阅读说明：本技术 一种低气味低voc耐刮擦车用聚丙烯内饰材料及其制备方法 (Low-odor low-VOC scratch-resistant polypropylene interior material for vehicles and preparation method thereof ) 是由 王伟 杨杰 申应军 高翔 刘荣亮 张丰 李德燊 张淼 于 2020-12-18 设计创作，主要内容包括：本发明公开一种低气味低VOC耐刮擦车用聚丙烯内饰材料及其制备方法。其中低气味低VOC耐刮擦车用聚丙烯内饰材料包含以下组分：聚丙烯63-66％,滑石粉18-22％,增韧剂8-12％,抗氧剂0.3-0.5％,润滑剂0.3-0.5％,光稳定剂0.1-0.3％,除味剂比例1-3％,耐刮擦剂比例1-3％；所述除味剂孔径10um-50um；所述耐刮擦剂为硅酮类、芥酸酰胺类按重量比1:2-2:1复配组成。采用含有微孔含水结构的除味剂,可有效降低材料的气味等级及VOC含量,从而满足各主机厂汽车内饰材料气味等级标准≤3.0和VOC含量标准。(The invention discloses a low-odor low-VOC scratch-resistant polypropylene interior material for a vehicle and a preparation method thereof. The low-odor low-VOC scratch-resistant polypropylene interior material for the automobile comprises the following components: 63-66% of polypropylene, 18-22% of talcum powder, 8-12% of toughening agent, 0.3-0.5% of antioxidant, 0.3-0.5% of lubricant, 0.1-0.3% of light stabilizer, 1-3% of deodorant and 1-3% of scratch-resistant agent; the pore size of the smell removing agent is 10-50 um; the scratch-resistant agent is prepared by compounding silicone and erucamide according to the weight ratio of 1:2-2: 1. The odor grade and VOC content of the material can be effectively reduced by adopting the deodorant with the micropore water-containing structure, so that the odor grade standard of automobile interior materials of various main engine plants is less than or equal to 3.0 and the VOC content standard is met.)

1. The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is characterized by comprising the following components in percentage by weight: 63-66% of polypropylene, 18-22% of talcum powder, 8-12% of toughening agent, 0.3-0.5% of antioxidant, 0.3-0.5% of lubricant, 0.1-0.3% of light stabilizer, 1-3% of deodorant and 1-3% of scratch-resistant agent; the pore size of the smell removing agent is 10-50 um; the scratch-resistant agent is prepared by compounding silicone and erucamide according to the weight ratio of 1:2-2: 1.

2. The low-odor low-VOC scratch-resistant polypropylene interior material for vehicles according to claim 1, which comprises the following components in percentage by weight: 63-65% of polypropylene, 20% of talcum powder, 10% of toughening agent, 0.4% of antioxidant, 0.4% of lubricant, 0.2% of light stabilizer, 1-3% of deodorant and 1-3% of scratch-resistant agent; the pore size of the smell removing agent is 10-50 um; the scratch-resistant agent is prepared by compounding silicone and erucamide according to the weight ratio of 1:2-2: 1.

3. The low-odor low-VOC scratch-resistant polypropylene interior material for vehicles according to claim 1, wherein: the polypropylene is one or more of copolymerized polypropylene.

4. The low-odor low-VOC scratch-resistant polypropylene interior material for vehicles according to claim 1, wherein: the talcum powder is one or more of DV50 talcum powder with particle size less than or equal to 5 um.

5. The low-odor low-VOC scratch-resistant polypropylene interior material for vehicles according to claim 1, wherein: the toughening agent is one or more of ethylene octene copolymer and ethylene butene copolymer.

6. The low-odor low-VOC scratch-resistant polypropylene interior material for vehicles according to claim 1, wherein: the antioxidant is one or more of hindered phenol antioxidant, thioester antioxidant and sulfite antioxidant.

7. The low-odor low-VOC scratch-resistant polypropylene interior material for vehicles according to claim 1, wherein: the lubricant is one or more of N, N' -ethylene bis stearamide, polyethylene wax, polypropylene wax, calcium stearate, zinc stearate and magnesium stearate.

8. The low-odor low-VOC scratch-resistant polypropylene interior material for vehicles according to claim 1, wherein: the light stabilizer is one or more of LA-402AF, 5590 produced by adiaceae.

