CN113698703A - Non-filling stress whitening-resistant polypropylene composition and preparation method and application thereof - Google Patents
Non-filling stress whitening-resistant polypropylene composition and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a filling-free stress whitening resistant polypropylene composition and a preparation method and application thereof. The non-filling stress whitening resistant polypropylene composition comprises the following components in parts by weight: 100 parts of polypropylene, 0.25-2.5 parts of peroxide adsorption master batch, 0.7-6 parts of activated titanium dioxide, 0.1-1 part of antioxidant, 0.05-0.5 part of light stabilizer, 0.05-0.5 part of nucleating agent and 0.1-0.5 part of lubricant; the peroxide adsorption master batch is a porous molecular sieve adsorbed with a peroxide initiator; the activated titanium dioxide is titanium dioxide with the surface treated by a silane coupling agent. The non-filling stress whitening-resistant polypropylene composition disclosed by the invention takes polypropylene as matrix resin, and the polypropylene is continuously subjected to slight micro-crosslinking through the synergistic effect of components such as a silane coupling agent, titanium dioxide, peroxide adsorption master batches, an antioxidant, a lubricant and the like, so that the stress whitening resistance of the material is greatly improved.
Description
Technical Field
The invention relates to the technical field of modified polypropylene, in particular to a filling-free stress whitening resistant polypropylene composition and a preparation method and application thereof.
Background
Stress whitening is a phenomenon in which plastic materials, under stress, produce a large number of areas of microcrack aggregation, which appear white due to a decrease in the refractive index of the areas.
Polypropylene (PP) has been widely used in automotive interior and exterior materials because of its low cost, easy processing and molding, low density, chemical resistance, excellent physical and mechanical properties, and the like. However, due to the structural characteristics of the PP material, stress whitening is a difficult problem of the PP material in the application process and often occurs when the PP material is subjected to the action of external force in the injection molding and assembling processes.
At present, the prior art reports the research aiming at the stress whitening problem of the PP material. In general, the solution generally consists in adding to the polypropylene resin containing reinforcing fillers components such as compatibilizers, anti-blushing agents or elastomers. For example, chinese patent application CN102295808A discloses a stress whitening resistant polypropylene composition, which comprises 35 to 82 wt.% of polypropylene resin, 2 to 12 wt.% of compatibilizer, 5 to 15 wt.% of stress whitening resistant agent, 10 to 40 wt.% of filler, and the like; chinese patent application CN106700232A discloses a stress whitening resistant polypropylene resin, which comprises 80-98 parts of polypropylene resin, 2-20 parts of low density polyethylene, 5-30 parts of glass fiber and other components. For the stress whitening resistant polypropylene materials reported in the prior art, the reinforcing filler is generally talcum powder, mica, calcium carbonate, glass fiber, silicon dioxide and the like, and can increase the strength and rigidity of the materials and avoid the phenomena of deformation and whitening of the materials due to stress to a certain extent.
With the development of the automobile industry, the light weight of automobile materials is a necessary choice in the market, and the density of polypropylene materials containing a large amount of reinforcing fillers is too high to meet the requirement of light weight. In the case of polypropylene materials without filled reinforcing fillers, the polypropylene material is more easily deformed due to the reinforcing effect without the filler, and thus stress whitening occurs. Particularly, for automotive interior parts such as light-colored door panels, columns and the like, although the stress whitening phenomenon does not occur in the injection molding or assembling process, after a period of use, the automotive interior parts are subjected to high-low temperature circulation and stress relaxation and then subjected to external force, and the stress whitening is easily generated.
Accordingly, there is a need to develop a stress whitening resistant polypropylene composition without a filled reinforcing filler.
Disclosure of Invention
The invention provides a non-filled stress whitening-resistant polypropylene composition for overcoming the defect of non-stress whitening resistance in the prior art, and the non-filled stress whitening-resistant polypropylene composition has excellent stress whitening resistance on the basis of no reinforcing filler.
Another object of the present invention is to provide a method for preparing the above unfilled stress whitening resistant polypropylene composition.
Another object of the present invention is to provide the use of the above unfilled stress whitening resistant polypropylene composition for the preparation of automotive interior trim parts.
