CN110964261A - Scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material and preparation method thereof - Google Patents
Scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material and preparation method thereof Download PDFInfo
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- CN110964261A CN110964261A CN201911319594.1A CN201911319594A CN110964261A CN 110964261 A CN110964261 A CN 110964261A CN 201911319594 A CN201911319594 A CN 201911319594A CN 110964261 A CN110964261 A CN 110964261A
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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
- C08L23/14—Copolymers of propene
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention provides a scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material and a preparation method thereof, and the material is characterized in that: the modified material is prepared from the following raw materials in parts by weight: 40-70 parts of polypropylene resin, 5-30 parts of glass wool, 1-15 parts of elastomer, 1-10 parts of polyethylene, 1-3 parts of scratch-resistant agent, 2-5 parts of odor adsorbent, 0.2-0.4 part of main antioxidant and 0.2-0.4 part of auxiliary antioxidant. The scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material disclosed by the invention is filled with glass wool, so that the scratch resistance of the material is obviously improved, and the addition of a scratch-resistant auxiliary agent can be reduced, so that the odor of the material is reduced, and the emission performance of the material is improved.
Description
Technical Field
The invention belongs to the technical field of modified plastics, and particularly relates to a scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material.
Background
In recent years, polypropylene materials are widely applied to the field of automobiles, the quality requirements of people on automotive interiors are continuously improved, the products are required to have good internal quality, the appearance of the products is also very important, the scratch resistance requirements of instrument panels, door panels, columns and the like which can contact interior parts are also increasingly strict, meanwhile, consumers are increasingly concerned about odor and Volatile Organic Compounds (VOC) in automobiles, the national regulation and control on automotive VOC have been carried out by new regulations, the low VOC and the low odor of automotive interior parts also become hard indexes of various major main engine plants, and the regulation and control are required to be started from raw materials. In order to improve the odor VOC of parts and to improve scratch resistance, various automobile manufacturers and raw material suppliers have invested a great deal of effort and research on materials. Although many reports in the prior art have reported research on solving the scratch resistance problem of polypropylene composite materials, the mere utilization of amide and silicone scratch resistance agents to improve the scratch resistance of the materials has limitations. The amide-based scratch resistant agent is likely to migrate to the surface of the material to lower the coefficient of friction of the material, and although the scratch resistance of the material is improved, the odor is large and there is a risk of precipitation of tackiness.
Disclosure of Invention
In view of the above, the invention aims to provide a scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material, which is filled with glass wool, so that the scratch resistance of the material is remarkably improved, the odor of the material is reduced by reducing the addition of a scratch-resistant auxiliary agent, the emission performance of the material is improved, and the low gloss of the material is maintained.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material is prepared from the following raw materials in parts by weight:
the polypropylene resin is one or more of homo-polypropylene or co-polypropylene, and the melt flow rate is 5-60g/10min under the test condition of 230 ℃/2.16 kg;
the glass wool is one or a mixture of two of glass wool powder or glass wool master batch;
the scratch resistant agent is polysiloxane.
Further, the flexural modulus of the polypropylene resin is 800-2000MPa, and the notch impact strength of the polypropylene resin is 1-50kJ/m2。
Further, the odor adsorbent is infilm 800.
Further, the elastomer is ethylene propylene diene monomer.
Further, the polyethylene is one or a mixture of more of high density polyethylene, low density polyethylene or linear low density polyethylene.
Further, the polyethylene is high density polyethylene.
Further, the primary antioxidant is a hindered phenol antioxidant.
Further, the auxiliary antioxidant is a phosphite ester compound.
The invention also provides a preparation method of the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material, which comprises the following steps:
step 1: weighing the polypropylene resin, the glass wool, the elastomer, the polyethylene, the scratch-resistant agent, the odor adsorbent, the main antioxidant and the auxiliary antioxidant according to the proportion, mixing the materials in a high-speed mixer for 1-3min, and mixing the materials uniformly to obtain the premix.
Step 2: feeding the premix obtained in the step 1 from a main feeding port of a double-screw extruder for melt extrusion, and then granulating and drying to obtain the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material, wherein the conditions of the melt extrusion step are as follows: the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 190-.
Further, the length-diameter ratio of the twin-screw extruder is 40: 1.
