CN102061036B - Low-odor polypropylene composite and preparation method thereof - Google Patents
Low-odor polypropylene composite and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-odor polypropylene composite material and a preparation method thereof. The polypropylene composite material disclosed in the invention comprises the following components in percentage by weight: 50%-78% of polypropylene, 7%-20% of flexibilizer, 0%-30% of mineral filler and 0.5%-4% of odor inhibitor, wherein the odor inhibitor comprises the following components in percentage by weight: 2%-50% of clay, 25%-75% of zeolite and 0%-50% of metallic oxide. The polypropylene composite material can be prepared by the steps of: premixing raw materials, extruding, pelleting and drying. The preparation method has a simple process and an excellent comprehensive performance, and the prepared polypropylene composite material has low odor. The odor grade of the low-ordor polypropylene composite material prepared from the odor inhibitor consisting of three components of the clay, the zeolite and the metallic oxide reaches grade 3 of a standard PV3900, which meets the use requirement of interior and exterior trimming parts of automobiles.
Description
Technical field
The present invention relates to material modified technical field, be specifically related to a kind of low odor polypropylene composition and method of making the same.
Background technology
Polypropylene (PP) material, due to its good over-all properties, is applied widely in each large assembly system of automobile.Automobile exterior trimming parts and inside gadget are used polypropylene composite material injection moulding mostly.Automotive upholstery is as dashboard, column, packaging tray, door-plate etc., and exterior trimming parts is as collision bumper, rubbing strip, interceptor etc.Automotive interior material, except having good mechanical property, processing characteristics, weather resistance and scratch resistant performance, also will have good low volatility, and wherein smell requirement is that volatile matter one of is evaluated.
In order to limit inside gadget material smell, each large automaker of the world sets about having carried out the research work of this respect, all and respectively formed to these volatile harmful materials standard of standard and control in addition, as the VW ' s PV3900E of Volkswagen standard, the BO131-03 standard of Ford Motor and the GMW3205 of General Motors etc.The evaluation test method of these standards is basic identical, and just assessment grade is different.PV3900 and BO131-03 adopt 1 ~ 6 grade of evaluation, and rank is higher, and smell is larger, is less than or equal to 3.5 grades and just can meets the demands.And GMW3205 adopts the evaluation of 1-10 level, rank is higher, and smell is lower, oder levels be more than or equal to 6 grades just can be judged to be qualified.This patent adopts PV3900 to grade to smell.
The reason that composite polypropylene inside gadget material smell produces is many-sided.First, the initiator using in acrylic resin building-up process and catalyst system itself contain the compound with pungent odour, for example phenolic compound, ethyl benzoate compounds or alkane derivative, this compounds and unreacted completely propylene monomer can not be removed completely after polymerization completes, they remain in acrylic resin, even if seldom, also can make polypropylene with overpowering odor.Secondly, polypropylene matrix is in carrying out the process of modification, and autoxidation degraded can occur the polypropylene of molten state, produces some low molecular compound, and these materials are included in the material after modification, in the use procedure of molded article and product, come out.Moreover, automobile-used polypropylene composite material is in order to meet car gage requirement, often add multiple auxiliary agent, as materials such as mineral filler, elastomerics, tinting material, oxidation inhibitor, damage resistant agent, these materials they itself or residual impurity evaporate, and produce pungent odour, or polyacrylic autoxidation degraded is accelerated in the catalysis in the course of processing of impurity wherein, the iron copper metal ion for example containing in talcum powder, can accelerate polypropylene and decompose, and produces larger smell.If smell is large, will severe contamination car in air, affect the healthy of driver and crew.Subduing smell is one of automobile-used polypropylene composite material important subject.
Reduce smell and can take several measures below: 1, by low smell substitute, substitute those unpleasant additives; 2, adopt more pure resin; 3, add sorbent material, comprise chemical reaction and physical adsorption method.
