more and more queried because these materials all can discharge some niff in varying degrees.And along with people's environment protection health consciousness constantly strengthens, suffered challenge will be more and more serious on the one hand at this for polypropylene material.For this reason, in order further to expand the application of polypropylene material, must search out an effective way to prepare low smell even scentless polypropylene material in association area.
Usually, it is believed that the smell of polypropylene material is owing to the following aspects causes.At first, the catalyst system that uses in acrylic resin matrix building-up process contains the compound that some have the pungency peculiar smell, as ester compound or alkane derivative.This compounds can not be removed after resin polymerization is finished fully, and they remain in the middle of the acrylic resin, thereby makes polypropylene material have the pungency peculiar smell.Secondly, carry out at the acrylic resin matrix in the middle of the process of modification processing, acrylic resin more or less can produce the low molecular compound of some degraded under the fused state, as ketone, aldehyde compound.These material parts rest in the middle of the material after the modification, progressively give out irritating smell in the use of product.Once more, some filler components that added in the modified polypropylene material, as talcum powder, they can have some irritating smell equally.At last, some stablizer that is added in the modified polypropylene material also has certain pungency peculiar smell.
Round the factor of above-mentioned several respects, people do a lot, and related basic skills is physical adsorption and chemical reaction two big classes nothing more than.
Chemical reaction method is meant and adds the additive that can discharge small molecules reaction of smell with these in the middle of material prescription, by the reaction between these additives and the small molecules produce molecular weight big, use under the thermal environment normal, as less than 100 ℃, can from material, not evaporate the another kind of compound that produces peculiar smell, thereby reach the effect of eliminating peculiar smell.Though the related reaction of this method is extremely complicated,, therefore progressively caused people's interest in recent years owing to can control other performances that do not influence material on this theoretical method.
In U.S. Pat P.4 Rifi etc. have pointed out in 851,499, have ester compound in the catalyst system in the middle of isotatic polypropylene resin polymerization process, as ethyl benzoate, residue, this class residue itself is some compounds that have the pungency peculiar smell.For removing contained these materials that have of acrylic resin matrix, the method that he proposes is: adopt a kind of esterification glyceride type compound, a kind of epoxy compounds, a kind of monohydroxy-alcohol or multicomponent alcoholics compound, a kind of fatty acid ester compound or the mixture of above-mentioned several compounds, by above-claimed cpd and acrylic resin are melt extruded, carry out transesterification reaction at the ester class residue that makes these compounds in the middle of the process of extruding and have a peculiar smell and form other macromolecular compounds and be fixed in the middle of the resin, thereby reach the purpose of removing this smell.
In U.S. Pat P.5 Fukui etc. have mentioned the another kind of media that exists in 109,056 in relevant catalyst system in the middle of the acrylic resin polymerization process, alkane derivative, the residue of this compounds also can exert an influence to the smell of polypropylene material.The solution that he proposes is to adopt the method for high temperature extruding pelletization, and adopts the mode that vacuumizes in the middle of the process of extruding, and again the particle of making is carried out flint dry at last, with this these residues is carried out physics and removes.
In U.S. Pat P.5 Burch etc. have mentioned the small molecules that the method for using a kind of rosin ester solves the polypropylene material peculiar smell with irritating that cracking goes out in the middle of modification is subjected to thermal process in 041,483.
Abe etc. are at U.S. Pat P5, have proposed to use the mixture of a kind of zinc oxide, titanium dioxide and water to solve the talcous smell problem of adding in the modified polypropylene material in 023,286.
Yui etc. are at U.S. Pat P4,080, adopt a kind of alkyl 3 in 359, the smell problem that some stablizers brought that the method for 5-two-Te-butyl-4-hydroxyl-carboxylation styracin and dialkyl group thiodipropionate acetate mixture solves in the modified polypropylene material to be added.