9. The low-odor low-VOC scratch-resistant polypropylene interior material for vehicles according to claim 1, wherein: the deodorant is a deodorant NSA-RSC486 produced by New materials works of Miro, Guangzhou.

10. A method for preparing the low-odor, low-VOC scratch-resistant polypropylene interior material for vehicles according to any one of claims 1 to 9, comprising the steps of:

(1) weighing polypropylene, talcum powder, toughening agent, antioxidant, lubricant, light stabilizer, scratch-resistant agent and deodorant according to the weight percentage, adding the weighed materials into a high-speed stirrer together, and uniformly mixing at high speed to obtain premix;

(2) adding the premix into a parallel double-screw extruder with the length-diameter ratio of 48:1, and extruding by shearing, melting, blending and extruding; the processing temperature of the double-screw extruder is 170-210 ℃, and the vacuum degree is less than or equal to-0.08 MPa;

(3) and cooling, drying and granulating the material strips extruded by the parallel double-screw extruder to obtain the low-odor low-VOC scratch-resistant polypropylene interior trim composite material for the vehicle.

Technical Field

The invention belongs to the field of high-molecular modified materials, and particularly relates to a low-odor low-VOC scratch-resistant polypropylene interior material for a vehicle and a preparation method thereof.

Background

The polypropylene (PP) modified material is widely applied to a plurality of fields of automobiles, household electrical appliances, food, medical treatment, building pipes and the like because of low cost, low density, excellent chemical resistance, outstanding physical and mechanical properties and good processability, and is one of the most rapidly-accelerated general plastics in the current market. As a main vehicle of daily life, the using amount and the demand of an automobile are steadily increased, and the automobile is favored by more and more consumers, along with the increasing health consciousness of people, the attention of the consumers to the internal environment of the automobile is improved, and higher requirements are provided for the aesthetic conditions (the scratch resistance of materials) of the odor, VOC (volatile organic compounds) and the door panel, the instrument panel and the ABC column of the internal part of the automobile. The odor released by the polypropylene modified material is mainly caused by the following aspects: firstly, a catalyst system used in the synthesis of a polypropylene resin matrix contains lipid compounds or peroxides with pungent odor; secondly, in the process of modifying and processing the polypropylene resin matrix, the polypropylene resin matrix is melted, sheared, extruded and granulated under the processing condition of 220 ℃ to generate thermal cracking small molecular compounds such as ketone and aldehyde compounds; in addition, some additives added in the modified polypropylene material, including antioxidants, lubricants, light stabilizers and the like, also have a certain pungent smell. The main reasons affecting the scratch resistance of automotive interior materials are: the automotive interior material is usually mineral filled (including talcum powder, calcium carbonate, mica and the like), the compatibility of the mineral filled and the PP resin is relatively poor, in addition, an interior part has certain requirements on the toughness of the material, the part is relatively soft, when the part is damaged by external acting force, the surface layer of the PP resin is damaged, the filling color of the mineral inside is exposed, the appearance of the part is whitish, and the poor scratch-resistant effect is shown.

With respect to the reduction of odor and VOC of polypropylene composite materials and the improvement of scratch resistance of the surface of material parts, some solutions are proposed in the related patents. The Chinese patent CN111057339A proposes to prepare a water-absorbing master batch, wherein the water-absorbing master batch can take away small molecular substances in the extrusion granulation process so as to reduce the odor grade and the VOC content of the material, the water-absorbing master batch is prepared by operating a German manufacturer raw material XP100-60 and free water according to a certain proportion in a specific process, and the master batch is imported to Germany and has higher price, so that the material cost is higher. Chinese patent application CN201010258937 utilizes aluminosilicate odor adsorption master batches to adsorb small molecules, reducing organic matter emission, but the final effect is affected by the desorption of small molecule compounds. Chinese patent CN201711432572 injects water into the polypropylene composite material melt in the extrusion process, and removes thermal cracking small molecules from the material by using the atomization extraction principle, thereby improving the odor and VOC of the material. The method has good effect on improving the odor and VOC of the material, but needs to modify equipment with higher cost. Chinese patent CN106589584A proposes a method for preparing a scratch-resistant material, which uses a method for producing homo-polypropylene with a nucleating agent, and improves the hardness of the surface of a workpiece by improving the rigidity and the crystallinity of the material, thereby improving the scratch-resistant performance of the material.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a low-odor low-VOC scratch-resistant polypropylene interior material for a vehicle and a preparation method thereof.