Chemical reaction method refers to the additive that some can react with scent of small-molecule substance, these additives and small molecules reaction, produce the another kind of compound that molecular chain is large, can not evaporate in general environment, thereby elimination smell, for example zinc ricinate reduces smell by chelating aldehyde ketone molecule.And for physical adsorption, theoretically, a large amount of cavities can be adsorbed the small molecules of any generation smell or other fugitive constituents, therefore may all produce effect to producing all respects of smell problem.And along with physical absorbent industrial expansion, physical adsorption system kind is very many at present.Comprise gac, silica gel, Attapulgite, clay mineral system, molecular sieve, zeolite, wollastonite, wilkinite etc., when they are dispersed in resin system, can adsorb the small-molecule substance that aperture is less than self micropore, thereby reduce smell.
Activated carbon is generally acknowledged and can be used as the absorber material of organic molecule and for the material of purifying air, have very large specific surface area (200-1000m
2/ gr), the carbon raw materials such as charcoal, shell, coal are made after charing.
Zeolite is as sodium, potassium, manganese, the elementary composition crystalline silico-aluminate of element HeIIA family of Gai Lei IA family, and it is to be connected and to be formed by oxo bridge key by silicon-oxy tetrahedron or aluminum-oxygen tetrahedron.In molecular sieve lattice, there is metallic cation (as Na, K, Ca etc.), with negative charge unnecessary in balance tetrahedron.In structure, there are uniform duct, a lot of apertures and marshalling, hole that internal surface area is very large.High-temperature activation loses after water, and crystals has just formed the micropore of many pore size homogeneous, has very strong adsorptive power, effective diameter can be less than in the molecule inspiration hole in its aperture, and can not adsorb the molecule that is greater than its aperture.Zeolite can comprise A type, Y type, X-type, ZSM-5 etc. for natural or manually acquisition, is divided into hydrophobic and hydrophilic composition.
Wollastonite is the silicon-dioxide that various crystal formations and amorphous form exist.Yet gac, Attapulgite, clay mineral system, micropore size skewness difference are very big, even maximum can reach 100 nanometers; Simultaneously these materials are water suction, and in absorption, smell is micromolecular can absorb water simultaneously, therefore must consider above-mentioned factor.
Around above-mentioned factor, people do a lot.
Patent USP.4, points out in 851,499, in isotatic polypropylene resin polymerization process, have catalyst system in ester compound: the residue of ethyl benzoate, with pungent odour.This smell of place to go proposes: one or more in compound, epoxy compounds, monohydroxy-alcohol compound, fatty acid compound that adopted esterification glyceryl ester, by above-claimed cpd and acrylic resin are melt extruded, these compounds and carry out transesterification reaction with the ester class residue of peculiar smell and form macromolecular cpd in extrusion, not volatile, thus reach the effect of removing such smell.
Patent USP.5, mentions catalyst system in polypropylene polymerization process in 106,056 and has alkane compound, and the residual of these materials also can be caused negative impact to acrylic resin smell.The solution that he proposes is to adopt in high temperature extruding pelletization process to vacuumize, and the granulation material flint dry of producing, thereby dry except residual small-molecule substance.
Patent USP.5,041,483 proposes to solve with rosin ester the micromolecular compound with pungent odour that polypropylene is produced by thermo-cracking.
Patent USP5, under proposing in 023,286 to exist with zinc oxide, titanium dioxide and water, solves the talcous smell problem of adding in filled modified polypropylene.
Patent USP4,080,359 adopts alkyl 3,5-di-tert-butyl-4-hydroxyl-carboxylation styracin and dialkyl group sulfo-diacrylate, acetate mixture solves the smell of stablizer in modified polypropene.
It is that resinogen material, stablizer, mineral filler and processing cracking produce that patent 200510026760.0 is mentioned smell, smell solution: nano zine oxide and nano titanium oxide.
Patent 200610064232.9 has proposed a kind of superabsorbent composition that absorbs smell, comprises smell sticking agent (amino acid, zinc ricinate mixture).
Patent USP6,376,741 have described the base material with odor control compositions, and this base material comprises silica and zeolite, yet, proved that conventional odor control compositions is not too effective to comprehensive odour control.
EPO 348978 discloses a kind of articles for use with scent of inhibitor, and odor control agent is wherein selected from carbon, clay, silica, zeolite and molecular sieve.