Above-mentioned these methods on some angle, all have in various degree solution to the smell problem of polypropylene material.Yet as the polypropylene material that the automotive trim product uses, its relevant smell factor that will consider at modifying process is not only certain discrete factor wherein.At first, the fundamental starting point that solves this class modified polypropylene material smell must consider that certainly acrylic resin matrix self some in the middle of polymerization process have the residue problem of pungency peculiar smell; Secondly, therefore this class modified polypropylene material all must will consider the thermo-cracking small molecules problem in the extruding pelletization process through melt extruding granulation; Once more, the smell problem of the mineral constituent of being added also must be taken into account; At last, it is common also very high that the thermo-oxidative ageing of this class polypropylene material requires, and therefore must add corresponding stabiliser system, and this must consider in the stabilizer component some the smell problem that may bring.And above-mentioned the whole bag of tricks all is to stress certain aspect is wherein improved, and can not solve the problem that all respects produce smells.
Physical adsorption can be adsorbed the small molecules of any generation smell or other fugitive constituents in theory, therefore an ideal effect might all be arranged to all respects that produce this problem.And along with the physical absorbent industrial expansion, multiple physical absorbent system has at present grown up.Mineral soil body system, molecular sieve system etc. such as gac system, silica gel system, attapulgite have been comprised in the middle of this.Based on adsorption effect, when above-mentioned serial sorbent systems was distributed in resin matrix with a definite form, they all can adsorb the small molecules that produces smell or other fugitive constituents in the resin material.Yet in the middle of the application of reality, they have deficiency separately again.For example, adopt traditional gac, can play adsorption to the small molecules that discharges smell in the macromolecular material fully, thereby reduce smell or other harmful fugitive constituent materials of material by the micropore in the gac as sorbent material.Yet the problem that this method produces is: at first, because gac is from the color as black, so can only use in black material.Secondly, the gac addition is very big to the mechanical property influence of material.Simultaneously, we find material added gac as sorbent material after, because the micropore size size distribution inequality in the gac, difference is very big, maximum aperture is greatly to the 1000 Izod right sides, therefore often other intermediate molecular weight additives that add are simultaneously adsorbed together, influenced other characteristics of material so again, as thermo-oxidative stability etc.Therefore, this method practical value is little.And when adopting mineral soil body system such as attapulgite to remove system, being faced with sorbent material micropore size size distribution inequality equally as smell, difference is very big, thereby causes other intermediate molecular weight additives that will add absorption problem together.And, all there is a common defective in above-mentioned all sorbent systems when being applied in the resin material as the smell remover, when being their smells in the middle of the polymeric adsorbent material or other fugitive constituent materials, the moisture that will exist on every side simultaneously adsorbs together inevitably, and this can cause the problem of comparatively serious following process moulding.
For this reason, must find a kind of above-mentioned each side factor that can fully take into account, solve the method for above-mentioned various smell problems comprehensively, thereby prepare a kind of low smell or odorlessness polypropylene composite material.
Summary of the invention
The object of the invention is to provide a kind of smell master batch, and then a kind of method of using the smell master batch to prepare the low odor polypropylene material is provided.
Among the present invention: a kind of smell master batch, to form by matrix and smell inhibitor, this smell master batch is mixed with by following materials of weight proportions: (%)
Matrix resin 20-70
Smell inhibitor 30-80
Wherein, matrix resin is the resin good with the polypropylene material consistency in the described smell master batch, comprise the multipolymer (POE) of polypropylene or ethylene-octene etc., described polypropylene can be the high crystallization homo-polypropylene of the moving property of various flows or a kind of or its combination in the block copolymerization propylene, polyacrylic melt flow rate (MFR) (230 ℃ * 2.16kg) be 5-50g/10min, the multipolymer of described ethylene-octene (POE) density is 0.88-0.90g/cm
3, melting index is 1-50g/10min; Described smell inhibitor is a physisorption material, comprise a kind of or its combination in molecular screen material or the Kiselgel A material, molecular screen material is a kind of alkali metal aluminosilicate powder of sodium type crystal structure, the Kiselgel A material be the diameter of particle requirement greater than 200 orders, micropore size requires to be the porous silica powder body material of 20-30 dust.