The polypropylene resin has high crystallinity and regular structure, thereby having excellent mechanical property and higher strength and hardness; at room temperature and low temperature, the molecular structure of the material is high in regularity, so that the impact strength is poor and the scratch resistance is low. Therefore, the invention adds the scratch resistant agent, and the scratch resistant agent is polysiloxane. The polysiloxane scratch-resistant agent has small molecular weight and small surface tension, can migrate to the surface of a polypropylene material in the forming process and form a polysiloxane molecular lubricating layer with a lubricating effect, and the surface lubricating effect can reduce the surface friction coefficient of the material so as to improve the surface friction resistance of the material. Moreover, because the polysiloxane main chain structure in the polysiloxane scratch resistant agent is a Si-O-Si structure, the polysiloxane molecular lubricating layer has regular structure, wear resistance and stable chemical property, and meanwhile, the polypropylene resin has high crystallinity and regular structure, so that the polysiloxane molecular lubricating layer can be uniformly and flatly paved on the surface of the polypropylene resin, and the appearance properties such as surface smoothness, flatness and the like of the polypropylene resin material can be improved. However, the surface migration amount of the polysiloxane-based scratch resistant agent is not easy to be too large, so that small molecules on the surface of the material are aggregated, the surface of the material is sticky, and the touch feeling is influenced, so that the defect is improved by adding one or a mixture of two of the glass cotton powder or the glass cotton master batch. The glass wool is made up by using natural minerals of quartz sand, limestone and dolomite as main raw material, and adding some chemical raw materials of soda ash and borax, etc. and melting them into glass, and in the molten state, using external force to blow and throw it into the flocculent fine fibre, and the fibre and fibre are crossed and mutually twisted together to form many fine gaps, i.e. the glass wool can be seen as porous material. The flocculent and fine glass wool such as glass wool powder or glass wool master batch is uniformly dispersed and filled in the polysiloxane scratch-resistant agent, so that the aggregation of micromolecules of the polysiloxane scratch-resistant agent on the surface can be interrupted, and the stickiness of the surface of the material can be prevented. Meanwhile, the smooth softness of the glass wool powder or the glass wool master batch further enhances the surface lubricating effect of the material, and prevents surface scraping. The mass filling of glass wool has the following effects: (1) the polypropylene glass wool modified material can be used as a dispersing agent to uniformly disperse components such as polyethylene, odor adsorbent and the like, so that the uniformity of the property of the whole polypropylene glass wool modified material is improved; (2) the scratch-resistant agent can be used as a scratch-resistant agent to be dispersed in and on the surface of the polypropylene glass cotton modified material, so that the scratch resistance of the whole polypropylene glass cotton modified material is improved; (3) the surface of polysiloxane molecules can be gathered in an advancing way, so that the surface of the polypropylene glass wool modified material is prevented from being bonded; (4) the polysiloxane scratch-resistant agent is expensive and can emit pungent odor, and only 1-3 parts of the scratch-resistant agent is added into 5-30 parts of glass wool, so that the addition of the scratch-resistant agent is effectively reduced and the generation of pungent odor is reduced on the premise of ensuring the scratch resistance of the polypropylene glass wool modified material.
Compared with the prior art, the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material has the following advantages:
(1) the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material is filled with glass wool, so that the scratch resistance of the material is remarkably improved, and meanwhile, the addition of a scratch-resistant auxiliary agent can be reduced, so that the odor of the material is reduced, and the emission performance of the material is improved.
(2) The glass wool filling in the invention has no negative influence on the product appearance, does not influence the color matching capability of the material, is easy to implement and has wide applicability, the addition of the glass wool reduces the dosage of the additional components of the scratch-resistant agent, and the polypropylene surface bonding caused by adding a large amount of the scratch-resistant agent is avoided.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified. The flexural modulus of the impact-resistant copolymerized polypropylene 1 is 1000-1400 MPa; the flexural modulus of the impact-resistant copolymerized polypropylene 2 is 1500-1800 MPa; the glass wool is glass wool master batch (80 percent content); the elastomer is POE 7447; the high density polyethylene is HDPE 7260; the scratch resistant agent is epoxy polysiloxane H52-3; the odor adsorbent is infilm 800; the main antioxidant is antioxidant 1010; the auxiliary antioxidant is antioxidant 168.
The present invention will be described in detail with reference to examples.
Example 1
Step 1: weighing 20 parts of impact-resistant co-polypropylene 1, 25 parts of impact-resistant co-polypropylene 2, 25 parts of glass wool master batch, 8 parts of POE7447, 10 parts of high-density polyethylene, 2 parts of epoxy polysiloxane H52-3, 2 parts of infilm 800, 0.3 part of antioxidant 1010 and 0.3 part of antioxidant 168, putting the weighed components into a high-speed mixer, and mixing for 3min at high speed in the high-speed mixer to obtain the premix.
Step 2: feeding the premix obtained in the step 1 from a main feeding port of a double-screw extruder for melt extrusion, wherein the temperature of a first zone is controlled to be 80 ℃, the temperature of a second zone is controlled to be 210 ℃, the temperature of a third zone is controlled to be 220 ℃, the temperature of a fourth zone is controlled to be 220 ℃, the temperature of a fifth zone is controlled to be 230 ℃, the temperature of a sixth zone is controlled to be 230 ℃, the temperature of a seventh zone is controlled to be 230 ℃, the temperature of an eighth zone is controlled to be 230 ℃, and the temperature of a ninth zone is controlled to. And after melt extrusion, granulating and drying to obtain the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material.
