WO2022206611A1

WO2022206611A1 - Polypropylene composition and preparation method therefor

Info

Publication number: WO2022206611A1
Application number: PCT/CN2022/083107
Authority: WO
Inventors: 苏娟霞; 杨波; 罗忠富; 黄险波; 叶南飚; 吴亦建; 卢朝亮; 彭莉; 吴国峰; 陈延安
Original assignee: 金发科技股份有限公司
Priority date: 2021-03-31
Filing date: 2022-03-25
Publication date: 2022-10-06
Also published as: CN113150436A; CN113150436B

Abstract

Disclosed in the present invention are a polypropylene composition and a preparation method therefor. The polypropylene composition comprises the following components in parts by weight: 40-90 parts of polypropylene, 10-35 parts of toughening agent, 5-25 parts of filler, and 0.2-1 parts of secondary amide adjuvant; the structural formula of the secondary amide adjuvant is R₁-CO-NH-R₂, wherein R₁ is a saturated chain segment with a carbon atom number of 15-22 or an unsaturated chain segment with a carbon atom number of 15-22, and R₂ is a saturated chain segment with a carbon atom number of 15-22 or an unsaturated chain segment with a carbon atom number of 15-22. The present invention uses the secondary amide adjuvant as a low surface tension adjuvant that can significantly reduce the surface tension of the polypropylene material, so that shoe polish droplets and stains can freely roll off the surface of a sample plate, thereby having the effect of improving the anti-stain adhesion of the surface of the material, and meeting the usage requirements of automobile interior trims.

Description

A kind of polypropylene composition and preparation method thereof

technical field

The invention relates to the technical field of polypropylene materials, in particular to a polypropylene composition and a preparation method thereof.

Background technique

The polarity of polypropylene molecular chain is low, and its own surface tension is relatively low. The surface of ordinary talc-filled elastomer-toughened modified polypropylene material has a certain low surface tension, but this level of low surface tension cannot be achieved like a lotus leaf. A state in which the stain droplets roll freely on the surface without sticking to the surface. In actual use, car interiors such as door panels, racks, etc. may often come into contact with some stains such as coffee, juice, tea, etc., leaving traces that are difficult to erase. With the popularization of new travel modes such as online car-hailing, the performance requirements for anti-stain adhesion on the surface of automobile interiors are getting higher and higher.

According to Young's equation, after the liquid pollution source is in contact with the material surface, there may be different states such as attachment, spreading, and penetration. For the same pollution source, reducing the surface tension of the material can increase the contact angle between the pollution source and the liquid. The larger the contact angle, the smaller the adhesion between the liquid and the material surface. In order to reduce the surface tension of materials, researchers have made a lot of efforts, and many low surface tension materials have been developed. CN101200524A discloses a low surface tension polypropylene material. By mixing polypropylene raw materials with low surface tension fluorochemical monomers with unsaturated double bonds and co-grafting monomers, the low surface tension is prepared by the method of grafting. Surface tension water resistant polypropylene material. CN105440604A discloses a low surface tension PBT resin, which uses polyethylene glycol, oxidized polyethylene wax, stearate, metal soap or stearamide to reduce the surface tension of the PBT body, instead of the application of TPX resin. However, there is no relevant report on the scheme of using secondary amide additives to modify polypropylene materials to reduce the surface tension of polypropylene systems, thereby improving the anti-stain adhesion effect on the surface of polypropylene materials.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the deficiencies of the prior art and provide a polypropylene composition, the polypropylene composition has low surface tension and good anti-stain adhesion effect, and can be used for preparing automobile interior parts.

To achieve the above object, the technical scheme adopted by the present invention is:

A polypropylene composition, comprising the following components in parts by weight: 40-90 parts of polypropylene, 10-35 parts of toughening agent, 5-25 parts of filler and 0.2-1 part of secondary amide auxiliary;

The structural formula of the secondary amide auxiliary agent is R ₁ -CO-NH-R ₂ , wherein R ₁ is a saturated chain segment with a carbon number of 15-22 or an unsaturated chain segment with a carbon number of 15-22, and R ₂ is a saturated segment having 15-22 carbon atoms or an unsaturated segment having 15-22 carbon atoms.