In order to solve the technical problems, the invention adopts the technical scheme that:
the non-filled stress whitening resistant polypropylene composition comprises the following components in parts by weight:
100 parts of polypropylene, namely 100 parts of polypropylene,
0.25 to 2.5 parts of peroxide adsorption master batch,
0.7 to 6 parts of activated titanium dioxide,
0.1 to 1 part of antioxidant,
0.05 to 0.5 portion of light stabilizer,
0.05 to 0.5 portion of nucleating agent,
0.1-0.5 part of a lubricant;
the peroxide adsorption master batch is a porous molecular sieve adsorbed with a peroxide initiator; the activated titanium dioxide is titanium dioxide subjected to surface treatment by a silane coupling agent.
The titanium dioxide is subjected to surface treatment by the silane coupling agent, and partial silicon-oxygen bonds of the silane coupling agent participate in micro-crosslinking reaction to form silicon-oxygen-silicon bonds, so that the titanium dioxide becomes a micro-crosslinked central body. After the peroxide initiator is adsorbed to the porous molecular sieve, the peroxide initiator is added in the form of peroxide adsorption master batch and is blended with other components, so that the degradation effect of the direct addition of the peroxide on the polypropylene is avoided, and meanwhile, the peroxide initiator can be continuously released at a slow speed, so that the micro-crosslinking effect is continuously carried out in the use process of the material. The silane coupling agent and the peroxide initiator in the system slightly crosslink the polypropylene matrix resin, and the micro crosslinking is continuously acted at a slower speed in the presence of titanium dioxide as a micro crosslinking center body and peroxide adsorption master batches, and the unfilled stress whitening resistant polypropylene composition can keep excellent stress whitening resistance under different use temperatures, use environments and stress relaxation conditions.
Preferably, the polypropylene is a homopolypropylene.
Compared with the copolymerization polypropylene or the random polypropylene, the homopolymerization polypropylene has the characteristics of high crystallization and high rigidity, and the stress whitening resistance is better.
Preferably, the melt flow rate of the homopolymerized polypropylene is 2-90 g/10min under the conditions of 230 ℃ and 2.16 kg.
The method for detecting the melt flow rate is in accordance with GB/T3682-2018.
Preferably, the mass ratio of the peroxide initiator to the porous molecular sieve in the peroxide adsorption master batch is (0.2-0.5) to 1.
Preferably, the specific surface area of the porous molecular sieve is more than or equal to 300m2(iii) a mean particle diameter of 200 to 1500 μm.
The detection method of the specific surface area of the porous molecular sieve comprises the following steps: GB/T19587-2004.
Preferably, the melting point of the peroxide initiator is less than or equal to 0 ℃.
More preferably, the peroxide initiator has a melting point of-35 ℃.
The melting point was determined according to GB/T19466.3-2004.
The melting point of the peroxide initiator can be below-60 ℃ at the lowest and can be above 100 ℃ at the highest. The invention selects peroxide initiator with melting point less than or equal to 0 deg.C, which is liquid at room temperature, and is convenient for adsorption by porous molecular sieve, so as to achieve slow release effect.
Preferably, the peroxide is one or more of di-tert-butyl peroxide (DTBP), ditert-amyl peroxide (DTAP) or 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane (301).
Preferably, the peroxide adsorption master batch is prepared by the following method:
placing the porous molecular sieve in a closed container, sealing, vacuumizing to ensure that the vacuum degree in the closed container is less than or equal to-0.15 MPa, adding a peroxide initiator into the closed container, and performing vacuum adsorption to obtain the peroxide adsorption master batch.
Preferably, the temperature of the vacuum adsorption is more than 0 ℃, and the time is more than or equal to 5 min.
Preferably, the activated titanium dioxide is prepared by the following method:
dispersing titanium dioxide in a silane coupling agent aqueous solution, and stirring, dehydrating and drying to obtain the activated titanium dioxide.
Preferably, the silane coupling agent is vinyltriethoxysilane.
Titanium dioxide is generally classified according to its crystal structure: rutile titanium dioxide, anatase titanium dioxide and brookite titanium dioxide. The rutile type titanium dioxide has the characteristics of stable crystal form and compact atomic arrangement, so the titanium dioxide is preferably the rutile type titanium dioxide.
Preferably, the titanium dioxide is coated with a silicon aluminum coating comprising silicon oxide and aluminum oxide.
Preferably, the silicon oxide accounts for 5-6.5 wt% of the total mass of the titanium dioxide and the silicon-aluminum coating, and the aluminum oxide accounts for 3-3.5 wt% of the total mass of the titanium dioxide and the silicon-aluminum coating.
