CN116063774A - Low-odor scratch-resistant polypropylene material and preparation method and application thereof - Google Patents
Low-odor scratch-resistant polypropylene material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a low-odor scratch-resistant polypropylene material in the field of modified plastics, and a preparation method and application thereof. The low-odor scratch-resistant polypropylene material comprises the following blended components: polypropylene resin, filler, surface crack remedy and shielding agent; the low-odor scratch-resistant polypropylene material comprises the following components in parts by weight based on 100 parts by weight of the total weight of the low-odor scratch-resistant polypropylene material: 10-30 parts of filler, 5-30 parts of surface crack remedy, 0-8 parts of masking agent and 32-85 parts of polypropylene resin; the low-odor scratch-resistant polypropylene material has low odor, scratch resistance, excellent processability and mechanical properties, and excellent thermo-oxidative aging resistance and photo-aging resistance. Can be applied to the fields of automotive interiors, household appliance shells and the like.
Description
Technical Field
The invention relates to the field of modified plastics, in particular to a low-odor scratch-resistant polypropylene material, and a preparation method and application thereof.
Background
The odor source of the polypropylene material is mainly that the polypropylene is aged and degraded due to the influence of the polypropylene itself or the surrounding environment in the processing and using process, and compounds such as aldehyde, ketone, ester and the like are generated, and the compounds volatilize and combine into unpleasant odor. How to reduce the odor is a hot spot in polypropylene processing applications in recent years. The current methods for reducing and removing the unpleasant odor of polypropylene materials include:
1. and (3) adding porous filler for adsorption.
2. Sample processing
(1) And the vacuum degree in the processing and blending process is increased.
(2) Samples were dried under vacuum for a long period of time prior to injection.
(3) And (5) preserving the sample in an air-isolated manner.
However, the method cannot fundamentally solve the problem that the polypropylene material generates odor during processing and use, which causes discomfort to people and damages to human bodies caused by aldehyde, ketone, ester and other compounds.
Nakatani H(H.Nakatani,H.Shibata,K.Miyazaki,et al.Studies on heterogeneous degradation of polypropylene/talc composite:Effect of iron impurity on the degradation behavior[J]Fe was studied at the same point as those of (Journal of Applied Polymer Science,2010,115 (1): 167-173.) 2 O 3 The aging mechanism of the PP/Talc composite material is accelerated. Research shows that Fe 2 O 3 Can decompose peroxide free radical, alkyl free radical and hydroperoxide generated by PP oxidative degradation, and convert the generated peroxide free radical and alkyl free radical into non-free radical productSome of the unconverted free radical energy migrates to the Fe 2 O 3 The particles induce degradation in a remote location. Therefore, at the initial stage of oxidation, fe 2 O 3 The photooxidation of the PP matrix near the particles is not obvious, but far from Fe 2 O 3 The PP matrix with particles of about 6 μm detected oxidation products. And as aging progresses, degradation will eventually spread throughout the system.
The typical structure of polypropylene products is a sheath-core structure, and the sheath layer has the advantages of high cooling speed, low crystallinity and high porosity, and is beneficial to oxygen diffusion and oxidation reaction. Li Jifang et al (Li Jifang, yang Rui, in the study of photo-oxidative degradation [ J ] spectroscopy and spectroscopic analysis of polypropylene nanocomposites by microscopic infrared spectroscopy, 2008,28 (8): 1758-1762.) found that the crystallinity and density of the surface skin layers were lower, and that it was beneficial to oxygen diffusion and oxidation reactions. Below the surface layer, the crystalline structure is relatively perfect, which is detrimental to oxygen diffusion and oxidation reactions. Photooxidation of PP is an oxygen diffusion controlled reaction, the progress of oxidation being controlled by the diffusion of oxygen. According to the study of White et al (C.S.Kwok, L.Tong, J.R.White.Generation oflarge residual stresses in injection moldings [ J ]. Polymer Engineering & Science,1996,36 (5): 651-657.), oxygen diffuses relatively freely in the amorphous region due to the lower density of the amorphous region, and hardly diffuses in the crystalline region, so that the place where oxidation occurs first is the amorphous region.