In the above structural formula, R ₁ and R ₂ may be the same or different.

The inventor's experiments found that the use of primary amide additives and bifunctional amide additives could not reduce the surface tension of polypropylene materials, and did not significantly improve the anti-stain adhesion on the material surface. In the present invention, the secondary amide auxiliary agent with the above structure is used as the low surface tension auxiliary agent, which can significantly reduce the surface tension of the polypropylene material, and realize the free rolling of shoe polish stains on the surface of the sample plate, thereby improving the anti-stain adhesion on the surface of the material. effect.

If the content of secondary amide additives in the system is too low, the surface tension reduction effect of the material and the anti-stain adhesion effect on the surface will not be significantly improved, while the content of secondary amide additives is too high, which will lead to poor anti-stain adhesion effect on the surface of the material. Slight deterioration, therefore, in order to ensure that polypropylene materials with low surface tension are obtained, the weight part of secondary amide additives in the formulation system of the present invention is controlled to be 0.2-1 part by weight.

Further, the weight part of the secondary amide auxiliary agent in the polypropylene composition is 0.3-0.4 part, within this content range, it is beneficial to reduce the surface tension of the system, and the surface of the prepared polypropylene material has an anti-stain adhesion effect. better and better mechanical properties.

By optimizing the composition of the polypropylene system in the present invention, the obtained polypropylene composition has lower surface tension and anti-stain adhesion effect, and can meet the use requirements of automobile interior parts.

Further, the secondary amide additives include oleic palmitic acid amide, stearyl stearic acid amide, stearyl erucic acid amide, oleic acid behenic acid amide, stearyl oleic acid amide, stearyl behenic acid amide At least one of uric acid amide and bis-erucic acid amide is beneficial to reduce the surface tension of the polypropylene material, realize the free rolling of shoe polish stains on the surface of the sample, and improve the anti-stain adhesion effect of the material.

Further, the polypropylene includes at least one of homo-polypropylene and copolymerized polypropylene, the polypropylene is tested according to ASTM D792-2013, and its density is 0.894-0.914 g/cm ³ , and the polypropylene is tested according to ASTM D792-2013 According to D1238-2013 standard, the melt mass flow rate under the test condition of 230℃ and 2.16kg is 0.5～100g/10min.

Further, the toughening agent is an ethylene-alpha olefin copolymer, and according to the ASTM D1238-2013 standard, the melt mass flow rate of the toughening agent under the test condition of 190 ° C and 2.16 kg is 0.1-30 g/10min.

Further, the filler includes at least one of talc, whisker, calcium carbonate, barium sulfate, and wollastonite.

Further, within the scope of not adversely affecting the surface tension of the polypropylene system of the present invention, the polypropylene composition further comprises the following components by weight: 0-12 parts of polyethylene, 0.1-0.5 parts of antioxidant , 0.1-0.5 part of light stabilizer and 0.5-1 part of color masterbatch.

Further, the polyethylene is high-density polyethylene (HDPE), and according to the ASTM D1238-2013 standard, its melt mass flow rate at 190° C. under the test condition of 2.16kg is 0.1～30g/10min.

Further, the antioxidants include hindered phenolic antioxidants and phosphite antioxidants.

Further, the light stabilizer is a hindered amine light stabilizer.

The present invention also provides a preparation method of the above polypropylene composition, comprising the following steps:

(1) each component is weighed by weight proportion and added to the high mixer to mix for 1 to 3 minutes, and the rotating speed is 1000 to 2000 rpm to obtain a premix;

(2) The premix is melted and extruded through a twin-screw extruder, the temperature of each zone of the screw is 190-230° C., and the polypropylene composition is obtained by vacuum granulation.

The present invention also provides the application of the above polypropylene composition in automobile interior parts.

The preparation process of the invention is simple and easy to control, suitable for industrial scale production, and the product has low surface tension and anti-stain adhesion effect, and can be widely used for preparing automobile interior decorations, such as instrument panels, door panels, glove boxes, storage racks, etc. Parts for anti-stain adhesion needs.

