CN115895168A - Polyolefin thermoplastic elastomer and preparation method thereof - Google Patents
Polyolefin thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyolefin thermoplastic elastomer and a preparation method thereof, belonging to the technical field of polymer composite materials. The polyolefin thermoplastic elastomer comprises the following components: block copolymerization polypropylene, ethylene-alpha-olefin copolymer, compatilizer, matte regulator, random copolymerization polypropylene, lubricant and antioxidant; the matte regulator is a compound of a copolymer of an ethylene-acrylic acid derivative and nano spherical powder. The polyolefin thermoplastic elastomer material disclosed by the invention has a good matte effect, excellent low-temperature toughness, good rigidity-toughness balance, excellent comprehensive mechanical properties, and good processing flowability and demolding property. The preparation method disclosed by the invention is simple in preparation process, can be used for continuous large-scale production, does not need to add reinforced powder, is low in density, does not need to add a cross-linking agent and alkane oil, is low in VOC (volatile organic compound) content, can be recycled, and accords with the trend of green development of the plastic industry.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a polyolefin thermoplastic elastomer and a preparation method thereof.
Background
Thermoplastic elastomer (TPE) is a high polymer material with rubber elasticity and Thermoplastic plastic processability, and because the TPE has the advantages of small pollution, wide hardness range, good mechanical property, excellent processability, light density, recyclability and the like, the TPE material gradually replaces the traditional rubber material, and the TPE material is more and more widely applied to the field of automobiles.
With the rapid development of the automobile industry, the safety of automobiles is receiving more and more attention while seeking high performance, high quality and energy saving. In recent years, various governments have issued serial laws and standards to ensure the safety of automobiles, and the development of an air bag system as a very important passive safety technology for automobiles is also considerably emphasized.
In addition to the main components of an automotive airbag system, such as sensors, microprocessors, gas generators, and airbags, an airbag cover is also an important component. Thermoplastic elastomers are the primary materials used for automotive airbag covers. Thermoplastic elastomers used as airbag covers are mainly polyolefin blend type thermoplastic elastomers (TPO and TPV), polyurethane type thermoplastic elastomers (TPU), polyester type thermoplastic elastomers (TPEE). Among them, polyolefin thermoplastic elastomers (TPO) are most commonly used because of their wide source of raw materials, simple preparation process, high cost performance, and light weight.
In order to smoothly open the airbag during the explosion, a weakening line is formed on the airbag cover so that the airbag cover can be easily torn along the weakening line when being pressed by the airbag, and the weakening line is generally formed by a laser. Currently, an integrated airbag that integrates safety, comfort, and aesthetic features has become a trend, but also puts higher demands on the materials used for the airbag cover. On one hand, the air bag cover plate is required to have certain pressure bearing performance so as to prevent the weakening line from being easily broken after being pressed; on the other hand, the air bag cover plate is required to have good normal temperature and low temperature toughness and proper tensile strength, so that the air bag cover plate can be smoothly unfolded during air bag blasting, and meanwhile, no fragment flies out to cause secondary damage to a human body. In addition, as the material of the automobile instrument panel, in order to avoid the problem of traffic safety caused by light reflection, a matte design is preferably adopted in principle.
The current TPO materials mainly have the defects of high glossiness (non-matte), poor rigidity and toughness balance, poor low-temperature toughness, poor melt flowability, large specific gravity and the like. Can not meet the higher requirements of the current automobile development on the safety airbag material. Therefore, further development and research of TPO materials are necessary.
Aiming at the defects existing in the current TPO material, the improvement is mainly carried out by the following scheme:
1. the surface glossiness of the material is reduced by blending modification and the like.
(1) The function of reducing the surface glossiness of the material is achieved by simply adding inorganic extinction powder, such as nano zinc oxide, aluminum oxide, magnesium oxide, silicon dioxide, multilayer graphene and the like. However, the inorganic matting powder has poor compatibility with TPO materials, is not easy to disperse uniformly when being directly added, is easy to agglomerate, has large addition amount, can generate large adverse effect on the mechanical property of the materials, and the obtained product has general matte effect.
(2) The purpose of matting is achieved by adding another polymer as a matte agent, but the organic matte agent has the problems of poor compatibility with the matrix resin and large addition amount, and the physical properties of the material are greatly reduced.