On the such scheme basis, the alkali metal aluminosilicate powder of described sodium type crystal structure, chemical formula is:
Na
86[(AlO
2)
86(SiO
2)
106] XH
2O, diameter of particle is greater than 10 dusts.
The comonomer of described block copolymerization propylene is an ethene, and its content is in the scope of 4-10mol%, and described melting index is 5-30g/10min, and the degree of crystallinity of high-crystallinity polypropylene is more than 70%, and degree of isotacticity is greater than 99%.
A kind of preparation method of smell agglomerate material:
(1) weighs raw material by the each component weight proportion;
(2) matrix resin and smell inhibitor were done in super mixer mixed 3-5 minute;
(3) raw materials mixed is placed dual-screw-stem machine through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
On the such scheme basis, the method for using the smell master batch to prepare the low odor polypropylene material is: with the smell master batch sealing of above-mentioned gained, then, mix moulding with polypropylene material again when the polypropylene material moulding earlier.
Mechanism of the present invention is: the smell master batch that smell inhibitor by effectively suppressing bad smell in the polypropylene composite material and matrix resin are made high density earlier, sealing then, when the polypropylene material moulding, mix moulding with polypropylene material more at last, thereby prepare the method for the polypropylene material of low smell, characteristics of the present invention are: can effectively suppress earlier the smell inhibitor of bad smell in the polypropylene composite material with smell master batch that matrix resin is made high density and seal, thereby avoid the smell inhibitor to suck moisture in first being processed, influence the forming process of material, and it is even master batch and material mixing to add man-hour at forming materials, the melting mixing of body material and smell inhibitor is distributed to the smell inhibitor in the middle of the material equably during by forming process, thereby performance smell inhibitor reaches the purpose of removing smell to the micromolecular adsorption effect of smell in the material.The smell inhibitor can be selected molecular screen material or the Kiselgel A material that pore size is specific and be evenly distributed for use, can not play adsorption to other intermediate molecular weight additives that add in the material simultaneously like this, to other characteristics of material, can not exert an influence as thermo-oxidative stability etc.
Advantage of the present invention is as follows:
1, the present invention has used effective smell to remove system, and obtained matrix material has the characteristic of low smell.
2, the polypropylene composite material of the prepared low smell of the present invention is when guaranteeing the low odor property of material, and the forming process of material is not affected.
3, the polypropylene composite material of the prepared low smell of invention is when guaranteeing the low odor property of material, every physical and mechanical property excellence of material.
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment
In the smell master batch of embodiment, matrix resin can be arbitrarily and the good resin of polypropylene material consistency, as the multipolymer (POE) of various polypropylene or ethylene-octene etc.Polypropylene can be the high crystallization homo-polypropylene and the block copolymerization propylene of the moving property of various flows.Wherein the comonomer of block copolymerization propylene is common is ethene, its content is in the scope of 4-10mol%, polyacrylic melt flow rate (MFR) (230 ℃ * 2.16kg) be 5-50g/10min, more commonly used is 5-30g/10min, the degree of crystallinity of high-crystallinity polypropylene is more than 70%, and degree of isotacticity is greater than 99%; The multipolymer of described ethylene-octene (POE) is 0.88-0.90g/cm for density
3, melting index is 1-50g/10min; Described smell inhibitor is the physisorption material that any pore size is specific and be evenly distributed, as molecular screen material or Kiselgel A material etc.Molecular screen material is a kind of alkali metal aluminosilicate powder of sodium type crystal structure, and chemical formula is Na
86[(AlO
2)
86(SiO
2)
106] XH
2O, diameter of particle require greater than 200 orders, and the microporous molecular sieve aperture requires greater than 10 dusts; The Kiselgel A material be the diameter of particle requirement greater than 200 orders, micropore size requires to be the porous silica powder body material of 20-30 dust.