Yet these methods are the only impact on smell for a certain component all, thereby add sorbent material, reduce smell, but in fact inside gadget material smell is the interactional result of various ingredients smell.
Summary of the invention
The object of the invention is to overcome the deficiency existing in existing low odor polypropylene, a kind of new low-odor polypropylene ene compositions is provided, said composition has comprised a kind of by zeolite, clay, the composite smell inhibitor forming of metal oxide, this smell inhibitor is cheaply easy to get, and when not affecting the mechanical property of product, multiple volatile constituent is had to stronger adsorption, therefore the automotive upholstery obtaining meets VW ' S PV3900-2000 standard with polypropene composition, and has good mechanical property.
Another object of the present invention is to provide a kind of method of preparing described low-odor polypropylene ene compositions.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A low-odor polypropylene ene compositions, the component of being calculated by following percentage ratio by weight forms:
Polypropylene 50 ~ 78%;
Toughner 7 ~ 20%;
Smell inhibitor 0.5 ~ 4%;
Mineral filler 0 ~ 30%;
Described smell inhibitor is the mixture of zeolite, clay, metal oxide composition.
The component that described smell inhibitor is calculated by following percentage ratio by weight forms:
Clay 2% ~ 50%;
Zeolite 25% ~ 70%;
Metal oxide 0% ~ 50%;
Described metal oxide is one or more the mixture in magnesium oxide, calcium oxide, zinc oxide.
As a kind of preferred version, the component that described smell inhibitor is calculated by following percentage ratio by weight forms:
Clay 20% ~ 35%;
Zeolite 50% ~ 70%;
Metal oxide 1% ~ 30%.
As a kind of more preferably scheme, the component that described smell inhibitor is calculated by following percentage ratio by weight forms:
Clay 20% ~ 30%;
Zeolite 50% ~ 65%;
Metal oxide 5% ~ 25%.
Described zeolite is hydrophilic zeolite; Described clay is hydrophobic type clay, SiO in described hydrophobic type clay
2/ Al
2o
3mol ratio be 35 ~ 500.
Described polypropylene is preferably second the third Co-polypropylene, and its melting index is 11 ~ 25g/min; Described toughner is POE, and its melting index is 0.3 ~ 10 g/min; Described mineral filler is one or more the mixture in talcum powder, calcium carbonate, barium sulfate; Described antiaging agent is one or more the mixture in suffocated amine antioxidant, Hinered phenols antioxidant, phosphite.
Described hydrophilic zeolite is the hydrophilic zeolite with high surface area, and specific surface area is 150 ~ 350m
2/ gr.
The aperture of described hydrophilic zeolite is 0.3 nanometer ~ 1.5 nanometer.
As a kind of preferred version, the aperture of described hydrophilic zeolite is preferably 0.3 nanometer ~ 1 nanometer.
A preparation method for described low-odor polypropylene ene compositions, comprises the steps:
(1), by the polypropylene taking, toughner, smell inhibitor premix, after then mineral filler being added, mix the starting material that obtain mixing;
(2) starting material that mix are placed in to twin screw extruder, temperature is controlled at 200 ℃～215 ℃, melt extrudes granulating and drying under the condition that screw speed is 450 revs/min.
Smell inhibitor described in step (1) is that described activation condition is: at 500 ℃, activate 2 hours through the smell inhibitor of retort furnace activation; Described doing time is in advance 1 ~ 3 minute, and described mixing time is 3 ~ 4 minutes.
The present invention also adopts gas chromatograph and organic mass spectrometer coupling (GC-MS) with the smell of polypropene composition, to carry out comprehensive analysis to automotive upholstery, determines that odoring substance forms and source.Research discovery, automotive upholstery is the one of the main reasons that affects smell with the contained volatile organic compounds of polypropene composition.By GC with Headspace-MS, analyze these volatile organic compound ingredients, find that they are mainly low-molecular-weight alkane, alkene, ester, aldehyde, letones, the boiling point of these materials is conventionally within the scope of 50～260 ℃.When temperature reach a certain height, under the effect of photo-thermal, uncomfortable smell is made us in generation, even causes the uncomfortable reactions such as headache, dry cough and allergy.The generation reason of modified polypropene inside gadget material smell is very complicated, in our Case Experiments On A, finds, talcum powder, acrylic resin are not the major cause that smell produces, but produces smell prerequisite.