Because the surface of the titanium dioxide has more active sites, the titanium dioxide has catalytic degradation effect on the polypropylene directly contacted with the titanium dioxide, so that the weather resistance of the titanium dioxide is reduced. In the application, after the oxide with stable performance of the titanium dioxide is coated, the active sites can be blocked, and the negative effect of resisting stress whitening can be avoided.
Preferably, the titanium dioxide is prepared by a chlorination method, and the average particle size is less than or equal to 0.25 mu m.
More preferably, the titanium dioxide has an average particle diameter of 0.15 to 0.23 μm.
Preferably, the antioxidant can be a single antioxidant or a combination of antioxidants. Preferably, the antioxidant is formed by compounding a main antioxidant and an auxiliary antioxidant.
Preferably, the primary antioxidant is a hindered phenol type antioxidant; the auxiliary antioxidant is aryl phosphite ester antioxidant.
More preferably, the mass ratio of the main antioxidant to the auxiliary antioxidant is (0.8-1.2) to 1.
Preferably, the light stabilizer is one or more of hindered amine light stabilizer, benzophenone ultraviolet absorbent and benzotriazole ultraviolet absorbent.
Alternatively, the hindered amine light stabilizer may be selected from UV-944, UV-770, UV-622, and the like.
Alternatively, the benzophenone-based ultraviolet absorber may be selected from UV-531, UV-1200, and the like.
Alternatively, the benzotriazole-based ultraviolet absorber may be selected from UV-5411, UV-326, and the like.
Preferably, the nucleating agent is a beta nucleating agent.
The beta-type nucleating agent is an unstable crystal form and can be changed into an alpha crystal form when the external conditions change, and the problem of stress concentration from the inside and the outside can be solved in the crystal form changing process, so that the stress whitening self-repairing function of the filling-free stress whitening resistant polypropylene composition is further enhanced.
More preferably, the nucleating agent is an arylamide β -type nucleating agent.
Optionally, the nucleating agent is TMB-5, N' -dicyclohexylterephthalamide.
Preferably, the lubricant is stearic acid.
Stearic acid is used as a lubricant, on one hand, the stearic acid can provide a lubricating effect, and on the other hand, the stearic acid can also be used as a hydrolysis supply agent of micro-crosslinking, so that the proceeding rate of a crosslinking reaction is greatly delayed, the micro-crosslinking is slowly and continuously performed, and further the micro-crosslinking reaction is continuously performed after the unfilled stress whitening-resistant polypropylene composition is manufactured into a product, and the problem of stress whitening of the material in the using process is effectively solved.
The invention also provides a preparation method of the unfilled stress whitening-resistant polypropylene composition, which comprises the following steps:
mixing polypropylene, activated titanium dioxide, an antioxidant, a light stabilizer, a nucleating agent and a lubricant, and adding the mixture into a main feeding port of an extruder; adding the peroxide adsorption master batch to a side feeding port of an extruder;
and carrying out melt mixing and extrusion granulation to obtain the filling-free stress whitening resistant polypropylene composition.
Preferably, the extruder is a double-screw extruder, the length-diameter ratio of screws is 48-72: 1, and the extrusion temperature is 180-200 ℃.
The invention also protects the application of the unfilled stress whitening resistant polypropylene composition in the preparation of automotive interior parts.
The automobile interior trim part can be an automobile door plate, an automobile upright post or an automobile guard plate.
Compared with the prior art, the invention has the beneficial effects that:
the non-filling stress whitening resistant polypropylene composition disclosed by the invention takes polypropylene as matrix resin, and adopts silane coupling agent and peroxide to slightly micro-crosslink the polypropylene, so that the material has better mechanical property, and the stress whitening resistant performance is excellent. Meanwhile, titanium dioxide is subjected to surface treatment by a silane coupling agent to be used as a micro-crosslinked center body; the peroxide is added in the form of adsorption master batch, so that the degradation effect on the polypropylene is avoided, and meanwhile, the peroxide can be continuously released at a slow speed, so that the micro-crosslinking effect is continuously carried out in the use process of the material.