Example 2
Step 1: weighing 30 parts of impact-resistant co-polypropylene 1, 25 parts of impact-resistant co-polypropylene 2, 15 parts of glass wool master batch, 10 parts of POE7447, 5 parts of high-density polyethylene, 1 part of epoxy polysiloxane H52-3, 3 parts of infilm 800, 0.35 part of antioxidant 1010 and 0.2 part of antioxidant 168, putting the weighed components into a high-speed mixer, and mixing for 2min at high speed in the high-speed mixer to obtain the premix.
Step 2: feeding the premix obtained in the step 1 from a main feeding port of a double-screw extruder for melt extrusion, wherein the temperature of a first zone is controlled to be 90 ℃, the temperature of a second zone is controlled to be 190 ℃, the temperature of a third zone is controlled to be 210 ℃, the temperature of a fourth zone is controlled to be 215 ℃, the temperature of a fifth zone is controlled to be 210 ℃, the temperature of a sixth zone is controlled to be 220 ℃, the temperature of a seventh zone is controlled to be 225 ℃, the temperature of an eighth zone is controlled to be 230 ℃, and the temperature of a ninth zone is controlled to. And after melt extrusion, granulating and drying to obtain the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material.
Example 3
Step 1: weighing 40 parts of impact-resistant co-polypropylene 1, 25 parts of impact-resistant co-polypropylene 2, 10 parts of glass wool master batch, 5 parts of POE7447, 5 parts of high-density polyethylene, 1 part of epoxy polysiloxane H52-3, 2 parts of infilm 800, 0.3 part of antioxidant 1010 and 0.3 part of antioxidant 168, putting the weighed components into a high-speed mixer, and mixing for 1min at high speed in the high-speed mixer to obtain the premix.
Step 2: feeding the premix obtained in the step 1 from a main feeding port of a double-screw extruder for melt extrusion, wherein the temperature of a first zone is controlled to be 120 ℃, the temperature of a second zone is controlled to be 200 ℃, the temperature of a third zone is 215 ℃, the temperature of a fourth zone is controlled to be 210 ℃, the temperature of a fifth zone is controlled to be 220 ℃, the temperature of a sixth zone is controlled to be 220 ℃, the temperature of a seventh zone is controlled to be 230 ℃, the temperature of an eighth zone is controlled to be 230 ℃, and the temperature of a ninth zone is controlled to be 230 ℃. And after melt extrusion, granulating and drying to obtain the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material.
Comparative example 1
Step 1: weighing 40 parts of impact-resistant co-polypropylene 1, 25 parts of impact-resistant co-polypropylene 2, 25 parts of talcum powder master batch, 5 parts of POE7447, 5 parts of high-density polyethylene, 1.5 parts of epoxy polysiloxane H52-3, 2 parts of infilm 800, 0.3 part of antioxidant 1010 and 0.3 part of antioxidant 168, putting the weighed components into a high-speed mixer, and mixing for 2min at high speed in the high-speed mixer to obtain the premix.
Step 2: feeding the premix obtained in the step 1 from a main feeding port of a double-screw extruder for melt extrusion, wherein the temperature of a first zone is controlled to be 80 ℃, the temperature of a second zone is controlled to be 210 ℃, the temperature of a third zone is controlled to be 220 ℃, the temperature of a fourth zone is controlled to be 220 ℃, the temperature of a fifth zone is controlled to be 220 ℃, the temperature of a sixth zone is controlled to be 230 ℃, the temperature of a seventh zone is controlled to be 230 ℃, the temperature of an eighth zone is controlled to be 230 ℃, and the temperature of a ninth zone is controlled to. And after melt extrusion, granulating and drying to obtain the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material.
Comparative example 2
Step 1: weighing 40 parts of impact-resistant co-polypropylene 1, 25 parts of impact-resistant co-polypropylene 2, 25 parts of calcium carbonate master batch, 5 parts of POE7447, 5 parts of high-density polyethylene, 1.5 parts of epoxy polysiloxane H52-3, 2 parts of infilm 800, 0.3 part of antioxidant 1010 and 0.3 part of antioxidant 168, putting the weighed components into a high-speed mixer, and mixing for 3min at high speed in the high-speed mixer to obtain the premix.