In the basic components of embodiment and Comparative Examples matrix material, polypropylene is different mobile high crystallization homo-polypropylene and block copolymerization propylene, and consumption is 50-90%.Wherein the comonomer of block copolymerization propylene is common is ethene, its content is in the scope of 4-10mol%, polyacrylic melt flow rate (MFR) (230 ℃ * 2.16kg) be 5-50g/10min, more commonly used is 5-30g/10min, the degree of crystallinity of high-crystallinity polypropylene is more than 70%, and degree of isotacticity is greater than 99%; Described talcum powder particle size range is the 1-10 micron; Described toughner poe is a kind of multipolymer of ethylene-octene, and density is 0.88-0.90g/cm
3, melting index is 1-50g/10min; Thermal oxidation stabilizer 3114 produces for Ciba company, and trade names are Irganox 3114, and chemical name is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid; Thermal oxidation stabilizer 618 produces for GE company, and trade names are Weston 618, and chemical name is a distearyl pentaerythritol diphosphite; Thermal oxidation stabilizer DSTP is that Britain ICE company produces, and trade names are Negonox DSTP, and chemical name is the thio-2 acid octadecyl ester;
Embodiment 1
The preparation of master batch: polypropylene 60%, molecular sieve 40% do were mixed in super mixer 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
Basic components: polypropylene 58.65%, talcum powder 40%, molecular sieve 3%, thermo-stabilizer DSTP 0.9%, thermo-stabilizer 3,114 0.3%, thermo-stabilizer 618 0.15% were done in super mixer mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
Adopt the aluminium foil bag vacuum packet to install the back the above-mentioned master batch for preparing and place a week, press master batch 4% then, the polypropylene material 96% of basic components preparation mixes the various samples of injection moulding on injection moulding machine.
Embodiment 2
The preparation of master batch: polypropylene 60%, molecular sieve 40% do were mixed in super mixer 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
Basic components: polypropylene 58.65%, talcum powder 40%, molecular sieve 3%, thermo-stabilizer DSTP 0.9%, thermo-stabilizer 3,114 0.3%, thermo-stabilizer 618 0.15% were done in super mixer mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
Adopt the aluminium foil bag vacuum packet to install the back the above-mentioned master batch for preparing and place a week, press master batch 3% then, the polypropylene material 97% of basic components preparation mixes the various samples of injection moulding on injection moulding machine.
Embodiment 3
The preparation of master batch: polypropylene 60%, molecular sieve 40% do were mixed in super mixer 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
Basic components: polypropylene 58.65%, talcum powder 40%, molecular sieve 3%, thermo-stabilizer DSTP 0.9%, thermo-stabilizer 3,114 0.3%, thermo-stabilizer 618 0.15% were done in super mixer mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
Adopt the aluminium foil bag vacuum packet to install the back the above-mentioned master batch for preparing and place a week, press master batch 2% then, the polypropylene material 98% of basic components preparation mixes the various samples of injection moulding on injection moulding machine.
Embodiment 4
The preparation of master batch: polypropylene 60%, molecular sieve 40% do were mixed in super mixer 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
Basic components: polypropylene 58.65%, talcum powder 40%, molecular sieve 3%, thermo-stabilizer DSTP 0.9%, thermo-stabilizer 3,114 0.3%, thermo-stabilizer 618 0.15% were done in super mixer mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
Adopt the aluminium foil bag vacuum packet to install the back the above-mentioned master batch for preparing and place a week, press master batch 1% then, the polypropylene material 99% of basic components preparation mixes the various samples of injection moulding on injection moulding machine.
Comparative Examples 1
Polypropylene 58.65%, talcum powder 40%, thermo-stabilizer DSTP 0.9%, thermo-stabilizer 3,114 0.3%, thermo-stabilizer 618 0.15% were done in super mixer mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
With the various samples of polypropylene material injection moulding on injection moulding machine that prepare.