2. Toughening modification, especially improving the low-temperature toughness of TPO.
Toughening modification of TPO is mainly aimed at polypropylene (PP), and although polypropylene copolymer (PPB) has high impact property at normal temperature, impact is poor at low temperature of-45 ℃ and is generally not higher than 10kJ/m 2 Brittle fracture was exhibited. Therefore, in order to improve the low temperature toughness of the copolymerized polypropylene, modification may be performed by adding ethylene- α -olefin copolymer (POE) or Ethylene Propylene Diene Monomer (EPDM). The research shows that the melt fluidity of PP is obviously reduced along with the increase of the amount of EPDM due to the high Mooney viscosity of EPDM, besides, EPDM is massive and is not beneficial to processing, the selection of the granules is few, and the shrinkage rate of EPDM to PP is not obviously improved, which limits the application of EPDM in PP modification. Compared with EPDM (ethylene-propylene-diene monomer), the Mooney viscosity of POE (polyolefin elastomer) is much smaller, the influence on the melt flowability of PP (polypropylene) is small along with the increase of the use amount of POE, POE is granules, the POE is easy to process, the reduction degree of the strength and the modulus of PP is not large like EPDM (ethylene-propylene-diene monomer), and in addition, the low-temperature toughness of PP can be obviously improved by POE. However, there is a disadvantage that the addition of POE does not significantly improve the elongation at break of PPB, and even decreases the elongation at break of PPB. Therefore, how to balance the strength and toughness of the TPO material and improve the low temperature toughness is still a problem to be further improved and solved.
In addition, there have been few studies on the relationship between physical properties of TPO materials and laser weakening quality. Therefore, the developed polyolefin thermoplastic elastomer with simplified process, matte, excellent low-temperature toughness, balanced rigidity and toughness, low shrinkage rate, light density and good melt fluidity has wide application prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyolefin thermoplastic elastomer and a preparation method thereof. The polyolefin thermoplastic elastomer has a good matte effect, and has excellent low-temperature toughness and melt flowability.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect, the present invention provides a polyolefin thermoplastic elastomer, comprising the following components in parts by weight: 40-70 parts of block copolymerization polypropylene, 10-40 parts of ethylene-alpha-olefin copolymer, 10-40 parts of compatilizer and 0.5-5 parts of matte regulator;
the matte regulator is a compound of a copolymer of an ethylene-acrylic acid derivative and nano spherical powder; the weight ratio of the copolymer of the ethylene-acrylic acid derivative to the nano spherical powder is (1-7): 1.
the polyolefin thermoplastic elastomer (TPO) material selects block copolymerization polypropylene (PPB) and ethylene-alpha-olefin copolymer (POE) as basic raw materials, and a compound of a copolymer of ethylene-acrylic acid derivatives and nano spherical powder is added as a matte regulator, so that the glossiness of the material can be obviously reduced, a matte surface is endowed to the material, and the material has good mechanical properties.
The weight ratio of the copolymer of the ethylene-acrylic acid derivative to the nano spherical powder is crucial, and the matte effect and the comprehensive performance of the material are influenced. If the addition amount of the nano powder is too large, agglomeration is easy to occur during processing, the nano powder is not easy to disperse, the melt flowability of the material is reduced, the processing performance is influenced, the mechanical property of the material is reduced, and particularly the tensile elongation at break and the impact strength (toughness) at normal temperature and low temperature of the material are greatly reduced.
The copolymer of ethylene-acrylic acid derivative is an amphiphilic copolymer, the ethylene unit is nonpolar and has good compatibility with materials such as POE, propylene-ethylene copolymer and the like, and the acrylic acid derivative unit is strong polarity and has poor compatibility with materials such as polypropylene, POE, propylene-ethylene copolymer and the like. The addition of the ethylene-acrylic acid derivative copolymer to the polyolefin raw material system of the present invention disturbs the flow and crystallization of the system, thereby forming micro-wrinkles on the surface of the article during injection molding. In addition, a small amount of nano spherical powder is added, a microscopic concave-convex structure can be formed on the surface of a product, and the reflectivity of the spherical powder to light is low. The microscopic wrinkles and the concave-convex structure on the surface of the product can diffuse light, so that the glossiness of the surface of the product is reduced, and a matte effect is generated.