Under the action of continuous micro-crosslinking, the unfilled stress whitening resistant polypropylene composition can maintain excellent stress whitening resistant performance under the conditions of high-temperature storage, low-temperature storage, high-temperature and low-temperature cyclic storage or stress relaxation.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The raw materials in the examples and comparative examples are all commercially available;
reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Examples 1 to 21
Examples 1 to 21 provide a no-filling stress whitening resistant polypropylene composition, the component contents of which are shown in table 1;
wherein the peroxide master batch-1 is a porous molecular sieve-1 for adsorbing DTBP, and the mass ratio of the DTBP to the porous molecular sieve-1 is 0.2: 1; the peroxide master batch-2 is a porous molecular sieve-1 for adsorbing DTAP, and the mass ratio of the DTAP to the porous molecular sieve-1 is 0.2: 1; the peroxide master batch-3 is a porous molecular sieve-1 for adsorbing 301, and the mass ratio of 301 to the porous molecular sieve-1 is 0.2: 1; the peroxide master batch-4 is a porous molecular sieve-2 for adsorbing DTBP, and the mass ratio of the DTBP to the porous molecular sieve-2 is 0.2: 1; the peroxide master batch-5 is a porous molecular sieve-1 for adsorbing DTBP, and the mass ratio of the DTBP to the porous molecular sieve-1 is 0.5: 1; the peroxide master batch-6 is a porous molecular sieve-1 for adsorbing DTBP, and the mass ratio of the DTBP to the porous molecular sieve-1 is 0.7: 1; the peroxide master batch-7 is a porous molecular sieve-1 for adsorbing DCP, and the mass ratio of the DCP to the porous molecular sieve-1 is 0.2: 1; the peroxide master batch-8 is a porous molecular sieve-3 for adsorbing DTBP, and the mass ratio of the DTBP to the porous molecular sieve-3 is 0.2: 1;
the preparation method of the peroxide master batch comprises placing the porous molecular sieve in a closed container, sealing, vacuumizing to make the vacuum degree in the closed container less than or equal to-0.15 MPa, adding peroxide initiator into the closed container, and performing vacuum adsorption at 20 deg.C for 10min to obtain peroxide adsorption master batch;
the activated titanium dioxide-1 is titanium dioxide-1 subjected to surface treatment by a silane coupling agent, the activated titanium dioxide-2 is titanium dioxide-2 subjected to surface treatment by the silane coupling agent, and the activated titanium dioxide-3 is titanium dioxide-3 subjected to surface treatment by the silane coupling agent; the activated titanium dioxide-4 is titanium dioxide-4 subjected to surface treatment by a silane coupling agent, and the activated titanium dioxide-5 is titanium dioxide-5 subjected to surface treatment by the silane coupling agent;
the preparation method of the activated titanium dioxide comprises the steps of dispersing the titanium dioxide in a silane coupling agent aqueous solution, stirring, dehydrating, drying and grading to obtain the activated titanium dioxide.
The preparation method of the unfilled stress whitening resistant polypropylene composition of examples 1-15 is as follows:
mixing polypropylene, activated titanium dioxide, an antioxidant, a light stabilizer, a nucleating agent and a lubricant, and adding the mixture into a main feeding port of a double-screw extruder; adding the peroxide adsorption master batch into a side feeding port of a double-screw extruder; the filling-free stress whitening-resistant polypropylene composition is obtained through melt mixing and extrusion granulation;
wherein the length-diameter ratio of screws of the double-screw extruder is 48-72: 1, and the extrusion temperature is 180-200 ℃.
TABLE 1 component content (parts by weight) of unfilled stress whitening resistant polypropylene compositions of examples 1 to 21
Comparative examples 1 to 7
Comparative examples 1 to 7 provide polypropylene compositions having the component contents shown in table 2, and the preparation methods are as follows:
mixing polypropylene, activated titanium dioxide (or titanium dioxide which is not treated by a silane coupling agent), an antioxidant, a light stabilizer, a nucleating agent and a lubricant, and adding the mixture into a main feeding port of a double-screw extruder; adding peroxide adsorption master batches (or peroxide initiators) into a side feeding port of a double-screw extruder; carrying out melt mixing and extrusion granulation to obtain a polypropylene composition;
wherein the length-diameter ratio of screws of the double-screw extruder is 48-72: 1, and the extrusion temperature is 180-200 ℃.
TABLE 2 component contents (parts by weight) of comparative examples 1 to 7 polypropylene compositions
And (3) performance testing:
the polypropylene compositions prepared in the above examples and comparative examples were injection molded into test square plaques of 100 × 3mm, and the stress whitening performance was tested under the conditions of initial injection molding, high-temperature standing, low-temperature standing, high-and low-temperature cyclic standing, and stress relaxation, respectively, according to the following test methods:
stress whitening performance: the method comprises the steps of adopting a ball dropping method, freely dropping 500g of balls on a test square plate at a height of 500mm, placing the test square plate under standard experimental conditions (23 +/-2 ℃ and 50 +/-5% of relative humidity) for 48 hours after dropping the balls, and comparing the color change conditions (delta L) of the ball dropping position and the ball dropping position of the test square plate, wherein the delta L is less than or equal to 1.0, so that the stress whitening resistance is good.