Comparative Examples 2
Polypropylene 56.65%, talcum powder 40%, 13X molecular sieve 2%, thermo-stabilizer DSTP0.9%, thermo-stabilizer 3,114 0.3%, thermo-stabilizer 618 0.15% were done in super mixer mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
With the various samples of polypropylene material injection moulding on injection moulding machine that prepare.Performance evaluation mode and implementation standard:
The tensile property test is undertaken by ISO 527-2, and specimen size is 150*10*4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO 179, and specimen size is 80*6*4mm, and notch depth is 1/3rd of a sample thickness; Heat-drawn wire is undertaken by ISO 75, and specimen size is 120*10*3.0mm, and load is 1.8MPa; The thermal-oxidative aging property of material is undertaken by ISO4577, and specimen size is 50*10*10mm, and probe temperature is 150 ℃; The odor property of material is tested by the PV3900 of Volkswagen, and sample mass is 40 ~ 60g, and the vessel content size is 1 liter; Material organic compound volatility is tested by self-defined standard, and sample mass is 10, and laying temperature is 100 ℃, and be 16 hours storage period; Smell is removed the adding of system the influence of forming materials processing is passed judgment on by self-defining standard, and specimen size is 150*100*3.22mm.
Comprehensive mechanical performance is passed through the tensile strength of test gained, elongation at break, and modulus in flexure, the numerical value of thermal denaturation temperature and shock strength is passed judgment on; The thermal-oxidative aging property of material is passed judgment on according to the heat oxygen aging resistance time length of measuring by standard: the time is long more, and the heatproof air aging performance of material is good more; The odor property of material is divided into according to standard code: 1 grade: odorlessness, 2 grades: scent of, but non interference smell, 3 grades: obvious smell is arranged, but the non interference smell, 4 grades: the interference smell is arranged, 5 grades: strong interference smell is arranged, 6 grades: insupportable smell is arranged; Material organic compound volatility is according to formula: volatility %=(material initial mass-material is transferred the quality of postpone in standard code)/material initial mass * 100%, calculate, the high more expression material of the numerical value organic compound volatility of calculating gained is big more, otherwise then more little; The adding that smell is removed system to the influence of forming materials processing according to self-defining standard by having phenomenon with out splash to pass judgment on to prepared specimen surface: if there is spray in the surface of prepared sample, the adding that then shows smell removal system is processed with influence to forming materials, the spray phenomenon is serious more, and then influence is big more; Otherwise then there is not influence.
Embodiment 1-4 and the every The performance test results of Comparative Examples 1-2 be each table as follows:
Table 1 embodiment 1-4 prescription and material property table
| The matrix material title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Unnotched impact strength (kJ/m 2) | 16 | 17 | 19 | 2 1 |
| Notched Izod impact strength (kJ/m 2 | 1.8 | 1.8 | 2.0 | 2.2 |
| Tensile strength (MPa) | 32 | 32 | 31.5 | 31.2 |
| Elongation at break (%) | 4.0 | 4.2 | 5.3 | 5.5 |
| Flexural strength (MPa) | 51 | 51 | 50.5 | 50 |
| Modulus in flexure (MPa) | 4100 | 4080 | 4060 | 4020 |
| Thermal-oxidative aging property (H) | 1410 | 1440 | 1470 | 1490 |
| Oder levels | 2.5 | 3.0 | 3.5 | 4.0 |
| Organic compound volatility (%) | 0.21 | 0.23 | 0.28 | 0.35 |
| Specimen surface spray situation | Do not have | Do not have | Do not have | Do not have |
Table 2 Comparative Examples 1-2 prescription and material property table
| The matrix material title | Comparative Examples 1 | Comparative Examples 2 |
| Unnotched impact strength (kJ/m 2) | 23 | 22.4 |
| Notched Izod impact strength (kJ/m 2 | 2.4 | 2.3 |
| Tensile strength (MPa) | 33 | 32 |
| Elongation at break (%) | 5.4 | 5.3 |