The present invention also provides the application of the above-mentioned secondary amide auxiliary agent in reducing the surface tension of the polypropylene composition, and the polypropylene composition includes the following components in parts by weight: 40-90 parts of polypropylene, 10-90 parts of toughening agent 35 parts, 5-25 parts of filler and 0.2-1 part of secondary amide additives;

Amide additives are added to the existing polypropylene system, and their function is generally to reduce the friction coefficient of the material, thereby improving the scratch resistance of the material or increasing the slippage to facilitate the release of the material. However, the inventor found through experiments that, in the above polypropylene system, adding an appropriate amount of secondary amide additives can be used as low surface tension additives, which can significantly reduce the surface tension of polypropylene materials, thereby improving the anti-stain adhesion on the surface of the material. effect.

Further, in the above application, the weight part of the secondary amide auxiliary agent in the polypropylene composition is 0.3-0.4 part. Within this content range, the prepared material has both good mechanical properties and surface anti-stain and stickiness. attached effect.

Further, in the above application, the secondary amide additives include oleic palmitic acid amide, stearyl stearic acid amide, stearyl erucic acid amide, oleic acid behenic acid amide, stearyl oleic acid At least one of amide, stearyl behenamide and bis-erucamide can significantly reduce the surface tension of the polypropylene material, thereby improving the anti-stain adhesion effect on the surface of the material.

Further, in the above application, the polypropylene includes at least one ^of homopolymer polypropylene and copolymer polypropylene. According to the ASTM D1238-2013 standard, the polypropylene has a melt mass flow rate of 0.5-100 g/10min under the test conditions of 230° C. and 2.16 kg.

Further, in the above application, the toughening agent is an ethylene-alpha olefin copolymer, and according to the ASTM D1238-2013 standard, the melt mass flow rate of the toughening agent under the test condition of 190 ° C and 2.16 kg is 0.1 ~30g/10min.

Further, in the above application, the filler includes at least one of talc, whisker, calcium carbonate, barium sulfate, and wollastonite.

Further, in the above application, the polypropylene composition further comprises the following components in parts by weight: 0-12 parts of polyethylene, 0.1-0.5 parts of antioxidants, 0.1-0.5 parts of light stabilizers and 0.5 parts of color masterbatches -1 serving.

Further, in the above application, the polyethylene is high-density polyethylene, and according to the ASTM D1238-2013 standard, its melt mass flow rate under the test condition of 190 ° C and 2.16 kg is 0.1 to 30 g/10min.

Further, in the above application, the antioxidants include hindered phenolic antioxidants and phosphite antioxidants.

Further, in the above application, the light stabilizer is a hindered amine light stabilizer.

Compared with the prior art, the beneficial effects of the present invention are:

The invention adopts the secondary amide type auxiliary agent as the low surface tension auxiliary agent, which can significantly reduce the surface tension of the polypropylene material, and realize the free rolling of shoe polish stains on the surface of the sample plate, so as to improve the anti-stain adhesion on the surface of the material, so that the Meet the use requirements of automotive interior parts.

Description of drawings

Figure 1 shows the traces left by the shoe polish droplets corresponding to each level of surface tension evaluation after rolling off the stain on the sample plate.

Detailed ways

In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments.

The raw materials used in the following examples and comparative examples are described as follows:

Polypropylene: Homopolypropylene, PPN-Z30S, according to ASTM D1238-2013, the melt mass flow rate is 26g/10min at 230℃, 2.16kg test condition; according to ASTM D792-2013, its density is 0.897 g/cm ³ ; Maoming Petrochemical;

HDPE: HDPE HMA025, according to ASTM D1238-2013, the melt mass flow rate at 190℃, 2.16kg test condition is 8g/10min; according to ASTM D1505-2018 test, density 0.964g/ ^cm3 ; ExxonMobil ;

Toughening agent: POE Engage 8137, according to ASTM D1238-2013 standard, the melt mass flow rate at 190 ° C, 2.16kg test condition is 13g/10min; according to ASTM D1505-2018 test, density 0.864g/ ^cm3 ; chemistry;

Oleic palmitamide: secondary amide additives, Croda, UK;

Stearyl stearic acid amide: secondary amide additives, British Croda;

Stearyl erucamide: secondary amide additives, British Croda;