The benefits of adding the copolymer of ethylene-acrylic acid derivatives and the nano spherical powder are: on one hand, the copolymer of ethylene-acrylic acid derivatives has amphiphilic property, can be used as a special compatible dispersant, improves the compatibility of the nano spherical powder and polyolefin, and promotes the dispersion of the nano spherical powder, thereby ensuring that the TPO product has good mechanical property. On the other hand, the synergistic effect of the two substances can ensure that the surface of the TPO product has good matt effect under the condition that the dosage of the matte surface regulator is relatively small. Meanwhile, the addition of the ethylene-acrylic acid derivative copolymer can properly improve the polarity of TPO, and further promote the adhesion of a TPO skin layer and an air bag cover plate foaming layer (mostly polar foaming materials such as PVC, TPU and the like).
The ethylene-alpha-olefin copolymer (POE) is mainly an ethylene-butylene or ethylene-octene copolymer, and has poor compatibility with PPB because propylene does not exist in a molecular chain. The invention improves the compatibility of POE and PPB by adding the compatilizer, endows the material with excellent low-temperature toughness, and ensures that the notch impact strength of the material is still higher than 60kJ/m even at the low temperature of minus 45 DEG C 2 And exhibits incomplete fracture in toughness.
According to the invention, by selecting the specific raw material components and the specific component proportion, the obtained polyolefin thermoplastic elastomer material has the advantages of good matt effect, excellent low-temperature toughness, good rigidity-toughness balance, good processing fluidity and demolding performance, and low molding shrinkage. The prepared TPO material has the gloss of less than 10 degrees, the flexural modulus of more than 450MPa, the elongation at break at normal temperature (23 ℃) of more than 500 percent, the Melt Flow Rate (MFR) of more than 6g/10min and the molding shrinkage of not more than 1.0 percent.
Preferably, the polyolefin thermoplastic elastomer comprises the following components in parts by weight: 50-60 parts of block copolymerization polypropylene, 15-30 parts of ethylene-alpha-olefin copolymer, 10-25 parts of compatilizer and 1-3 parts of matte regulator; the total weight of the ethylene-alpha-olefin copolymer and the compatilizer accounts for 25 to 60 percent of the total weight of the components.
Under the preferable component ratio, the bending modulus of the prepared TPO material is more than 460MPa, the normal temperature elongation at break is more than 520%, and the Melt Flow Rate (MFR) is more than 6.8g/10 min.
Preferably, the weight part of the nano spherical powder is 0.3-2 parts. When the weight portion of the added nano powder is in the range, the TPO product surface has good matt effect and excellent mechanical property.
Preferably, the weight part of the nano spherical powder in the matte conditioning agent is 0.5-1. The bending modulus of the prepared TPO material can reach more than 500 Mpa.
Preferably, the ethylene-acrylic acid derivative copolymer is at least one of ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate copolymer (EBA); the nano spherical powder is at least one of nano titanium dioxide, nano calcium carbonate, nano zinc oxide and nano zinc sulfide.
Preferably, the compatilizer is a propylene-ethylene copolymer, and the content of the propylene unit in the propylene-ethylene copolymer is 40-90% by weight.
The invention improves the compatibility of the block copolymerization polypropylene and the ethylene-alpha-olefin copolymer by using the propylene-ethylene copolymer as the compatilizer, and the low-temperature toughness of the material is obviously improved. When the weight percentage content of the propylene unit in the propylene-ethylene copolymer is 40-90%, the compatibility of the PPB and the POE can be obviously improved, and the elongation at break of the PPB is obviously improved.
When the compatilizer is not added, the tensile strength and the elongation at break of the obtained polyolefin thermoplastic elastomer at normal temperature (23 ℃) and low temperature (-30 ℃) are reduced, and especially the elongation at break at low temperature is obviously reduced; at the same time, the notched impact strength at normal temperature (23 ℃) and low temperature (-45 ℃) also decreases.
Preferably, the content of the propylene unit in the compatilizer is 70-85% by weight.