| Flexural strength (MPa) | 51 | 50.5 |
| Modulus in flexure (MPa) | 4010 | 4040 |
| Thermal-oxidative aging property (H) | 1480 | 1450 |
| Oder levels | 4.5 | 2.5 |
| Organic compound volatility (%) | 1.23 | 0.25 |
| Specimen surface spray situation | Do not have | Seriously |
Can see with the contrast of Comparative Examples 1,2 from embodiment 1-4, smell removal system with the interpolation of master batch form all makes the smell of PP material significantly reduce with the smell removal system of directly adding with the molecular sieve powder, and the content of organic compound volatile matter also has minimizing in various degree in the while material.The generation of this phenomenon illustrate this in two system the volatile matter that produces smell is all had the good adsorption effect.But remove system with the smell that the master batch form is added bad influence is not appearred in the forming process of material, the surface of sample does not have any spray phenomenon and occurs; And remove system with the smell that the molecular sieve powder directly adds the shaping processing of material has been produced serious detrimentally affect, serious spray phenomenon has appearred in the surface of sample.
It is about 3% the most suitable to it can also be seen that from embodiment 1-4 the addition of the smell remover that this master batch form is added is controlled at.At this moment, material not only possesses good odor property and the low characteristic of organic volatile content, and the basic physical and mechanical property of material might as well simultaneously.
Claims (5)
1. a smell master batch is made up of matrix and smell inhibitor, and this smell master batch is mixed with by following materials of weight proportions: (%)
Matrix resin 20-70
Smell inhibitor 30-80 wherein, matrix resin is the resin good with the polypropylene material consistency in the described smell master batch, the multipolymer that comprises polypropylene or ethylene-octene, described polypropylene is different mobile high crystallization homo-polypropylenes or a kind of or its combination in the block copolymerization propylene, polyacrylic melt flow rate (MFR) (230 ℃ * 2.16kg) be 5-50g/10min, the multipolymer of described ethylene-octene (POE) density is 0.88-0.90g/cm
3, melting index is 1-50g/10min; Described smell inhibitor is a physisorption material, comprise a kind of or its combination in molecular screen material or the Kiselgel A material, molecular screen material is a kind of alkali metal aluminosilicate powder of sodium type crystal structure, the Kiselgel A material be the diameter of particle requirement greater than 200 orders, micropore size requires to be the porous silica powder body material of 20-30 dust.
2. smell master batch according to claim 1 is characterized in that, the alkali metal aluminosilicate powder of described sodium type crystal structure, and chemical formula is:
Na
86[(AlO
2)
86(SiO
2)
106] XH
2O, diameter of particle is greater than 10 dusts.
3. a kind of low odor polypropylene material that uses the preparation of smell master batch according to claim 1, it is characterized in that, the comonomer of described block copolymerization propylene is an ethene, its content is in the scope of 4-10mol%, described melting index is 5-30g/10min, the degree of crystallinity of high-crystallinity polypropylene is more than 70%, and degree of isotacticity is greater than 99%.
4. press the preparation method of one of claim 1 to 3 described a kind of smell agglomerate material:
(1) weighs raw material by the each component weight proportion;
(2) matrix resin and smell inhibitor were done in super mixer mixed 3-5 minute;
(3) raw materials mixed is placed dual-screw-stem machine through melt extruding, granulation, its technology is: 200～210 ℃ in a district, 210～220 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
5. the method for preparing a kind of low odor polypropylene material by the described a kind of smell master batch of claim 4: the smell master batch sealing with claim 4 gained then, mixes moulding with polypropylene material again when the polypropylene material moulding.