Step 2: feeding the premix obtained in the step 1 from a main feeding port of a double-screw extruder for melt extrusion, wherein the temperature of a first zone is controlled to be 100 ℃, the temperature of a second zone is controlled to be 190 ℃, the temperature of a third zone is 210 ℃, the temperature of a fourth zone is 215 ℃, the temperature of a fifth zone is controlled to be 220 ℃, the temperature of a sixth zone is controlled to be 230 ℃, the temperature of a seventh zone is controlled to be 230 ℃, the temperature of an eighth zone is controlled to be 230 ℃, and the temperature of a ninth zone is controlled to be 230 ℃ in the melting process of the double-screw extruder, and the rotating speed of. And after melt extrusion, granulating and drying to obtain the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material.
The flexural modulus test of the material is carried out according to ASTM D790, the thickness of a spline is 6.4mm, the bending speed is 30mm/min, the cantilever beam notch impact test of the material is carried out according to ASTM D256, the thickness of the spline is 6.4mm, the scratch resistance test of the material is carried out according to PV3952, a grid tester (German Erichsen electric grid tester 430P type) is used, the test load is 10N, the marking speed is 1000mm/min, the marking distance is 2mm, the diameter of a test head is 1mm, dL values of samples before and after marking are measured by a color difference meter, the difference of the dL values is calculated by △ L, the sample is a popular K3A leather plate, the gloss test of the material is a minitype triangle gloss meter (German Bikker-Katner K-GANERDR), the sample is a popular K3A leather plate, the odor test method is a popular VW's PV3900E test method of zero-part odor in an automobile compartment odor interference-free odor test method, the odor judgment standard is classified as class 1, 2 class 3 grade odor-free odor-smell-class, 4 odor-interference-class strong odor-interference-class 5 odor-interference-class 4 odor-interference.
The ratios of the components of examples 1 to 3 and comparative examples 1 to 2 are shown in Table 1, and the flexural modulus, notched Izod impact strength, scratch resistance, gloss and odor test results of the materials prepared in examples 1 to 3 and comparative examples 1 to 2 are shown in Table 2.
TABLE 1 formulation tables for examples 1-3 and comparative examples 1-2 (parts by weight)
TABLE 2 results of Performance test of examples 1-3 and comparative examples 1-2
As can be seen from the detection results of the examples and the comparative examples, the scratch resistance, the glossiness and the smell of the examples are better than those of the comparative examples, the addition of the glass wool master batch can replace the effect of the scratch resistance auxiliary agent, and the addition of the scratch resistance agent is reduced, so that the smell and the glossiness effect of the material are improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material is characterized in that: the modified material is prepared from the following raw materials in parts by weight:
the polypropylene resin is one or more of homo-polypropylene or co-polypropylene, and the melt flow rate is 5-60g/10min under the test condition of 230 ℃/2.16 kg;
the glass wool is one or a mixture of two of glass wool powder or glass wool master batch;
the scratch resistant agent is polysiloxane.
2. The scratch resistant, low odor, low gloss polypropylene glass wool modified material of claim 1 wherein: the flexural modulus of the polypropylene resin is 800-2000MPa, and the notch impact strength of the polypropylene resin is 1-50kJ/m2。
3. The scratch resistant, low odor, low gloss polypropylene glass wool modified material of claim 1 wherein: the odor adsorbent is infilm 800.
4. The scratch resistant, low odor, low gloss polypropylene glass wool modified material of claim 1 wherein: the elastomer is ethylene propylene diene monomer.
5. The scratch resistant, low odor, low gloss polypropylene glass wool modified material of claim 1 wherein: the polyethylene is one or a mixture of more of high-density polyethylene, low-density polyethylene or linear low-density polyethylene.
6. The scratch resistant, low odor, low gloss polypropylene glass wool modified material of claim 5, wherein: the polyethylene is high density polyethylene.
7. The scratch resistant, low odor, low gloss polypropylene glass wool modified material of claim 1 wherein: the main antioxidant is hindered phenol antioxidant.
8. The scratch resistant, low odor, low gloss polypropylene glass wool modified material of claim 1 wherein: the auxiliary antioxidant is a phosphite ester compound.
9. The process for preparing the scratch-resistant, low-odor, low-gloss polypropylene glass wool modified material according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
step 1: weighing the polypropylene resin, the glass wool, the elastomer, the polyethylene, the scratch-resistant agent, the odor adsorbent, the main antioxidant and the auxiliary antioxidant according to the proportion, mixing the materials in a high-speed mixer for 1-3min, and mixing the materials uniformly to obtain the premix.
Step 2: feeding the premix obtained in the step 1 from a main feeding port of a double-screw extruder for melt extrusion, and then granulating and drying to obtain the scratch-resistant, low-odor and low-gloss polypropylene glass wool modified material, wherein the conditions of the melt extrusion step are as follows: the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 190-.
10. The process for preparing a scratch resistant, low odor, low gloss polypropylene glass wool modified material according to claim 9 wherein: the length-diameter ratio of the twin-screw extruder is 40: 1.
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Cited By (1)
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Application publication date: 20200407 |