Preferably, the melt flow rate of the block copolymerization polypropylene under the conditions of the temperature of 230 ℃ and the load of 2.16kg is 3-35 g/10min.
Preferably, the notched Izod impact strength of the block copolymer polypropylene at normal temperature is 10kJ/m 2 As described above.
Preferably, the ethylene- α -olefin copolymer is an ethylene-1-butene copolymer or an ethylene-1-octene copolymer; the ethylene-alpha-olefin copolymer has a tensile strength of 5MPa or more.
Preferably, the polyolefin thermoplastic elastomer further comprises the following components in parts by weight: 3 to 15 portions of random copolymerization polypropylene, 0.1 to 0.7 portion of lubricant and 0.2 to 0.8 portion of antioxidant.
The random copolymerization polypropylene is mainly used as a melting enthalpy regulator of a system, and the random copolymerization polypropylene mainly has the function of adjusting the melting peak temperature and the melting enthalpy of a material, so that the material can form a weakening line with more stable depth, thickness and the like during laser weakening processing. The addition of the random copolymerization polypropylene, the POE, the compatilizer and the like can jointly influence the melting crystallization behavior of the system, thereby influencing the melting enthalpy.
The invention endows the material with high melt fluidity by selecting the polypropylene with high melt fluidity and a proper amount of lubricant, so that the material is easy to process and demould.
Laser weakening is essentially the process of converting light energy into heat energy, causing melting, vaporization and decomposition of the plastic. Laser weakening is one of the most critical technologies in the production of the airbag cover plate, and in order to ensure the safety of the airbag, the depth, the diameter and the like of the weakening line of the airbag cover plate must be precisely controlled. The inventor finds through experiments that the added random copolymer polypropylene can reduce the melting temperature and the melting enthalpy of TPO, even regulate and control the melting temperature and the melting enthalpy to a specific range, so that laser weakening processing is completed under relatively low power, adjustment of laser weakening parameters is reduced, and the processing precision of a weakening line is ensured.
Preferably, 3 to 10 parts of random copolymerization polypropylene, 0.3 to 0.6 part of lubricant and 0.4 to 0.6 part of antioxidant.
Preferably, the melting peak temperature of the random copolymer polypropylene is 10 to 20 ℃ lower than that of the block copolymer polypropylene; the melting enthalpy of the random copolymerization polypropylene is 3 to 14J/g smaller than that of the block copolymerization polypropylene.
Random copolymerization polypropylene with melting peak temperature and melting enthalpy lower than PPB is selected, so that the method is favorable for matching with the existing laser weakening processing technology, and the processing precision of the weakening line is ensured. In addition, the used random copolymerization polypropylene has good compatibility with a system, small addition amount and better impact strength, so that the TPO material has excellent comprehensive mechanical properties.
Preferably, the lubricant is at least one of hyperbranched silicone, silicone oil and silicone.
The selection of the high-fluidity block copolymerization polypropylene raw material is the first step of ensuring the high fluidity of the TPO material, and the addition of a proper amount of lubricant can also play a role in reducing the shearing force of the raw material during screw processing and improving the fluidity of a melt. In addition, suitable lubricants aid in demolding after cooling of the melt injection molding, reducing deformation and damage to the article. The invention selects special hyperbranched organosilicon, silicone oil, silicone and the like as the lubricant, has less addition amount, good lubricating property and demoulding property and little influence on the comprehensive performance of the product.
Preferably, the antioxidant is at least one of antioxidant 168, antioxidant 1010 and antioxidant 1076.
The antioxidant used in the invention is an antioxidant commonly used in plastic processing, and aims to reduce decomposition or aging of raw materials in the processing and using processes.
In a second aspect, the present invention provides a method for preparing the above polyolefin thermoplastic elastomer, comprising the steps of:
and (2) uniformly mixing the block copolymerization polypropylene, the ethylene-alpha-olefin copolymer, the compatilizer, the matte regulator, the random copolymerization polypropylene, the lubricant and the antioxidant, and performing double-screw melt extrusion, granulation and drying to obtain the polyolefin thermoplastic elastomer.