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Cited By (18)
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|---|---|---|---|---|
| CN102061036A (en) * | 2010-12-16 | 2011-05-18 | 金发科技股份有限公司 | Low-odor polypropylene composite and preparation method thereof |
| CN101817953B (en) * | 2009-10-30 | 2012-05-23 | 苏州旭光聚合物有限公司 | Low-diffusion modified polypropylene composite material and preparation method thereof |
| CN102532710A (en) * | 2011-12-28 | 2012-07-04 | 台州市黄岩明江塑胶有限公司 | Low-odor scraping-resistant polypropylene material and preparation method thereof |
| CN102532776A (en) * | 2011-12-21 | 2012-07-04 | 中国石油化工股份有限公司 | Low-smell rigid-tough high-performance polypropylene composite material and preparation method thereof |
| CN101759928B (en) * | 2008-11-21 | 2012-12-05 | 上海普利特复合材料股份有限公司 | Filling and flame-retardant polypropylene composition |
| CN103030885A (en) * | 2012-12-17 | 2013-04-10 | 上海普利特复合材料股份有限公司 | Long glass-fiber reinforced polypropylene material with low emission and high performance and production method thereof |
| CN103804745A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Polyethylene resin composition with improved appearance and odor |
| CN105524350A (en) * | 2014-10-21 | 2016-04-27 | 中国石油化工股份有限公司 | VOC (Volatile Organic Compounds)-inhibited master batch for polypropylene, and preparation method and applications thereof |
| CN106496796A (en) * | 2016-11-17 | 2017-03-15 | 大河宝利材料科技(苏州)有限公司 | PP composite material and preparation method thereof |
| CN106519546A (en) * | 2016-11-17 | 2017-03-22 | 大河宝利材料科技(苏州)有限公司 | Deodorant, preparation method thereof, and high-molecular composite material containing deodorant |
| CN107868331A (en) * | 2017-10-27 | 2018-04-03 | 中广核俊尔新材料有限公司 | One kind is low to distribute low smell dust reduction capability master batch and preparation method thereof |
| CN108219259A (en) * | 2018-01-17 | 2018-06-29 | 江林（贵州）高科发展股份有限公司 | A kind of polypropylene material for manufacturing automotive upholstery and preparation method thereof and purposes |
| CN108342020A (en) * | 2018-01-17 | 2018-07-31 | 江林（贵州）高科发展股份有限公司 | Suitable for polypropylene material for manufacturing automotive upholstery and preparation method thereof and purposes |
| CN109096598A (en) * | 2018-06-15 | 2018-12-28 | 武汉金发科技有限公司 | A kind of automobile polypropylene odor adsorption master batch and preparation method thereof |
| CN110903551A (en) * | 2019-12-19 | 2020-03-24 | 天津金发新材料有限公司 | Low-odor calcium silicate filling master batch and preparation method and application thereof |
| CN112574440A (en) * | 2020-12-17 | 2021-03-30 | 武汉金发科技有限公司 | Adsorption type low-odor master batch for polypropylene and preparation method thereof |
| CN114805939A (en) * | 2021-06-25 | 2022-07-29 | 安徽星贝达新材料科技有限公司 | Porous adsorption type odor removal master batch, preparation method and application |
| CN115044131A (en) * | 2022-06-15 | 2022-09-13 | 一汽丰田汽车(成都)有限公司长春丰越分公司 | Low-odor-emission polypropylene plastic and preparation method thereof |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759928B (en) * | 2008-11-21 | 2012-12-05 | 上海普利特复合材料股份有限公司 | Filling and flame-retardant polypropylene composition |
| CN101817953B (en) * | 2009-10-30 | 2012-05-23 | 苏州旭光聚合物有限公司 | Low-diffusion modified polypropylene composite material and preparation method thereof |
| CN102061036A (en) * | 2010-12-16 | 2011-05-18 | 金发科技股份有限公司 | Low-odor polypropylene composite and preparation method thereof |