On the other hand, in the test method, it should be noted that the odor is a subjective judgment, and the amount of VOC cannot be simply used as a judgment criterion for odor. A simpler experiment was to add 20g of test sample pellets with VOC above 200 in a 1L volumetric flask, and heat the flask in an oven at 80℃for 2hr after sealing the flask. After the time is up, the volumetric flask is quickly taken out and the bottle stopper is opened to smell. Most people feel pleasant and even have a light fragrance. There are also few people who consider the smell as annoying. Therefore, subjective judgment is determination judgment for determining odor, and odor grade cannot be determined by the content and type of organic volatile matters alone.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a low-odor scratch-resistant polypropylene material. In particular to a low-odor scratch-resistant polypropylene material, a preparation method and application thereof.
The invention takes the mechanism of odor generation as the research direction for inhibiting the odor generation. The inventor of the present application found in practice that polypropylene degrades during use, generating an unpleasant smell, mainly affected by the combination of the following aspects: the catalyst, filler, polypropylene product surface pore, stabilizing system and colorant remained in polypropylene itself. Therefore, the method has the advantages of inhibiting the surface cracking of the product, increasing the crystallinity of the skin layer, shielding ultraviolet rays and reducing the contact area with oxygen, and has the scratch resistance. The low-odor scratch-resistant polypropylene material has low odor, scratch resistance, excellent processability and mechanical properties, and excellent thermo-oxidative aging resistance and photo-aging resistance. Can be applied to automotive interiors, household appliance shells and the like.
One of the purposes of the invention is to provide a low-odor scratch-resistant polypropylene material which can comprise the following blended components: polypropylene resin, filler, surface crack remedy and shielding agent;
calculated by taking the weight of the low-odor scratch-resistant polypropylene material as 100 parts by weight,
the dosages of the components are as follows:
10 to 30 parts by weight, preferably 10 to 25 parts by weight, more preferably 12 to 20 parts by weight,
5 to 30 parts by weight, preferably 5 to 25 parts by weight, more preferably 5 to 22 parts by weight,
0 to 8 parts by weight, preferably 0 to 6 parts by weight, more preferably 0 to 6 parts by weight of a shielding agent,
32 to 85 parts by weight, preferably 44 to 84 parts by weight, more preferably 52 to 80 parts by weight of polypropylene resin.
In some of the embodiments of the present invention,
the filler can be a composite filler of talcum powder and barium sulfate, and is formed by mixing the talcum powder and the barium sulfate, and the weight ratio of the talcum powder to the barium sulfate can be 3:1-1:1; the talcum powder can be selected from medicinal talcum powder; the filler may be used in a specific amount of 10 to 30 parts by weight (for example, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 parts by weight or any value or range of values between any two of the above values, preferably 10 to 25 parts by weight, more preferably 12 to 20 parts by weight).
Preferably, the talc may have a particle size of 1250 mesh to 2500 mesh; and/or the number of the groups of groups,
the particle size of the barium sulfate may be 5000 mesh. The particle size of the selected filler is smaller, so that the surface defects are reduced to a certain extent.
In some of the embodiments of the present invention,
the crack-making agent can be at least one of metallocene linear low-density polyethylene (mLLDPE), low-density metallocene polypropylene and medium-density metallocene polypropylene; preferably, the melt index of the mLLDPE is 3-10 g/10min (the test condition is that the temperature is 190 ℃ C., and the load is 2.16 Kg). The alloy material is prepared from the metallocene polyethylene and the polypropylene by utilizing the characteristic of relatively low crystallinity and excellent ageing resistance. On the one hand, the crystal area content of the polypropylene surface layer is improved, meanwhile, the cracks of the surface layer are reduced, and the oxygen diffusion is reduced. On the other hand, "dilute" the tertiary alkyl group. It is particularly pointed out that the crystallinity of mLLDPE is only low compared to ordinary PE, that the crystallization rate of mLLDPE is much faster than that of polypropylene, and that the crystallinity is high. The mLLDPE flaky alpha crystals are firstly formed, so that the surface of the product is flat, the hardness is improved, the formation of large spherulites of the cortex polypropylene is limited, and the amorphous area is reduced. Can effectively limit the diffusion of oxygen and improve the scratch resistance. The specific amount of the surface crack-making agent may be 5 to 30 parts by weight (for example, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 parts by weight or any value or range of values between any two of the above values, preferably 5 to 25 parts by weight, more preferably 5 to 22 parts by weight).