Compared with prior art, the present invention has following beneficial effect:
(1) diluted acid existing in polypropylene material can decompose by catalysis polypropylene, and generation odoring substance, the present invention uses metal oxide as smell inhibitor, react the corresponding metal-salt of generation with the diluted acid in polypropylene material, thereby suppressed the polypropylene that the existence due to diluted acid causes, decompose, play and reduce the effect that odoring substance produces;
(2) smell inhibitor of the present invention is simple and easy to get, can adsorb multiple volatile constituent, thereby reach the taste removal effect of application demand;
(3) component proportion of smell inhibitor of the present invention works by synergistic effect, therefore adsorbs taste removal effect higher than using separately a kind of smell inhibitor of component;
(4) smell inhibitor of the present invention can not impact mechanical property;
(5) automotive upholstery polypropene composition of the present invention, smell is low, satisfactory mechanical property, preparation technology is simple, and cost is low.
Accompanying drawing explanation
Fig. 1 is the contained odoring substance of the composition of comparative example 1;
Fig. 2 is the contrast of the contained odoring substance of composition of embodiment 1 and comparative example 1; As can be seen from Figure 2, after having added smell inhibitor, the odoring substance in polypropylene material greatly reduces.
Embodiment
Below in conjunction with embodiment, further explain the present invention; but embodiment does not limit in any form the present invention; and specific embodiment can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field some nonessential improvement that content is made the present invention according to the present invention and adjustment still belong to protection scope of the present invention.
Described clay, zeolite, metal oxide is self-control product.
Testing method:
In the following example, press VW ' S PV3900-2000 standard testing oder levels, and measure the absorption analysis to smell volatile matter with static headspace-GC-MS combined instrument.Headspace gas chromatography experiment head space is the dynamic head space of 8000 sample concentrator type of CDS Analytial Inl; Helium is carrier gas.
The preparation method of described smell inhibitor: clay, zeolite, metal oxide is 500 ~ 600 ℃ of activation treatment of retort furnace 2 hours, takes out that to be placed in 100 ℃ of odorlessness baking ovens cooling standby.
For same modified polypropene formula system, we have prepared comparative example 1 ~ 5 and embodiment 1, investigate the ability that odor control compositions absorbs odoring substance.
We investigate by comparative example 6 ~ 8 and embodiment 2 variation that different odor control group compound proportionings and addition are investigated smell.
Because the odoring substance contamination that different modified polypropene formula systems contains is different, we investigate by embodiment 2 and embodiment 3.
Before and after adding smell composition, contrast, although add after suitable composition and suitable proportioning, smell obviously reduces, but it should be understood that the pore structure of any given odor control agent composition and surface chemical property all can not be applicable to reducing all types of smells, we are for the substance classes and the source that produce smell in polypropylene modification material, filter out suitable smell inhibitor combination, find that the low absorptivity for the bad compound of one or more smells can be by compensating the good absorption of other unpleasant odor materials.
Comparative example 1
Table 1 formulation content
| Component | Manufacturer | Weight percentage |
| ? | Sinopec, Singapore's polyolefine | 69 |
| POE | Mitsui | |
| 10% | ||
| Talcum powder | Heshan Chemical Group | 20% |
| Antiaging agent | Vapour Bagong department | 1% |
Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm by weight percentage and mix 3 minutes, and then put into twin screw extruder, temperature is controlled at: 200 ℃～215 ℃, and extruding pelletization and get final product under 450 revs/min of conditions of screw speed.This formula is studied by GC with Headspace-MS, as Fig. 1, finds that odoring substance is carbonyl compound and alkanes substance.
Comparative example 2
Table 2 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 69 |
| POE | Mitsui | |
| 10% | ||
| Talcum powder | Heshan Chemical Group | 18% |
| Smell inhibitor | Self-control | 2% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, wherein, and the SiO in clay
2/ Al
2o
3mol ratio is 135.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.