| CN102061036B (en) * | 2010-12-16 | 2014-04-09 | 金发科技股份有限公司 | Low-odor polypropylene composite and preparation method thereof |
| CN102532776A (en) * | 2011-12-21 | 2012-07-04 | 中国石油化工股份有限公司 | Low-smell rigid-tough high-performance polypropylene composite material and preparation method thereof |
| CN102532710A (en) * | 2011-12-28 | 2012-07-04 | 台州市黄岩明江塑胶有限公司 | Low-odor scraping-resistant polypropylene material and preparation method thereof |
| CN103804745A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Polyethylene resin composition with improved appearance and odor |
| CN103030885A (en) * | 2012-12-17 | 2013-04-10 | 上海普利特复合材料股份有限公司 | Long glass-fiber reinforced polypropylene material with low emission and high performance and production method thereof |
| CN103030885B (en) * | 2012-12-17 | 2015-07-01 | 上海普利特复合材料股份有限公司 | Long glass-fiber reinforced polypropylene material with low emission and high performance and production method thereof |
| CN105524350B (en) * | 2014-10-21 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of polypropylene suppresses master batch and preparation method and application with VOC |
| CN105524350A (en) * | 2014-10-21 | 2016-04-27 | 中国石油化工股份有限公司 | VOC (Volatile Organic Compounds)-inhibited master batch for polypropylene, and preparation method and applications thereof |
| CN106519546B (en) * | 2016-11-17 | 2019-05-28 | 大河宝利材料科技(苏州)有限公司 | It dispels the polymer composite of taste agent and preparation method thereof, taste agent of dispelling including this |
| CN106519546A (en) * | 2016-11-17 | 2017-03-22 | 大河宝利材料科技(苏州)有限公司 | Deodorant, preparation method thereof, and high-molecular composite material containing deodorant |
| CN106496796A (en) * | 2016-11-17 | 2017-03-15 | 大河宝利材料科技(苏州)有限公司 | PP composite material and preparation method thereof |
| CN106496796B (en) * | 2016-11-17 | 2019-04-05 | 大河宝利材料科技(苏州)有限公司 | PP composite material and preparation method thereof |
| CN107868331A (en) * | 2017-10-27 | 2018-04-03 | 中广核俊尔新材料有限公司 | One kind is low to distribute low smell dust reduction capability master batch and preparation method thereof |
| CN108219259A (en) * | 2018-01-17 | 2018-06-29 | 江林（贵州）高科发展股份有限公司 | A kind of polypropylene material for manufacturing automotive upholstery and preparation method thereof and purposes |
| CN108342020A (en) * | 2018-01-17 | 2018-07-31 | 江林（贵州）高科发展股份有限公司 | Suitable for polypropylene material for manufacturing automotive upholstery and preparation method thereof and purposes |
| CN109096598A (en) * | 2018-06-15 | 2018-12-28 | 武汉金发科技有限公司 | A kind of automobile polypropylene odor adsorption master batch and preparation method thereof |
| CN109096598B (en) * | 2018-06-15 | 2021-04-27 | 武汉金发科技有限公司 | Polypropylene odor adsorption master batch for automobile and preparation method thereof |
| CN110903551A (en) * | 2019-12-19 | 2020-03-24 | 天津金发新材料有限公司 | Low-odor calcium silicate filling master batch and preparation method and application thereof |
| CN112574440A (en) * | 2020-12-17 | 2021-03-30 | 武汉金发科技有限公司 | Adsorption type low-odor master batch for polypropylene and preparation method thereof |
| CN114805939A (en) * | 2021-06-25 | 2022-07-29 | 安徽星贝达新材料科技有限公司 | Porous adsorption type odor removal master batch, preparation method and application |
| CN115044131A (en) * | 2022-06-15 | 2022-09-13 | 一汽丰田汽车(成都)有限公司长春丰越分公司 | Low-odor-emission polypropylene plastic and preparation method thereof |
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