Double erucamide: secondary amide auxiliary, Jiangxi Weike;

Oleic acid amide: primary amide auxiliary, British Croda;

Ethylene biserucamide: Bifunctional amide auxiliary, Jiangxi Weltco;

Masterbatch: PE2772, Cabot;

Talc powder: TYT-777A, Beihai Tianyuan;

Antioxidant: including main antioxidant and auxiliary antioxidant, main antioxidant is hindered phenolic antioxidant, model: Irganox 1010, BASF; auxiliary antioxidant is phosphite antioxidant, model: Irganox 168,BASF;

Light stabilizer: LA-402XP, Adico, Japan.

Examples 1-10 and Comparative Examples 1-6: Polypropylene compositions

The components of the polypropylene compositions of Examples 1-10 and Comparative Examples 1-6 are shown in Table 1, and the preparation method of the polypropylene compositions includes the following steps:

The polypropylene compositions prepared in the above examples and comparative examples were injection-molded to obtain samples, and the samples were subjected to surface tension evaluation and mechanical property testing:

1. Evaluation of surface tension

The device for evaluating the surface tension of the sample includes a bracket that can be used to place the sample stably. The bracket can adjust the angle through the gear of the rear seat buckle. The specific operation method is as follows:

(1) Select a certain buckle gear to fix;

(2) Place the template to be compared on the bracket;

(3) absorb liquid stains with a 5ml plastic straw, drop 2 drops on the sample surface at about 1cm above the sample plate, and the liquid stains are commercially available old man's head liquid shoe polish;

(4) Observe the traces left after the liquid stain rolls off, and evaluate the surface tension level according to the traces.

Among them, as shown in Figure 1, the surface tension evaluation grades are as follows:

Level 1: droplets do not shrink and adhere;

Level 2: The droplet shrinks and adheres continuously;

Level 3: The droplet shrinkage breakpoint adheres and there are more than 10 adhesion points;

Level 4: droplet shrinkage breakpoint adhesion and less than 10 adhesion points;

Grade 5: Droplets roll off freely and do not stick at all.

2. Mechanical properties test

Mechanical properties: Flexural modulus was tested according to ISO 178-2001.

Table 1 shows the surface tension evaluation grades and mechanical properties test results of the polypropylene compositions prepared in the above examples and comparative examples.

Table 1 Formulations and surface tension evaluation grade results of polypropylene compositions of Examples and Comparative Examples

Comparing the results of Examples 1-3, Example 10, Comparative Example 1 and Comparative Example 4, or comparing Example 7 and Comparative Example 5, it can be seen that the addition of secondary amide additives can significantly reduce the surface tension of polypropylene materials, and realize shoe polish. The droplets roll freely on the surface of the sample plate, thereby improving the anti-stain adhesion on the surface of the material, but the content of secondary amide additives in the system is too low, and the anti-stain adhesion effect on the surface of the material is not significantly improved. The weight part of the secondary amide auxiliary is preferably 0.2-1 part, but the content of the secondary amide auxiliary is too high, the effect of improving the anti-stain adhesion effect on the surface of the material is not obvious, but it will also lead to the reduction of the mechanical properties of the material. To ensure that polypropylene materials with low surface tension, good anti-stain adhesion effect and good mechanical properties are obtained, the weight part of secondary amide additives in the formulation system of the present invention is preferably 0.3-0.4 parts.

Comparing Example 2, Example 4-6 and Comparative Example 2-3, it was found that under the same content of amide additives, compared with oleic palmitic acid amide, stearyl stearic acid amide, stearin Secondary amide additives such as base erucamide and bis-erucamide, primary amide additives (oleic acid amide) and bifunctional amide additives (ethylene bis-erucamide) can not reduce the surface tension of the system, which has a negative impact on the material. There is no improvement in the surface anti-stain adhesion.

From the results of Examples 7-9, it can be seen that the addition of polyethylene can reduce the surface tension of the system to a certain extent, improve the anti-stain adhesion effect on the surface of the material, and improve the mechanical properties of the material, while antioxidants, light stabilizers and color masterbatches. The anti-stain adhesion effect on the surface of the material is not significantly affected.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.