Comparative example 3
Table 3 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 69 |
| POE | Mitsui | |
| 10% | ||
| Talcum powder | Heshan Chemical Group | 18% |
| Smell inhibitor | Self-control | 2% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is zeolite, and wherein, zeolite is hydrophilic zeolite, and aperture is 1.5 nanometers.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.
Comparative example 4
Table 4 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 69 |
| POE | Mitsui | |
| 10% | ||
| Talcum powder | Heshan Chemical Group | 18% |
| Smell inhibitor | Self-control | 2% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is zeolite, and its mesolite is the zeolite with bigger serface, and specific surface area is 150 ~ 350m
2/ gr, this zeolite is hydrophilic zeolite, aperture is less than or equal to 1 nanometer.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in example 1.
Comparative example 5
Table 5 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 69 |
| POE | Mitsui | |
| 10% | ||
| Talcum powder | Heshan Chemical Group | 19% |
| Smell inhibitor | Self-control | 1% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite compositions, and the weight percent that they account for smell inhibitor is: clay 50%, zeolite 50%.Wherein, the SiO in clay
2/ Al
2o
3mol ratio is 135, and zeolite is the zeolite with high surface area, and specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.
Embodiment 1
Table 6 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 69 |
| POE | Mitsui | |
| 10% | ||
| Talcum powder | Heshan Chemical Group | 19% |
| Smell inhibitor | Self-control | 1% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite compositions, and the weight percent that they account for smell inhibitor is: clay 30%, zeolite 70%.Wherein, the SiO in clay
2/ Al
2o
3mol ratio is 135, and zeolite is the zeolite with high surface area, and specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.
The properties of sample that comparative example 1 ~ 5 and embodiment 1 make is as follows:
Table 7 performance table
Table 7 is the impact of different odor inhibitor kind and proportioning smell.As can be seen from Table 7, select suitable smell inhibitor to play a multiplier role.Use separately a kind of mode in clay, zeolite cannot reach two kinds of composite effects, this may be owing to having complementary relationship between them, having synergistic effect simultaneously, and the suitable best effect of ratio competence exertion.Smell inhibitor is clay, zeolite compositions, and the weight percent that they account for smell inhibitor is: clay 30%, zeolite 70%.When smell inhibitor adds 1%, the material smell making is minimum, can see that some volatile organic matter peak value disappears from Fig. 2, and part volatile organic matter peak value weakens, and has further proved the effect of smell inhibitor.
From table 7, we can also find out, add after smell inhibitor, and the mechanical property of composition changes little.
Comparative example 6
Table 8 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 75% |
| POE | Mitsui | 7% |
| Talcum powder | Heshan Chemical Group | 17% |
| Antiaging agent | Vapour Bagong department | 1% |
Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.
Comparative example 7
Table 9 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 75% |
| POE | Mitsui | 7% |
| Talcum powder | Heshan Chemical Group | 16% |
| Smell inhibitor | Self-control | 1% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite compositions, and the weight percent that they account for smell inhibitor is: clay 30%, zeolite 70%.Wherein, the SiO in clay
2/ Al
2o
3mol ratio is 135, and zeolite is the hydrophilic zeolite with high surface area, and specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.
Comparative example 8
Table 10 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 75% |
| POE | Mitsui | 7% |
| Talcum powder | Heshan Chemical Group | 13% |
| Smell inhibitor | Self-control | 4% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite compositions, and the weight percent that they account for smell inhibitor is: clay 30%, zeolite 70%.Wherein, the SiO in clay
2/ Al
2o
3mol ratio is 135, and zeolite is the zeolite with high surface area, and specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.
Embodiment 2
Table 11 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 75% |
| POE | Mitsui | 7% |
| Talcum powder | Heshan Chemical Group | 13% |
| Smell inhibitor | Self-control | 4% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, and zeolite 50%, metal oxide 25%, wherein metal oxide is calcium oxide.Wherein, the SiO in clay
2/ Al
2o
3ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The performance of comparative example 6 ~ 8 and embodiment 2 is as shown in table 12.