One of the technical schemes adopted by the invention for solving the technical problems is as follows:

the polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 63-66% of polypropylene, 18-22% of talcum powder, 8-12% of toughening agent, 0.3-0.5% of antioxidant, 0.3-0.5% of lubricant, 0.1-0.3% of light stabilizer, 1-3% of deodorant and 1-3% of scratch-resistant agent; the pore size of the smell removing agent is 10-50 um; the scratch-resistant agent is prepared by compounding silicone and erucamide according to the weight ratio of 1:2-2: 1.

Further, the low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle comprises the following components in percentage by weight: 63-65% of polypropylene, 20% of talcum powder, 10% of toughening agent, 0.4% of antioxidant, 0.4% of lubricant, 0.2% of light stabilizer, 1-3% of deodorant and 1-3% of scratch-resistant agent; wherein the odor removing agent is one or more of water containing with micropores or other extraction devolatilization agents; the scratch-resistant agent is prepared by compounding silicone and erucamide according to the weight ratio of 1:2-2: 1.

Specific classes of silicones include at least one of the following: such as MB50-001, Ramoplastic crystals 680, 503, etc.;

specific classes of erucamides include at least one of the following: such as EBS, amide waxes, etc.;

further, the polypropylene is one or more of copolymerized polypropylene.

Further, the talcum powder is one or more of DV50 talcum powder with particle size less than or equal to 5 um.

Further, the toughening agent is one or more of ethylene octene copolymer and ethylene butene copolymer.

Further, the antioxidant is one or more of hindered phenol antioxidant, thioester antioxidant and sulfite antioxidant.

Further, the lubricant is one or more of N, N' -ethylene bis stearamide, polyethylene wax, polypropylene wax, calcium stearate, zinc stearate and magnesium stearate.

Further, the light stabilizer is at least one of the following: such as LA-402AF, 5590, etc.

Further, the smell removing agent is a smell removing agent NSA-RSC486 produced by New materials works of Miluo, Guangzhou.

The second technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a low-odor low-VOC scratch-resistant polypropylene interior material for a vehicle comprises the following steps:

(1) weighing polypropylene, talcum powder, toughening agent, antioxidant, lubricant, light stabilizer, scratch-resistant agent and deodorant according to the weight percentage, adding the weighed materials into a high-speed stirrer together, and stirring and mixing the materials uniformly at a high speed to obtain premix;

(2) adding the premix into a parallel double-screw extruder with the length-diameter ratio of 48:1 from a main feeding hopper, and shearing, melting, blending and extruding all component materials in the parallel double-screw extruder; the processing temperature of the double-screw extruder is 170-;

(3) and cooling, drying and granulating the material strips extruded from the die of the parallel double-screw extruder to obtain the low-odor low-VOC scratch-resistant polypropylene interior trim composite material for the vehicle.

Compared with the background technology, the technical scheme of the invention has the following beneficial effects:

1. by compounding the silicone and the amide scratch-resistant agents, the silicone macromolecules are compatible with the polypropylene resin, and simultaneously, the erucic acid micromolecules migrate to the surface of the material, so that the external lubrication of the surface of a material part is increased, the friction coefficient is reduced, the scratch-resistant color difference can be reduced to be within 0.5, and the scratch-resistant performance of the part made of the polypropylene interior material for the automobile is greatly improved.

2. The deodorant containing the microporous water-containing structure is adopted, so that small molecular substances released from the material can be absorbed when the material is extruded by an extruder, the small molecular substances are almost completely removed along with the evaporation of water vapor under the pressure of high vacuum, and the odor grade and TVOC (total volatile organic compound) of the material can be effectively reduced

The content of (total volatile organic compounds) so as to meet the odor grade standard of the automotive interior material of each host factory being less than or equal to 3.0 and the TVOC content standard. When the automobile odor-resistant toilet seat is used by a consumer, the toilet seat cannot be interfered by peculiar smells in an automobile, and meanwhile, the toilet seat cannot be damaged by VOC (volatile organic compounds) to the health of a human body, so that the toilet seat has great practical benefit. The pore diameter of the smell removing agent is 10-50 um, if the pore diameter is too small to be adsorbed, the pore diameter is too large, and small molecules are easy to be separated.