The polyolefin thermoplastic elastomer with good matte effect, excellent low-temperature toughness, balanced rigidity and toughness, low shrinkage rate, low density and good melt fluidity can be prepared by compounding block copolymerization polypropylene, ethylene-alpha-olefin copolymer, compatilizer, matte regulator, random copolymerization polypropylene, lubricant, antioxidant and the like with proper varieties and dosage, and performing melt blending, extrusion and granulation by a screw extruder. The preparation method has the advantages of simple preparation process, easy large-scale production, no need of adding reinforcing powder, low density, no need of adding a cross-linking agent and alkane oil, low content of Volatile Organic Compounds (VOC), recycling and reutilization and good application prospect.
The polyolefin thermoplastic elastomer prepared by the invention is very suitable for being applied to automotive interior trim, such as automobile instrument panels, airbag cover plates and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a polyolefin thermoplastic elastomer, which is prepared by compounding block copolymerization polypropylene, ethylene-alpha-olefin copolymer, compatilizer, matte regulator, random copolymerization polypropylene, lubricant, antioxidant and other components, and the obtained polyolefin thermoplastic elastomer material has good matte effect, excellent low-temperature toughness, balanced rigidity and toughness, low shrinkage rate, excellent comprehensive mechanical property, and good processing fluidity and demolding property.
(2) The preparation process is simple, can realize continuous large-scale production, does not need to add reinforcing powder, has low density, does not need to add a cross-linking agent and alkane oil, has low VOC content, can be recycled, and accords with the trend of green development of the plastic industry.
Detailed Description
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples, but the scope of the present invention and the embodiments are not limited thereto.
Example 1
In one embodiment of the polyolefin thermoplastic elastomer of the present invention, the raw material formulation of the polyolefin thermoplastic elastomer is shown in table 1, and the preparation method of the polyolefin thermoplastic elastomer of this embodiment comprises the following steps:
weighing block copolymerization polypropylene, ethylene-alpha-olefin copolymer, compatilizer, random copolymerization polypropylene, matte regulator, lubricant and antioxidant according to a formula proportion, uniformly mixing, and performing double-screw melt extrusion, granulation and drying to obtain the polyolefin thermoplastic elastomer.
Examples 2 to 7
The compounding ratios of the raw materials of the polyolefin thermoplastic elastomers of examples 2 to 7 of the polyolefin thermoplastic elastomer of the present invention are shown in Table 1. The polyolefin thermoplastic elastomer was prepared in the same manner as in example 1.
TABLE 1 compositions in parts by weight of the components of the polyolefin thermoplastic elastomers of examples 1 to 7
Comparative examples 1 to 8
The compounding ratios of the polyolefin thermoplastic elastomers of the present invention and those of the polyolefin thermoplastic elastomers of comparative examples 1 to 8 are shown in Table 2. The preparation method of the polyolefin thermoplastic elastomer is the same as that of example 1.
TABLE 2 composition in parts by weight of the components of comparative examples 1 to 8 for polyolefin thermoplastic elastomers
The sources of the raw material information in tables 1 and 2 of the present invention are as follows:
1) PPB1: the material is a Taiwan chemical K9010, MFR =9g/10min and normal-temperature notch impact strength of 50kJ/m 2 Low temperature notched impact at-45 ℃ of 7.5kJ/m 2 ；
2) PPB2: the medium petrochemical Yanshan petrochemical K9026 has MFR =18g/10min and normal-temperature notch impact strength of 53kJ/m 2 Low temperature notched impact at-45 ℃ of 7.7kJ/m 2 ；
3) POE1: LG chemical, lucene-LC670, tensile strength 5.5MPa;
4) POE2: korea SK chemical, solumer-871L, tensile strength 9.6MPa;
5) 1 part of compatilizer: exxonmobil, vistamaxx-8780, with a propylene unit content of 88%;
6) A compatilizer 2: dow chemical, intune-05545, propylene unit content 52%;
7) PPR1: medium petrochemical, HT9025NX, melt flow rate MFR =25g/10min;
8) PPR2: medium petrochemical metallocene, UT8012M, MFR =11.4g/10min;
9) EAA: du pont, usa, 3440;
10 EMA): du pont, usa, 1124AC;
11 EBA): the number of the acalma, france,
12 EEA): the process is carried out by a French acama,
13 Hyperbranched silicones: KJ-A001, KJ plastics technologies, inc., KJ, hangzhou Kaije;
14 Silicone oil): dow Corning Chemicals, PMX-200-100;
15 Silicone: KJ-B01, KJ plastics technologies, inc., KJ, kyozhou Kanji.
Performance testing
The polyolefin thermoplastic elastomers obtained in examples 1 to 7 and comparative examples 1 to 8 were subjected to low-temperature impact strength, average shrinkage, gloss, melting enthalpy and laser weakening test.