From comparative example 6 ~ 8 and embodiment 2, find, after adding calcium oxide, smell can further reduce, optimum smell inhibitor can play a multiplier role, when smell addition is 4%, the weight percent of smell inhibitor is: clay 25%, zeolite 50%, metal oxide 25%, the material smell of preparation is minimum.Fig. 2 can further illustrate and add after suitable smell inhibitor simultaneously, and odoring substance peak disappears or weakens.It should be noted that the oxide compound in this example is not limited in calcium oxide.The present embodiment is for illustrating that our smell inhibitor used combination can reduce the smell of modified polypropene in various degree, only has suitable combination just can reach best low odor effect.That is to say, different formula systems, certain specific smell inhibitor combination might not reach best effect.
Table 12 performance table
Embodiment 3
Table 13 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Sinopec, Singapore's polyolefine | 75% |
| POE | Mitsui | 20% |
| Talcum powder | Heshan Chemical Group | 0% |
| Smell inhibitor | Self-control | 4% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, and zeolite 50%, metal oxide 25%, wherein metal oxide is calcium oxide.Wherein, the SiO in clay
2/ Al
2o
3mol ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The properties of sample making is as follows:
Table 14 performance table
From table 13 and table 14, see, add 4% suitable smell inhibitor, smell inhibitor is clay, zeolite, metal oxide composition, the weight percent that they account for smell inhibitor is: clay 25%, zeolite 50%, metal oxide 25%, wherein metal oxide is calcium oxide.Embodiment 2 and embodiment 3 material smells can reach 3 grades.The present embodiment only, for explanation additive smell inhibitor combination and proportioning, is not limited in 4% addition.
Embodiment 4
Table 15 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Singapore's polyolefine | 70% |
| POE | Mitsui | 15% |
| Talcum powder | Heshan Chemical Group | 13.5% |
| Smell inhibitor | Self-control | 0.5% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, and zeolite 50%, metal oxide 25%, wherein metal oxide is calcium oxide.Wherein, the SiO in clay
2/ Al
2o
3mol ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The properties of sample making is as follows:
Table 16 performance table
From table 15 and table 16, see, add 0.5% suitable smell inhibitor, smell inhibitor is clay, zeolite, metal oxide composition, the weight percent that they account for smell inhibitor is: clay 25%, zeolite 50%, metal oxide 25%, wherein metal oxide is calcium oxide.Material smell can reach 3 grades.
Embodiment 5
Table 17 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Singapore's polyolefine | 67% |
| POE | Mitsui | 15% |
| Talcum powder | Heshan Chemical Group | 16% |
| Smell inhibitor | Self-control | 1% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, and zeolite 50%, metal oxide 25%, wherein metal oxide is calcium oxide.Wherein, the SiO in clay
2/ Al
2o
3mol ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The properties of sample making is as follows:
Table 18 performance table
From table 17 and table 18, see, add 1% suitable smell inhibitor, smell inhibitor is clay, zeolite, metal oxide composition, the weight percent that they account for smell inhibitor is: clay 25%, zeolite 50%, metal oxide 25%, wherein metal oxide is calcium oxide.Material smell can reach 3 grades.
Embodiment 6
Table 19 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Singapore's polyolefine | 59% |
| POE | Mitsui | 7% |
| Talcum powder | Heshan Chemical Group | 30% |
| Smell inhibitor | Self-control | 3% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, and zeolite 50%, metal oxide 25%, wherein metal oxide is calcium oxide.Wherein, the SiO in clay
2/ Al
2o
3mol ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The properties of sample making is as follows:
Table 20 performance table
From table 19 and table 20, see, add 3% smell inhibitor, smell inhibitor is clay, zeolite, calcium oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, zeolite 50%, calcium oxide 25%.Material smell can reach 3 grades.
Embodiment 7
Table 21 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Singapore's polyolefine | 59% |
| POE | Mitsui | 7% |
| Talcum powder | Heshan Chemical Group | 30% |
| Smell inhibitor | Self-control | 3% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, and zeolite 50%, metal oxide 25%, wherein metal oxide is zinc oxide.Wherein, the SiO in clay
2/ Al
2o
3ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The properties of sample making is as follows:
Table 22 performance table
From table 21 and table 22, see, add 3% smell inhibitor, smell inhibitor is clay, zeolite, zinc oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, zeolite 50%, zinc oxide 25%.Material smell can reach 3 grades.