Detailed Description

In order to better understand the technical solution of the present invention, the following description is made with reference to specific examples, but the scope of the present invention is not limited thereto.

The raw materials used in the example grade comparative examples are as follows:

polypropylene: the middle melting impact block copolymerization polypropylene produced by a gas phase hydrogen regulation method has the polypropylene melting index of 20-30g/10min and the cantilever beam notch impact strength of 8-15kJ/m²The following examples and comparative examples are medium impact co-polypropylene from Zhonghai Shell;

talc powder: DV50 particle size is less than or equal to 5um, and in the following examples and comparative examples, there is Quanzhou Xufeng talc;

a toughening agent: ethylene octene copolymers or ethylene butene copolymers, common commercial products; 875L to SK in korea in the following examples and comparative examples;

antioxidant: hindered phenol, thioester or sulfite antioxidants, common commercial products; 1010,168 for linaloon in the following examples and comparative examples;

lubricant: n, N' -ethylene bis stearamide, polyethylene wax, polypropylene wax, calcium stearate, zinc stearate or magnesium stearate, common commercial products; in the following examples and comparative examples, calcium stearate is based on Italian hair;

light stabilizer: a common commercially available product; the main component is hindered amine compound, in the following examples and comparative examples, it is adico LA-402 AF;

scratch-resistant agent: silicone and erucamide scratch-resistant agents, common commercial products; in the following examples and comparative examples, specifically Dow Corning's MB50-001, Xeno's amide wax;

odor removing agent: the product model of the deodorant produced by new Guangzhou Miluo materials factory is NSA-RSC 486.

Example 1

The polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 65% of co-polypropylene, 20% of talcum powder, 10% of toughening agent, 0.4% of antioxidant, 0.4% of lubricant, 0.2% of light stabilizer, 2% of silicone scratch-resistant agent, 1% of erucic acid scratch-resistant agent and 1% of odor remover.

The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is prepared according to the following method:

(1) weighing the co-polypropylene, the talcum powder, the toughening agent, the antioxidant, the lubricant, the scratch-resistant agent and the deodorant according to the weight percentage, adding the materials into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;

(2) adding the obtained premix into a parallel double-screw extruder from a main feeding hopper, wherein the length-diameter ratio of the double-screw extruder is required to be 48:1, and shearing, melting, blending and extruding all component materials in the parallel double-screw extruder, wherein the processing temperatures of the double-screw extruder are respectively 175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,200 ℃,210 ℃,205 ℃,200 ℃,195 ℃ and 190 ℃, the vacuum degree of the double-screw extruder is required to be less than or equal to-0.08 MPa, and the vacuum degree of the double-screw extruder is-0.10 MPa in the embodiment;

(3) and cooling, drying and granulating the material strips extruded from the die of the parallel double-screw extruder to obtain the low-odor low-VOC scratch-resistant polypropylene interior trim composite material for the vehicle.

Example 2

The polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 64% of co-polypropylene, 20% of talcum powder, 10% of toughening agent, 0.4% of antioxidant, 0.4% of lubricant, 0.2% of light stabilizer, 2% of silicone scratch-resistant agent, 1% of erucic acid scratch-resistant agent and 2% of odor removing agent.

The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is prepared according to the preparation method of example 1.

Example 3

The polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 63% of co-polypropylene, 20% of talcum powder, 10% of toughening agent, 0.4% of antioxidant, 0.4% of lubricant, 0.2% of light stabilizer, 2% of silicone scratch-resistant agent, 1% of erucic acid scratch-resistant agent and 3% of odor removing agent.

The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is prepared according to the preparation method of example 1.

Comparative example 1

The polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 69% of co-polypropylene, 20% of talcum powder, 10% of flexibilizer, 0.4% of antioxidant, 0.4% of lubricant and 0.2% of light stabilizer.

The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is prepared according to the preparation method of example 1.

Comparative example 2

The polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 66% of co-polypropylene, 20% of talcum powder, 10% of toughening agent, 0.4% of antioxidant, 0.4% of lubricant, 0.2% of light stabilizer and 3% of silicone scratch-resistant agent.

The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is prepared according to the preparation method of example 1.