Claims

A kind of polypropylene composition is characterized in that, comprises the following components by weight:

The structural formula of the secondary amide auxiliary agent is R 1 -CO-NH-R 2 , wherein R 1 is a saturated chain segment with a carbon number of 15-22 or an unsaturated chain segment with a carbon number of 15-22, and R 2 is a saturated segment having 15-22 carbon atoms or an unsaturated segment having 15-22 carbon atoms.
The polypropylene composition according to claim 1, wherein the secondary amide auxiliary agent comprises oleic palmitic acid amide, stearyl stearic acid amide, stearyl erucic acid amide, oleic acid behenic acid amide At least one of acid amide, stearyl oleic acid amide, stearyl behenic acid amide, and bis-erucic acid amide.
The polypropylene composition according to claim 1, characterized in that it has at least one of the following features (a)-(d):

(a) The polypropylene includes at least one of homo-polypropylene and copolymerized polypropylene, the density of the polypropylene is 0.894-0.914 g/cm 3 , and the polypropylene is tested at 230° C. under the condition of 2.16 kg The melt mass flow rate is 0.5 ~ 100g/10min;

(b) the toughening agent is an ethylene-alpha olefin copolymer, and the melt mass flow rate of the toughening agent at 190° C. and 2.16 kg is 0.1-30 g/10min;

(c) the filler comprises at least one of talc, whisker, calcium carbonate, barium sulfate, wollastonite;

(d) The weight part of the secondary amide auxiliary agent in the polypropylene composition is 0.3-0.4 part.
The polypropylene composition according to any one of claims 1-3, further comprising the following components by weight: 0-12 parts of polyethylene, 0.1-0.5 parts of antioxidants, 0.1-0.5 parts of light stabilizers 0.5 part and color masterbatch 0.5-1 part.
The preparation method of the polypropylene composition according to any one of claims 1-4, characterized in that, comprising the following steps:

(1) Weigh each component by weight ratio, add it into a high-mixer and mix for 1 to 3 minutes, and the rotating speed is 1000 to 2000 rpm to obtain a premix;

(2) The premix is melted and extruded through a twin-screw extruder, the temperature of each zone of the screw is 190-230° C., and the polypropylene composition is obtained by vacuum granulation.
Application of the polypropylene composition according to any one of claims 1-4 in automotive interior parts.
The application of secondary amide auxiliary agent in reducing the surface tension of polypropylene composition, characterized in that, the polypropylene composition comprises the following components in parts by weight:

The structural formula of the secondary amide auxiliary agent is R 1 -CO-NH-R 2 , wherein R 1 is a saturated chain segment with a carbon number of 15-22 or an unsaturated chain segment with a carbon number of 15-22, and R 2 is a saturated segment having 15-22 carbon atoms or an unsaturated segment having 15-22 carbon atoms.
The application according to claim 7, wherein the secondary amide auxiliary agents include oleic palmitic acid amide, stearyl stearic acid amide, stearyl erucic acid amide, oleic acid behenic acid amide, At least one of stearyl oleic acid amide, stearyl behenic acid amide, and bis-erucic acid amide.
The application according to claim 7, characterized in that it has at least one of the following features (a)-(d):

(a) The polypropylene includes at least one of homo-polypropylene and copolymerized polypropylene, the density of the polypropylene is 0.894-0.914 g/cm 3 , and the polypropylene is tested at 230° C. under the condition of 2.16 kg The melt mass flow rate is 0.5 ~ 100g/10min;

(b) the toughening agent is an ethylene-alpha olefin copolymer, and the melt mass flow rate of the toughening agent at 190° C. and 2.16 kg is 0.1-30 g/10min;

(c) the filler comprises at least one of talc, whisker, calcium carbonate, barium sulfate, wollastonite;

(d) The weight part of the secondary amide auxiliary agent in the polypropylene composition is 0.3-0.4 part.
The application according to claims 7-9, wherein the polypropylene composition further comprises the following components in parts by weight: 0-12 parts of polyethylene, 0.1-0.5 parts of antioxidants, 0.1-0.5 parts of light stabilizers 0.5 part and color masterbatch 0.5-1 part.