The present embodiment is only for illustrating that interpolation clay, zeolite, zinc oxide composition his-and-hers watches 21 formula system smells can reduce, and are not limited in this formula.
Embodiment 8
Table 23 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Singapore's polyolefine | 65 |
| POE | Mitsui | |
| 10% | ||
| Talcum powder | Heshan Chemical Group | 21% |
| Smell inhibitor | Self-control | 3% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, and zeolite 65%, metal oxide 10%, wherein metal oxide is zinc oxide.Wherein, the SiO in clay
2/ Al
2o
3ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The properties of sample making is as follows:
Table 24 performance table
From table 23 and table 24, see, add 3% smell inhibitor, smell inhibitor is clay, zeolite, zinc oxide composition, and the weight percent that they account for smell inhibitor is: clay 25%, zeolite 65%, zinc oxide 10%.Material smell can reach 3 grades.
The present embodiment is only for illustrating that interpolation clay, zeolite, zinc oxide composition his-and-hers watches 23 formula system smells can reduce, and are not limited in this formula.
Embodiment 9
Table 25 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Singapore's polyolefine | 75% |
| POE | Mitsui | 20% |
| Talcum powder | Heshan Chemical Group | 2% |
| Smell inhibitor | Self-control | 2% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 5%, and zeolite 55%, metal oxide 40%, wherein metal oxide is zinc oxide.Wherein, the SiO in clay
2/ Al
2o
3ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The properties of sample making is as follows:
Table 26 performance table
From table 25 and table 26, see, add 2% smell inhibitor, smell inhibitor is clay, zeolite, zinc oxide composition, and the weight percent that they account for smell inhibitor is: clay 5%, zeolite 55%, zinc oxide 40%.Material smell can reach 3 grades.
The present embodiment is only for illustrating that interpolation clay, zeolite, zinc oxide composition his-and-hers watches 25 formula system smells can reduce, and are not limited in this formula.
Table 27 formulation content
| Component | Manufacturer | Weight percentage |
| PP | Singapore's polyolefine | 50% |
| POE | Mitsui | 15% |
| Talcum powder | Heshan Chemical Group | 30% |
| Smell inhibitor | Self-control | 4% |
| Antiaging agent | Vapour Bagong department | 1% |
In this programme, smell inhibitor is clay, zeolite, metal oxide composition, and the weight percent that they account for smell inhibitor is: clay 20%, and zeolite 50%, metal oxide 30%, wherein metal oxide is zinc oxide.Wherein, the SiO in clay
2/ Al
2o
3ratio is 135, and zeolite is the zeolite with high surface area, and its specific surface area is 150 ~ 350m
2/ gr, aperture is less than or equal to 1 nanometer, and this zeolite is hydrophilic zeolite.Above-mentioned starting material are first put into the super mixer that rotating speed is about 1000rpm and mix 3 minutes, extruding and pelletizing process is shown in comparative example 1.The properties of sample making is as follows:
Table 28 performance table
From table 27 and table 28, see, add 4% smell inhibitor, smell inhibitor is clay, zeolite, zinc oxide composition, and the weight percent that they account for smell inhibitor is: clay 20%, zeolite 50%, zinc oxide 30%.Material smell can reach 3 grades.
The present embodiment is only for illustrating that interpolation clay, zeolite, zinc oxide composition his-and-hers watches 27 formula system smells can reduce, and are not limited in this formula.
Claims (5)
1. a low-odor polypropylene ene compositions, is characterized in that the component of being calculated by following percentage ratio by weight forms:
Polypropylene 50 ~ 78%;
Toughner 7 ~ 20%;
Smell inhibitor 0.5 ~ 4%;
Mineral filler 0 ~ 30%;
The content of each component in described smell inhibitor, percentage ratio calculates by weight, as follows:
Clay 20% ~ 35%;
Zeolite 50% ~ 70%;
Metal oxide 1% ~ 30%;
Described metal oxide is one or more the mixture in magnesium oxide, calcium oxide, zinc oxide;
Described zeolite is hydrophilic zeolite, and described hydrophilic zeolite is the hydrophilic zeolite with high surface area, and specific surface area is 150 ~ 350m
2/ g, aperture is 0.3 nanometer ~ 1 nanometer; Described clay is hydrophobic type clay, SiO in described hydrophobic type clay
2/ Al
2o
3mol ratio be 35 ~ 500.