In some of the embodiments of the present invention,
the shielding agent can be rutile TiO 2 . Penetration of ultraviolet light can be suppressed, limiting oxidation of the material to areas of smaller surface. It is found by research that: 1) Rutile TiO 2 The protection effect of the dye on molecular degradation is stronger than that of the light stabilization system; 2) For adding TiO 2 The antioxidation effect of the sample after the coloring agent is added with the photostable system can be improved little; 3) The degree of crosslinking and chain scission of the molecular chains in the sample is related to whether an auxiliary agent is added or not and the depth of the sample, wherein the molecular chains have higher degree of chain scission when the oxidative degradation rate is high, and the molecules tend to crosslink when the degradation rate is low. The addition of titanium dioxide seriously affects the mechanical property of the product, so that the product has excellent performance in improving the light stability of the product, but can only be used under the condition of special requirements. The masking agent may be used in an amount of 0 to 9 parts by weight (for example, 0,1, 2, 3, 4, 5, 6, 7, 8, 9 parts by weight or any value or range of values between any two of the above values, preferably 0 to 6 parts by weight).
Addition of rutile TiO 2 The coloring agent can inhibit the penetration of ultraviolet light and limit the oxidation of the material to a region with a smaller surface. The degree of crosslinking and chain scission of the molecular chains in the sample is related to whether an auxiliary agent is added or not and the depth of the sample, wherein the molecular chains have higher degree of chain scission when the oxidative degradation rate is high, and the molecules tend to crosslink when the degradation rate is low.
In some of the embodiments of the present invention,
the selection standard of the polypropylene resin is that no chain-breaking agent is added in the preparation process, and the ash content is as low as possible. The melt index of the polypropylene resin is 5-30 g/10min (the test condition is that the temperature is 230 ℃ and the load is 2.16 Kg); preferably, the polypropylene resin has an ash content of 180ppm or less. Ash in polypropylene raw material particles is mainly catalyst residue, contains atoms of titanium and aluminum, and can accelerate degradation of products to generate odor molecules. The polypropylene resin may be used in a specific amount of 32 to 85 parts by weight (for example, 32, 33, 34, 35, 38, 40, 42, 44, 46, 48, 50, 52, 55, 57, 60, 62, 65, 67, 70, 72, 75, 77, 80, 82, 84 parts by weight or any value or range of values between any two of the above values, preferably 44 to 84 parts by weight, more preferably 52 to 80 parts by weight).
In some of the embodiments of the present invention,
the low-odor scratch-resistant polypropylene material can also comprise color master batches; the color master batch is prepared by mixing colors by taking rutile titanium dioxide as a base color; the masterbatch may be used in an amount of 1.5 to 2 parts by weight (e.g., 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 parts by weight or any value or range of values between any two of the foregoing values) based on 100 parts by weight of the total weight of the low odor scratch resistant polypropylene material, e.g., 2 parts by weight, i.e., 50:1 masterbatch. The colour is recommended to be light, for example grey or beige, both in rutile titanium dioxide (rutile TiO 2 ) The color is adjusted as the ground color. A certain amount of masking agent is introduced to a certain extent, so that a stabilizing effect is achieved.
In some of the embodiments of the present invention,
the low-odor scratch-resistant polypropylene material can also contain a lubricant;
the lubricant may be used in an amount of 0.1 to 1.0 parts by weight (e.g., may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 parts by weight, or any value therebetween or a range of values therebetween) based on 100 parts by weight of the total weight of the low odor scratch resistant polypropylene material; the lubricant may be a methyl silicone oil, and the viscosity of the methyl silicone oil may be 2000S-8000S. In our research, it is found that methyl silicone oil can refine the crystallization of polypropylene in the skin layer of polypropylene product to prevent the formation of large spherulites, thus improving the flatness and compactness of the product surface and reducing the content of amorphous regions. And the oxygen is isolated by the infiltration of cracks caused by the migration of the methyl silicone oil to the surface. The methyl silicone oil has high migration speed and can effectively improve the scratch resistance.