Initial conditions: standing at 23 deg.C for 48 h;
high-temperature standing conditions: standing at 110 deg.C for 400h, standing under standard experimental conditions for 48h, and testing stress whitening performance;
and (3) low-temperature placing conditions: standing at-40 deg.C for 400h, standing under standard experimental conditions for 48h, and testing stress whitening performance;
high-low temperature circulation placing conditions: standing at 110 deg.C for 3h, at 23 deg.C for 0.5h, at-40 deg.C for 2h, at 23 deg.C for 0.5h, performing ten cycles, standing under standard experimental conditions for 48h, and testing stress whitening performance;
stress relaxation conditions: and bending the test square plate by 30 degrees, fixing the test square plate by using a clamp, placing the test square plate for 48 hours under the standard experiment condition, removing the clamp, and then placing the test square plate for 48 hours under the standard experiment condition for performing a stress whitening performance test.
The test results were as follows:
TABLE 3 test results of examples 1 to 21
TABLE 4 test results for comparative examples 1 to 7
According to the test results in Table 3, the unfilled stress-whitening resistant polypropylene compositions of the present invention have a Δ L of 1 or less under the stress whitening performance test under the conditions of initial, high temperature placement, low temperature placement, high and low temperature cycling placement and stress relaxation, which indicates that the unfilled stress-whitening resistant polypropylene compositions of the present application have excellent stress whitening resistance.
In examples 1, 5 and 6, when the mass ratio of the peroxide initiator to the porous molecular sieve in the peroxide adsorption master batch is (0.2-0.5) to 1, the porous molecular sieve can adsorb the peroxide initiator more sufficiently, and the prepared unfilled stress whitening resistant polypropylene composition has better stress whitening resistance.
From examples 1, 2, 3 and 7, when the melting point of the peroxide initiator in example 7 is not less than 0 ℃, the peroxide initiator is incompletely adsorbed by the porous molecular sieve at room temperature, so that the stress whitening resistance of example 7 is slightly inferior to that of examples 1 to 3.
From examples 1, 9, 10 and 20, activated titania-1 used in example 1 had a titania particle size of 0.2 μm with a silicon-aluminum clad coating; activated titanium dioxide used in example 9-2, wherein the titanium dioxide had a particle size of 0.35 μm and a silicon-aluminum overcoat; the particle size of the titanium dioxide in the activated titanium dioxide-3 used in example 10 was 0.2 μm, with no silicon-aluminum clad coating; example 20 used activated titania-5 where the titania particle size was 0.2 μm with only the alumina coating. According to the test results of the stress whitening resistance, the Δ L value of example 1 is relatively the lowest. The grain size of the titanium dioxide is less than or equal to 0.25 mu m, and when the polypropylene composition is coated with the silicon-aluminum coating, the stress whitening resistance of the prepared polypropylene composition is better.
From the embodiment 1 and the embodiment 21, when the nucleating agent is the aryl amide type beta nucleating agent, the prepared polypropylene composition has better stress whitening resistance.