1. Low-temperature impact strength: the standard specimens were frozen at-45 ℃ for 4h and then tested rapidly.
2. Average shrinkage: and (3) injection molding TPO granules into platelets of 100mm x 100mm, standing at 23 ℃ for 24 hours, measuring the transverse and longitudinal sizes of the platelets, respectively calculating the transverse and longitudinal shrinkage rates of the platelets by taking the size of a mold as a reference, and then calculating an average value.
3. Gloss: and (3) carrying out injection molding on TPO granules to form small plates, and testing the glossiness of the surfaces of the small plates by using a glossiness tester, wherein the testing angle is 60 degrees.
4. Enthalpy of fusion: melting enthalpy of TPO particles was measured by DSC under the following conditions: 25-220 ℃ and 5 ℃/min.
5. Laser weakening condition: the TPO particles are made into an airbag cover plate, a weakening line is processed on the surface of the TPO particles by adopting a specific laser weakening process, the weakened test piece is cut along the central line of a weakening hole, a ZEISS image measuring system is opened, the test piece to be tested is placed under a micro camera and focused on the surface to be tested, and the processing depth of the weakening line is measured. The diameter of the weakening hole is measured at the same time. And measuring for multiple times (more than 10 times), calculating an average value, and calculating corresponding deviation.
The results of the property tests of the polyolefin thermoplastic elastomers prepared in examples 1 to 7 are shown in Table 3.
TABLE 3
As can be seen from Table 3, the polyolefin thermoplastic elastomers prepared in examples 1 to 7 have excellent low temperature toughness and the TPO material prepared by compounding block copolymerized polypropylene, ethylene-alpha-olefin copolymer (POE), propylene-ethylene copolymer and the like, and the notch impact strength at-45 ℃ is more than 60kJ/m 2 Incomplete fracture of toughness, good balance of rigidity and toughness, and bending modulus greater than that of450MPa, the elongation at break at normal temperature (23 ℃) is more than 500 percent, and the average molding shrinkage is less than 1.0 percent.
According to the invention, through selection of high-fluidity raw materials and addition of special silicon lubricants, the prepared TPO material has good processing fluidity and demolding property, the melt flow index is greater than 6g/10min, and the TPO material is particularly suitable for production of large-block thin-wall products. In addition, the ethylene-acrylic acid derivative copolymer and the spherical nano silicon dioxide are compounded to be used as a matte regulator, so that the glossiness of TPO can be obviously reduced, the glossiness of the prepared TPO material is less than 10 degrees, a good matte effect is presented, and meanwhile, the cohesiveness of the TPO surface layer and polar materials such as PVC, TPU and the like is increased. In addition, compared with the traditional matte conditioning agent, the matte conditioning agent provided by the invention can realize a good matte effect under a small addition amount, and has small influence on the comprehensive performance of the TPO material.
The results of the property tests of the polyolefin thermoplastic elastomers obtained in comparative examples 1 to 8 are shown in Table 4.
TABLE 4
As can be seen from Table 4, in comparison with example 1, in comparative example 1, the tensile strength and elongation at break of the obtained polyolefin thermoplastic elastomer are reduced at both normal temperature (23 ℃) and low temperature (-30 ℃), and especially the elongation at break is reduced significantly at low temperature, without adding a compatibilizer; meanwhile, the notch impact strength at normal temperature (23 ℃) and low temperature (45 ℃) is also reduced, which shows that the compatilizer of the invention has great influence on the tensile strength, the elongation at break and the notch impact strength of the prepared product. Comparative example 2, which is lower in the addition of the compatibilizer compared to example 2, also results in a large decrease in the elongation at break and the notched impact strength.