In some of the embodiments of the present invention,
the low-odor scratch-resistant polypropylene material can also comprise a light stabilizer;
the light stabilizer may be used in an amount of 0.1 to 0.5 parts by weight (e.g., may be 0.1, 0.2, 0.3, 0.4, 0.5 parts by weight or any value therebetween or a range of values therebetween) based on 100 parts by weight of the total weight of the low odor scratch resistant polypropylene material; and/or the number of the groups of groups,
the light stabilizer may be a general light stabilizer or a compound light stabilizer in the art, preferably a compound light stabilizer, for example, light stabilizer T81.
In some of the embodiments of the present invention,
the low-odor scratch-resistant polypropylene material can also contain an antioxidant;
the antioxidant may be used in an amount of 0.1 to 0.5 parts by weight (e.g., 0.1, 0.2, 0.3, 0.4, 0.5 parts by weight, or any value therebetween or a range of values therebetween) based on 100 parts by weight of the total weight of the low odor scratch resistant polypropylene material;
the antioxidant can be at least one selected from hindered phenols and hindered amine antioxidants; for example, the compounding of the synergistic stabilizer B225 and Irganox PS802, preferably, the weight ratio of the stabilizer B225 to the Irganox PS802 may be (1.5-2.5): 1. can greatly improve the oxidation induction period and the stability of the product. In order to achieve better anti-aging effect, the antioxidant and the light stabilizer adopted by the method are all composite stabilizers with synergistic effect.
More specifically, the low odor scratch resistant polypropylene material described herein comprises the following components blended: polypropylene resin, filler, surface crack remedy agent, lubricant, light stabilizer, antioxidant, masking agent and color master batch. The low-odor scratch-resistant polypropylene material comprises the following components in parts by weight based on 100 parts by weight of the total weight of the low-odor scratch-resistant polypropylene material: 10 to 30 parts by weight of filler (preferably 10 to 25 parts by weight, more preferably 12 to 20 parts by weight), 5 to 30 parts by weight of surface crack remedy (preferably 5 to 25 parts by weight, more preferably 5 to 22 parts by weight), 0.1 to 1.0 part by weight of lubricant, 0.1 to 0.5 part by weight of light stabilizer, 0.1 to 0.5 part by weight of antioxidant, 0 to 8 parts by weight of masking agent (preferably 0 to 6 parts by weight, more preferably 1 to 6 parts by weight), 1.5 to 2 parts by weight of masterbatch, and the balance polypropylene resin.
The inventor of the present application found in a large number of practices that the degradation of polypropylene resin during use and the generation of unpleasant odor are mainly affected by the following aspects:
1. the catalyst remaining in the polypropylene itself. The remaining catalyst and light act together to accelerate the formation of alcohols, ketones, acids, and the like. The amount of catalyst remaining is determined by the catalyst activity, and the higher the catalyst activity, the less the catalyst remains, and vice versa. In polypropylene, mainly in the form of ash, the elemental constituents are mainly titanium and aluminum.
2. And (3) filling. Mineral fillers such as mica commonly used for polypropylene, and these natural minerals generally contain Fe 2 O 3 While Fe 2 O 3 Accelerates the aging degradation speed of polypropylene, thus minimizing or eliminating Fe when selecting filler or reinforcing fiber for preparing low-odor polypropylene material 2 O 3 。
3. Surface pores of polypropylene products. From the mechanism of degradation by aging of polypropylene, it can be analyzed that oxygen is a critical factor, both for heat aging and for photoaging. The larger the contact area with oxygen, the faster the aging degradation speed and the larger the odor.