Comparative example 3

The polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 66 percent of polypropylene copolymer, 20 percent of talcum powder, 10 percent of flexibilizer, 0.4 percent of antioxidant, 0.4 percent of lubricant, 0.2 percent of light stabilizer and 3 percent of erucic acid scratch-resistant agent.

The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is prepared according to the preparation method of example 1.

Comparative example 4

The polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 66% of co-polypropylene, 20% of talcum powder, 10% of flexibilizer, 0.4% of antioxidant, 0.4% of lubricant, 0.2% of light stabilizer, 1% of silicone scratch-resistant agent and 2% of erucic acid scratch-resistant agent.

The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is prepared according to the preparation method of example 1.

Comparative example 5

The polypropylene interior material for the low-odor low-VOC scratch-resistant vehicle comprises the following components in percentage by weight: 66% of co-polypropylene, 20% of talcum powder, 10% of flexibilizer, 0.4% of antioxidant, 0.4% of lubricant, 0.2% of light stabilizer, 2% of silicone scratch-resistant agent and 1% of erucic acid scratch-resistant agent.

The low-odor low-VOC scratch-resistant polypropylene interior material for the vehicle is prepared according to the preparation method of example 1.

The polypropylene interior materials prepared in the above examples 1 to 3 and comparative examples 1 to 5 were tested for their properties, and the test results are shown in the following table 1. The components of the polypropylene material and the test results in table 1 show that, for the polypropylene material for the automotive interior, a small amount of the scratch-resistant agent and the deodorant is added, so that the conventional mechanical properties of the material are slightly affected, and the caused change is almost negligible like the test error. As can be seen from the analysis of comparative examples 1-3, for the scratch resistance of the material, the scratch resistance of the automotive interior material can be improved by singly using the silicone type scratch resistance agent or the erucic acid type scratch resistance agent, wherein the color difference data before and after the material is scratched by using the silicone type scratch resistance agent is smaller, namely the improvement effect on the scratch resistance of the material is more obvious. The silicone scratch-resistant agent has relatively large molecular weight, has certain compatibility with polypropylene resin, can be well distributed in the polypropylene resin, can remarkably reduce the surface friction of the polypropylene material due to the low surface tension and lubricity of the silicone, and can achieve good scratch-resistant effect when a workpiece is damaged by external force. The erucic acid scratch-resistant agent has relatively small molecular weight, and the micromolecules slowly migrate to the surface of the material after injection molding, so that the friction coefficient of the surface of the material is reduced, and the scratch-resistant effect of a workpiece is improved. As can be seen from the results of the scratch resistance tests of the comparative examples 2 to 5, when the erucic acid type scratch resistance agent and the silicone type scratch resistance agent are compounded and used according to a certain proportion, a better scratch resistance effect can be obtained compared with the case of singly using the silicone type scratch resistance agent. The reason is that while the silicone macromolecules are compatible with the polypropylene resin, the erucic acid macromolecules migrate to the surface of the material, so that the external lubrication of the surface of a material part is increased, the friction coefficient is reduced, and the silicone macromolecules and the polypropylene resin are combined to obtain a better scratch-resistant effect. Particularly, the scratch-resistant effect of the material prepared by compounding the silicone and erucic acid scratch-resistant agents according to the proportion of 2:1 is the best.

TABLE 1 Material formulation

Table 2 results of performance testing

Comparing examples 1-3 with comparative example 5, it can be seen that the odor grade and VOC content of the material can be significantly improved by adding the odor eliminating agent, because the structure of the odor eliminating agent is selected to be a microporous water-containing structure, which can absorb the small molecular substances released from the material when the material is extruded by an extruder, and the small molecular substances are removed along with the evaporation of water vapor under the pressure of high vacuum, thereby achieving the effect of reducing the odor and VOC content of the material. As can be seen from examples 2 and 3, the odor grade effect and VOC content achieved by adding 2% of the deodorant and 3% of the deodorant are basically the same, because the content of the deodorant is saturated, and the odor grade and VOC content of the small molecular substances in the machine are not changed greatly because the small molecular substances are absorbed and evaporated by water molecules by adding 2% of the deodorant.

The above description is only for the purpose of describing some embodiments of the present invention, and therefore should not be construed as limiting the scope of the present invention, i.e. the present invention is intended to cover all modifications, improvements and substitutions within the scope of the present invention and the scope of the present invention.