Compared with example 3, in comparative example 3, the random copolymer polypropylene of the present application is not added as the random copolymer polypropylene, and the amount of the block copolymer polypropylene is correspondingly increased, so that the melting enthalpy of the prepared polyolefin thermoplastic elastomer is higher under the condition of keeping the total weight parts of the raw material components unchanged, which is not beneficial to laser weakening processing, and the depth and diameter fluctuation of the weakening line is large. Compared with example 4, the matte conditioning agent in comparative example 4 only contains calcium carbonate, and the TPO material prepared in comparative example 4 has higher glossiness and poorer matte effect, and the comprehensive performance of the TPO material is reduced. Compared with the prior art, the matte regulator is not added in the comparative example 5, the POE weight is correspondingly increased, the glossiness of the prepared TPO material reaches 56.2 degrees, the reflecting effect is shown, and the use requirement cannot be met. In comparative examples 6 to 8, the ethylene-acrylic acid derivative copolymer or the nano spherical powder is not added according to the type and the amount of the invention, so that the prepared TPO material has higher glossiness, poorer matte effect and reduced mechanical property to a certain extent, and the fact that the TPO material has good matte effect by properly proportioning, using amount and compounding the ethylene-acrylic acid derivative copolymer and the nano spherical powder is shown.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The polyolefin thermoplastic elastomer is characterized by comprising the following components in parts by weight: 40-70 parts of block copolymerization polypropylene, 10-40 parts of ethylene-alpha-olefin copolymer, 10-40 parts of compatilizer and 0.5-5 parts of matte regulator;
the matte regulator is a compound of a copolymer of ethylene-acrylic acid derivatives and nano spherical powder; the weight ratio of the copolymer of the ethylene-acrylic acid derivative to the nano spherical powder is (1-7): 1.
2. the polyolefin thermoplastic elastomer of claim 1, comprising the following components in parts by weight: 50-60 parts of block copolymerization polypropylene, 15-30 parts of ethylene-alpha-olefin copolymer, 10-25 parts of compatilizer and 1-3 parts of matte regulator; the total weight of the ethylene-alpha-olefin copolymer and the compatilizer accounts for 25 to 60 percent of the total weight of the components.
3. The polyolefin thermoplastic elastomer of claim 1, wherein the nano spherical powder is present in an amount of 0.3 to 2 parts by weight.
4. The polyolefin thermoplastic elastomer of claim 3, wherein the weight portion of the nano spherical powder is 0.5 to 1 portion.
5. The polyolefin thermoplastic elastomer of any one of claims 1 to 4, wherein the copolymer of ethylene-acrylic acid derivative is at least one of an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-butyl acrylate copolymer; the nano spherical powder is at least one of nano titanium dioxide, nano calcium carbonate, nano zinc oxide and nano zinc sulfide.
6. The polyolefin thermoplastic elastomer of any one of claims 1 to 4, wherein said compatibilizer is a propylene-ethylene copolymer having a propylene unit content of 40 to 90% by weight.
7. The polyolefin thermoplastic elastomer of any one of claims 1 to 4, wherein said block copolypropylene has a melt flow rate of 3 to 35g/10min at a temperature of 230 ℃ and a load of 2.16 kg; the ethylene-alpha-olefin copolymer is an ethylene-1-butene copolymer or an ethylene-1-octene copolymer.
8. The polyolefin thermoplastic elastomer of any of claims 1-4, further comprising the following components in parts by weight: 3 to 15 portions of random copolymerization polypropylene, 0.1 to 0.7 portion of lubricant and 0.2 to 0.8 portion of antioxidant.
9. The polyolefin thermoplastic elastomer of claim 8, wherein the melting peak temperature of said random copolymer polypropylene is 10 to 20 ℃ lower than the melting peak temperature of said block copolymer polypropylene; the melting enthalpy of the random copolymerization polypropylene is 3-14J/g less than that of the block copolymerization polypropylene.
10. A process for the preparation of a polyolefin thermoplastic elastomer according to any of claims 8 to 9, comprising the steps of:
and (2) uniformly mixing the block copolymer polypropylene, the ethylene-alpha-olefin copolymer, the compatilizer, the matte regulator, the random copolymer polypropylene, the lubricant and the antioxidant, and performing double-screw melt extrusion, granulation and drying to obtain the polyolefin thermoplastic elastomer.
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