4. A stabilizing system. The stabilizing system has the function of capturing free radicals and inhibiting the generation of odor components. Comparing the pure PP sample with the added stabilizer system, it was found that the internal oxidation level of the PP sample with the added stabilizer was much higher than that of the pure PP sample. The photooxidation of the PP is controlled by the diffusion of oxygen, so that the surface of a pure PP sample is aged more severely, the oxygen is consumed more quickly on the surface, and the oxygen is prevented from diffusing deeper, so that no obvious aging phenomenon exists inside the PP sample.
5. A colorant. The generation of odor of polypropylene by the colorant is mainly reflected in the inhibition of odor caused by photo-aging, mainly in the shielding of ultraviolet rays. Carbon black dyes are also effective UV stabilizers, the light stabilization effect being inversely proportional to the carbon black particle size, the greater the particle concentration, the more uniform the dispersion the better the light stabilization effect.
Based on the above aspects, the inventor of the application proposes the low-odor scratch-resistant polypropylene material compounded by specific components, which has low odor, scratch resistance, excellent processability and mechanical properties, and takes the mechanism of odor generation as the research direction for inhibiting the odor generation.
The second purpose of the invention is to provide a preparation method of the low-odor scratch-resistant polypropylene material, which comprises the following steps:
the low-odor scratch-resistant polypropylene material is prepared by melt blending components comprising the polypropylene resin, a surface crack compensation agent and a masking agent according to the dosage;
preferably, the blending vacuum degree is kept higher than-0.08 MPa during melt blending;
preferably, the blending temperature may be 190 to 230 ℃.
More specifically, the preparation method of the low-odor scratch-resistant polypropylene material disclosed by the invention can comprise the following steps of: the low-odor scratch-resistant polypropylene material is prepared by uniformly stirring components comprising the polypropylene resin, a surface crack compensation agent, a lubricant (if any), an antioxidant (if any), a light stabilizer (if any), a masking agent (if any) and a color master batch (if any) in a mixing device according to the dosage, carrying out melt blending extrusion by a blending device, keeping the vacuum degree of a vacuum system of the device higher than-0.08 MPa, and granulating.
In the processing process of the low-odor scratch-resistant polypropylene material, the material melt blending temperature is the blending temperature used in the common polypropylene processing, namely 190-230 ℃.
The mixing apparatus for mixing materials in the preparation method can be various mixing apparatuses used in the prior art, such as a stirrer, a kneader, etc. The melt blending equipment used in the method of the invention is general blending equipment in the rubber and plastic processing industry, and can be a double screw extruder, a BUSS mixing unit and the like.
The third object of the invention is to provide the application of the low-odor scratch-resistant polypropylene material of one of the objects of the invention or the low-odor scratch-resistant polypropylene material prepared by the preparation method of the second object of the invention.
The low-odor scratch-resistant polypropylene material has low odor, scratch resistance, excellent processability and mechanical properties, and excellent thermo-oxidative aging resistance and photo-aging resistance. Can be applied to automotive interiors, household appliance shells and the like.
Drawings
FIG. 1 is an electron micrograph of the surface crystalline state of the low odor scratch resistant polypropylene material of example 3;
FIG. 2 is an electron micrograph of the surface crystalline state of the low odor scratch resistant polypropylene material of comparative example 2;
wherein the magnification of fig. 1 is the same as that of fig. 2.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Raw material source
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Examples 1 to 5 and comparative examples 1 to 2:
adding PP resin (HHP 4), filler (talcum powder, gui Lingui, 1250 mesh of talcum powder for general purpose, barium sulfate, 5000 mesh of Hebei Jiji chemical Co., ltd., according to the proportion of 2:1), crack remedy (mLLDPE, exxon Mobil, 4518 PA), lubricant (methyl silicone oil, beijing chemical two factories, 3000 s), antioxidant (BasfuChinese Co., ltd., hindered phenol antioxidant irganoxB225, irganox PS 802), light stabilizer (Beijing Tian Gao auxiliary agent Co., T81), shielding agent (stone original chemical, R930), color master batch (Beijing Kernen color master batch Co., miy, dark gray) into a high-speed mixer, stirring uniformly, granulating the mixture by a double-screw mixer, wherein the mixing temperature is 190-230 ℃, and the vacuum degree of a vacuum system of equipment is kept to be higher than-0.08 MPa; thus obtaining the low-odor scratch-resistant polypropylene material. The specific formulation is shown in Table 2.