According to the test results in Table 4, comparative example 1 contains no titanium dioxide or activated titanium dioxide, comparative example 3 contains no peroxide-adsorbing master batch, the polypropylene composition has poor stress whitening resistance, and DeltaL is not less than 3 under certain standing conditions. In the comparative example 2, the titanium dioxide is not treated by the silane coupling agent, so that the micro-crosslinking effect of the polypropylene composition is poor, and the Delta L is not less than 1 except for the initial condition, and the requirements cannot be met. In comparative example 4, the peroxide initiator is not added in the form of master batch, but is directly blended with other components, so that the polypropylene is easily degraded, the peroxide initiator is released too fast and cannot be subjected to micro-crosslinking continuously, the Delta L of the polypropylene composition reaches 3.7 after being placed at high temperature, and the Delta L reaches 3.8 after being subjected to stress relaxation. The polypropylene composition does not contain a nucleating agent in the comparative example 5, so that the polypropylene composition has poor stress whitening self-repairing performance, and the Delta L is 1.5 after cyclic placement at high and low temperatures. In comparative example 6, the number of peroxide master batches is large, and the crosslinking rate of the polypropylene composition is too high, so that the slow and slow micro-crosslinking is not facilitated, and the stress whitening resistance of the polypropylene composition is poor. In comparative example 7, the content of activated titanium dioxide was too large, and although the polypropylene composition had good stress whitening resistance under the initial conditions, after high-temperature standing, high-and low-temperature cyclic standing, or stress relaxation, the Δ L was 1.0 or more, and the stress whitening resistance was poor.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The non-filling stress whitening resistant polypropylene composition is characterized by comprising the following components in parts by weight:
100 parts of polypropylene, 0.25-2.5 parts of peroxide adsorption master batch, 0.7-6 parts of activated titanium dioxide, 0.1-1 part of antioxidant, 0.05-0.5 part of light stabilizer, 0.05-0.5 part of nucleating agent and 0.1-0.5 part of lubricant;
the peroxide adsorption master batch is a porous molecular sieve adsorbed with a peroxide initiator; the activated titanium dioxide is titanium dioxide with the surface treated by a silane coupling agent.
2. The unfilled stress-whitening-resistant polypropylene composition according to claim 1, wherein the mass ratio of the peroxide initiator to the porous molecular sieve in the peroxide-adsorbing masterbatch is (0.2-0.5) to 1.
3. The unfilled stress-whitening-resistant polypropylene composition of claim 1, wherein the porous molecular sieve has a specific surface area of 300m or more2(iii) a mean particle diameter of 200 to 1500 μm.
4. The unfilled stress-whitening-resistant polypropylene composition of claim 1, wherein the peroxide-based initiator has a melting point of 0 ℃ or less.
5. The unfilled stress-whitening resistant polypropylene composition of claim 4, wherein the peroxide-based initiator has a melting point of-35 ℃.
6. The unfilled stress-whitening resistant polypropylene composition of claim 1, wherein the titanium dioxide is coated with a silica-alumina coating comprising silica and alumina.
7. The unfilled stress-whitening-resistant polypropylene composition of claim 6, wherein the silica comprises 5 to 6.5 wt.% of the total mass of the titania and silica-alumina coating, and the alumina comprises 3 to 3.5 wt.% of the total mass of the titania and silica-alumina coating.
8. The unfilled stress-whitening resistant polypropylene composition of claim 1, wherein the nucleating agent is an arylamide-type β nucleating agent.
9. The method for preparing the unfilled stress whitening resistant polypropylene composition of any one of claims 1 to 8, comprising the steps of:
mixing polypropylene, activated titanium dioxide, an antioxidant, a light stabilizer, a nucleating agent and a lubricant, and adding the mixture into a main feeding port of an extruder; adding the peroxide adsorption master batch to a side feeding port of an extruder;
and carrying out melt mixing and extrusion granulation to obtain the filling-free stress whitening resistant polypropylene composition.
10. Use of the unfilled stress whitening resistant polypropylene composition of any one of claims 1 to 8 for the preparation of an automotive interior part.
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| CN1050397A (en) * | 1989-09-21 | 1991-04-03 | 黎功成 | The modified polypropene process for preparing thermo-melting rubber stripe for tension last of leather shoe with |
| CN106279982A (en) * | 2016-08-11 | 2017-01-04 | 厦门建霖工业有限公司 | Polypropylene that a kind of creep resistance strengthens and preparation method thereof |
| CN110105601A (en) * | 2019-05-08 | 2019-08-09 | 合肥原然新材料有限公司 | A kind of preparation method of peroxide master batch |
-
2021
- 2021-08-30 CN CN202111006171.1A patent/CN113698703B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050397A (en) * | 1989-09-21 | 1991-04-03 | 黎功成 | The modified polypropene process for preparing thermo-melting rubber stripe for tension last of leather shoe with |
| CN106279982A (en) * | 2016-08-11 | 2017-01-04 | 厦门建霖工业有限公司 | Polypropylene that a kind of creep resistance strengthens and preparation method thereof |
| CN110105601A (en) * | 2019-05-08 | 2019-08-09 | 合肥原然新材料有限公司 | A kind of preparation method of peroxide master batch |
Non-Patent Citations (1)
| Title |
|---|
| 王红卫等: "表面处理对TiO_2/PP复合材料界面的影响", 《合成技术及应用》 * |
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| CN113698703B (en) | 2023-06-06 |
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