2. low-odor polypropylene ene compositions as claimed in claim 1, is characterized in that the content of each component in described smell inhibitor, and percentage ratio calculates by weight, as follows:
Clay 20% ~ 30%;
Zeolite 50% ~ 65%;
Metal oxide 5% ~ 25%.
3. low-odor polypropylene ene compositions as described in any one claim in claim 1 or 2, is characterized in that also comprising the antiaging agent of 0.2 ~ 1 % by weight; Described antiaging agent is one or more the mixture in suffocated amine antioxidant, Hinered phenols antioxidant, phosphite.
4. a preparation method for low-odor polypropylene ene compositions described in any one claim in claim 1 or 2, is characterized in that comprising the steps:
(1), by the polypropylene taking, toughner, smell inhibitor premix, then mineral filler is added to rear mixing, the starting material that obtain mixing;
(2) starting material that mix are placed in to twin screw extruder, temperature is controlled at 200 ℃～215 ℃, melt extrudes granulating and drying under the condition that screw speed is 450 revs/min.
5. the preparation method of low-odor polypropylene ene compositions as claimed in claim 4, is characterized in that smell inhibitor described in step (1) is for the smell inhibitor after 500 ~ 600 ℃ of activation of retort furnace; Described doing time is in advance 1 ~ 3 minute, and described mixing time is 3 ~ 4 minutes.
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| CN102532703A (en) * | 2011-12-16 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Low-odor high-luster modified polypropylene material and preparation method thereof |
| CN103374180A (en) * | 2012-04-26 | 2013-10-30 | 滁州格美特科技有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN103724799B (en) * | 2013-12-09 | 2016-03-09 | 天津金发新材料有限公司 | A kind of low smell, low diffusion polypropylene composition and preparation method thereof |
| CN104693605A (en) * | 2015-03-27 | 2015-06-10 | 博富科技股份有限公司 | Polypropylene composite material for automobile interior parts and preparing method thereof |
| CN104910516A (en) * | 2015-06-15 | 2015-09-16 | 常州塑金高分子科技有限公司 | Special antimicrobial mould-proof low-odor regenerative polypropylene modified material for automobile instrument desk and preparation method thereof |
| CN105001525B (en) * | 2015-07-29 | 2017-12-05 | 博富科技股份有限公司 | Low VOC, low smell environment-protection flame-proof fiberglass enhancing PP composites and preparation method thereof |
| CN110527182A (en) * | 2018-05-23 | 2019-12-03 | 天津泰煜辉新材料科技有限公司 | A kind of low-odor polypropylene ene compositions and preparation method thereof |
| CN109370042A (en) * | 2018-08-31 | 2019-02-22 | 王雪峰 | A kind of preparation method of anti-oxidant zeolite reinforced polypropylene material |
| 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 |
| CN113248829A (en) * | 2021-05-25 | 2021-08-13 | 金发科技股份有限公司 | Low-odor polypropylene composition and preparation method and application thereof |
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Effective date of registration: 20190522 Address after: 610200 Industrial Concentration Zone of Southwest Airport Economic Development Zone, Shuangliu District, Chengdu City, Sichuan Province Co-patentee after: Kingfa Technology Co., Ltd. Patentee after: Chengdu golden hair science and technology new material Co Ltd Co-patentee after: Shanghai Kingfa Science and Technology Development Co., Ltd. Address before: 510520 Golden Hair Technology Co., Ltd. of Gaotang Industrial Zone, Kemu Long, Tianhe District, Guangzhou City, Guangdong Province Co-patentee before: Shanghai Blonde Technology Development Co., Ltd. Patentee before: Kingfa Technology Co., Ltd. Co-patentee before: SICHUAN KINGFA TECHNOLOGY DEVELOPMENT CO., LTD. |
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