The low odor scratch resistant polypropylene material prepared above was dried in a cyclone drying oven at 90℃for 4 hours and tested by injection molding with an injection machine (Ningbo sea Tian Plastic machine group Co., ltd., MA 900), and the results of the spline test are shown in Table 2.
The test includes:
1. scratch properties Δe: public standard PV3952 with a load of 10N
2. Odor rating: public standard PV3900
Note that: odor rating: 20g of test specimen pellets were added to a 1L volumetric flask, and the flask was sealed and heated in an oven at 80℃for 2hr. After the time is up, the volumetric flask is quickly taken out and the bottle stopper is opened to smell. Grade 1, imperceptible; level 2, perceivable, undisturbed; the level 3 can be obviously felt without disturbing the human body; 4, disturbing the human body; grade 5, strong dislike; grade 6, intolerable.
The above manner of evaluating the smell can only evaluate the smell generated by short-term thermo-oxidative aging. However, during the actual use of the product, light, stress, fungi, etc. may have a far too high thermo-oxidative effect on the smell generated by the product. And this process is continuous over a long period of time, which is a concern for low odor products. This is also of interest for the present application.
The low odor scratch resistant polypropylene described herein is characterized by long-term performance, which is also responsible for the natural aging of the article more closely to the conditions of actual application. Table 1 is the natural aging conditions of the present application.
The specific test method comprises the following steps: 20g of the test specimen pellets were put into a 1L volumetric flask, and after the flask was sealed, aging was performed in a natural aging oven (aging conditions are shown in Table 1, aging time is 1 year). After the test time is over, the volumetric flask is quickly taken out and the bottle stopper is opened to smell. Grade 1, imperceptible; level 2, perceivable, undisturbed; the level 3 can be obviously felt without disturbing the human body; 4, disturbing the human body; grade 5, strong dislike; grade 6, intolerable.
TABLE 1 annual dose (TNR) and temperature statistics for Hainan Jones natural aging Chamber
Table 2 ratio and test Performance data of examples 1 to 5 and comparative examples 1 to 2
1. As can be seen from examples 3 and 4, the color has a great influence on scratch resistance of scratch-resistant polypropylene, and the light color should be selected as much as possible.
2. Example 5 uses rutile titanium dioxide screening agent, which can reflect ultraviolet, and is suitable for outdoor strong light exposure condition.
3. The filler added in comparative example 1 was 1250 mesh talc from DalianFuji mineral company, and the test result was grade 4, and the odor was disturbing. Therefore, the existence of metal ions such as iron ions in the filler can rapidly catalyze the generation of free radicals in polypropylene, and further aldehyde, ketone, ester and other odor compounds are generated.
4. As can be seen from a comparison of the data in Table 2 of example 3 and comparative example 2, methyl silicone oil is a highly effective lubricant that effectively improves the scratch resistance of the article.
3. As can be seen from a comparison of fig. 1 and 2, fig. 1 is the surface crystalline state of example 3, and fig. 2 is the surface crystalline state of comparative example 2. The addition of the methyl silicone oil can break down the surface crystallization, thereby reducing the proportion of the amorphous region and making the diffusion of oxygen difficult.
From the above, the low-odor scratch-resistant polypropylene material of the invention has low odor, scratch resistance, excellent processability and mechanical properties, and excellent thermo-oxidative aging resistance and photo-aging resistance. Can be applied to automotive interiors, household appliance shells and the like.
Claims (11)
1. A low odor scratch resistant polypropylene material comprising the following components blended: polypropylene resin, filler, surface crack remedy and shielding agent;
calculated by taking the total weight of the low-odor scratch-resistant polypropylene material as 100 parts by weight,
the dosages of the components are as follows:
2. the low odor scratch resistant polypropylene material of claim 1, wherein:
the filler is a mixture of talcum powder and barium sulfate, wherein the weight ratio of the talcum powder to the barium sulfate is 3:1-1:1;
preferably, the method comprises the steps of,
the particle size of the talcum powder is 1250-2500 meshes; and/or the number of the groups of groups,
the particle size of the barium sulfate is 5000 meshes.
3. The low odor scratch resistant polypropylene material of claim 1, wherein:
the surface crack remedy agent is at least one of metallocene linear low-density polyethylene, low-density metallocene polypropylene and medium-density metallocene polypropylene; preferably a metallocene linear low density polyethylene, more preferably the metallocene linear low density polyethylene has a melt index of 3 to 10g/10min.
4. The low odor scratch resistant polypropylene material of claim 1, wherein:
the shielding agent is rutile type TiO 2 。
5. The low odor scratch resistant polypropylene material of claim 1, wherein:
the melt index of the polypropylene resin is 5-30 g/10min;
preferably, the polypropylene resin has an ash content of 180ppm or less.
6. The low odor scratch resistant polypropylene material according to claim 1, characterized by comprising color master batch; preferably, the low odor scratch resistant polypropylene material is used in an amount of 100 parts by weight based on the total weight of the low odor scratch resistant polypropylene material,
the dosage of the color master batch is 1.5 to 2 weight parts;
preferably, the base pigment of the color master batch is rutile titanium dioxide.
7. The low odor scratch resistant polypropylene material according to claim 1, characterized in comprising a lubricant;
the amount of the lubricant is 0.1 to 1.0 weight parts based on 100 weight parts of the low-odor scratch-resistant polypropylene material;
preferably, the lubricant is methyl silicone oil, and the viscosity of the methyl silicone oil is 2000S-8000S.
8. The low odor scratch resistant polypropylene material according to claim 1, characterized in comprising a light stabilizer;
the light stabilizer is used in an amount of 0.1 to 0.5 part by weight based on 100 parts by weight of the low-odor scratch-resistant polypropylene material.
9. The low odor scratch resistant polypropylene material according to claim 1, characterized in comprising an antioxidant;
the dosage of the antioxidant is 0.1 to 0.5 part by weight based on 100 parts by weight of the low-odor scratch-resistant polypropylene material;
preferably, the antioxidant is selected from the group consisting of a mixture of stabilizer B225 and Irganox PS 802.
10. The method for producing a low-odor scratch-resistant polypropylene material according to any one of claims 1 to 9, comprising the steps of:
the components comprising the polypropylene resin, the surface crack remedy agent and the masking agent are melt blended according to the dosage to prepare the low-odor scratch-resistant polypropylene material;
preferably, the blending vacuum degree is kept higher than-0.08 MPa during melt blending;
preferably, the blending temperature is 190-230 ℃.
11. Use of a low-odor scratch-resistant polypropylene material according to any one of claims 1 to 9 or a low-odor scratch-resistant polypropylene material produced according to the production method of claim 10, preferably in automotive interiors, household appliance housings.
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| CN102924773A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Master batch for scratch-resistant polypropylene and preparation method thereof |
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| CN109021380A (en) * | 2017-06-09 | 2018-12-18 | 武汉金发科技有限公司 | It is a kind of with low smell, damage resistant, the PP composite material of low gloss performance and preparation method thereof |
| CN112708211A (en) * | 2021-01-12 | 2021-04-27 | 南京宝利通新材料科技有限公司 | High-fluidity, low-odor and scratch-resistant polypropylene material special for automotive interior and preparation method thereof |
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| CN102924773A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Master batch for scratch-resistant polypropylene and preparation method thereof |
| CN106317743A (en) * | 2016-09-19 | 2017-01-11 | 南京德尔隆工程塑料有限公司 | High-mobility low-odor scratch-resistant automobile trim polypropylene material and preparation method thereof |
| CN109021380A (en) * | 2017-06-09 | 2018-12-18 | 武汉金发科技有限公司 | It is a kind of with low smell, damage resistant, the PP composite material of low gloss performance and preparation method thereof |
| CN112708211A (en) * | 2021-01-12 | 2021-04-27 | 南京宝利通新材料科技有限公司 | High-fluidity, low-odor and scratch-resistant polypropylene material special for automotive interior and preparation method thereof |
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