阅读说明：本技术 一种聚丙烯组合物及其制备方法和应用 (Polypropylene composition and preparation method and application thereof ) 是由 尹朝清 王亚南 杨泽 张爽爽 周杰 杨磊 叶南飚 陈平绪 杨霄云 于 2021-08-26 设计创作，主要内容包括：本发明提供了一种聚丙烯组合物及其制备方法和应用,所述组合物包括如下按重量份计算的组分：聚丙烯树脂50～93份；改性氯化聚丙烯2～20份；极性乙烯类嵌段共聚物2～20份；极性小分子助剂0.5～5份；增韧剂2～20份；抗氧剂0.1～1份；润滑剂0.1～1份；填料0～20份；所述改性氯化聚丙烯中接枝有极性官能团。本发明将接枝有极性官能团的氯化聚丙烯与极性乙烯类嵌段共聚物共混制备得到聚丙烯树脂组合物与涂料的附着力效果明显,使得制备得到聚丙烯组合物与涂料具有高的附着力和长效附着能力。(The invention provides a polypropylene composition, a preparation method and an application thereof, wherein the composition comprises the following components in parts by weight: 50-93 parts of polypropylene resin; 2-20 parts of modified chlorinated polypropylene; 2-20 parts of polar ethylene block copolymer; 0.5-5 parts of polar small molecular auxiliary agent; 2-20 parts of a toughening agent; 0.1-1 part of antioxidant; 0.1-1 part of a lubricant; 0-20 parts of a filler; the modified chlorinated polypropylene is grafted with polar functional groups. According to the invention, the polypropylene resin composition prepared by blending the chlorinated polypropylene grafted with the polar functional group and the polar ethylene block copolymer has an obvious adhesive force effect with the coating, so that the prepared polypropylene resin composition and the coating have high adhesive force and long-acting adhesive capacity.)

1. The polypropylene composition is characterized by comprising the following components in parts by weight:

the modified chlorinated polypropylene is grafted with polar functional groups.

2. The polypropylene composition according to claim 1, wherein the mass ratio of the modified chlorinated polypropylene to the polar ethylene block copolymer is 1: (0.25-2).

3. The polypropylene composition according to claim 1, wherein the modified chlorinated polypropylene grafted with polar functional groups is one or more of methyl methacrylate modified chlorinated polypropylene, maleic anhydride modified chlorinated polypropylene or methacrylic acid modified chlorinated polypropylene.

4. The polypropylene composition according to claim 1, wherein the polar functional group has a grafting ratio of 0.6 to 1.5%.

5. The polypropylene composition of claim 1, wherein the polar ethylene block copolymer is one or more of an acrylic acid-ethylene block copolymer, a vinyl acetate-ethylene block copolymer, or a vinyl alcohol-ethylene block copolymer.

6. The polypropylene composition according to claim 1, wherein the polar small molecule assistant is one or more selected from stearic acid ethoxy amide, erucic acid ethoxy amide, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, triglycerol monooleate, triglycerol fatty acid ester, triglycerol laurate or triglycerol myristate.

7. The polypropylene composition of claim 1, wherein the toughening agent is one or more of an ethylene-octene copolymer, ethylene-propylene-diene monomer rubber, or styrene-ethylene-butylene-styrene copolymer.

8. The polypropylene composition according to claim 1, wherein the polypropylene resin is a co-polypropylene and/or a homo-polypropylene.

9. A process for the preparation of a polypropylene composition according to any one of claims 1 to 8, comprising the steps of:

s1, uniformly blending polypropylene resin, modified chlorinated polypropylene, a polar ethylene block copolymer, a polar small molecular auxiliary agent, a toughening agent, an antioxidant, a lubricant and a filler to obtain a premix;

s2, melting, extruding and granulating the premix obtained in the step S1 to obtain the polypropylene composition.

10. An easily sprayable article prepared from the composition of any of claims 1 to 8.

Technical Field

The invention relates to the technical field of high polymer materials, and particularly relates to a polypropylene composition and a preparation method and application thereof.

Background

Polypropylene (PP) material is one of five general plastics, has the advantages of light weight, low price, excellent chemical resistance, good heat-resistant stability and the like, and is widely applied to the fields of household appliances, transportation, electric tools and the like. However, polypropylene also has some disadvantages such as poor printing properties, poor surface wetting properties, the need for surface treatment for spraying, etc., which limits its wider application. Polypropylene materials are commonly used as appearance parts in the fields of household appliances and automobiles, when the polypropylene materials are applied to the fields of coffee machines, refrigerators, washing machines, toys and the like, in order to present delicate appearances, part of the parts need to be sprayed to reduce corrosion, abrasion, scratch damage and the like of the appearances, and certain special facilities and equipment need to be sprayed with various functional coatings such as heat-conducting coatings, electric-conducting coatings, antifouling coatings, high-temperature resistant coatings, infrared stealth coatings and the like due to the needs of actual special functions; in the automotive field, filled polypropylene is mainly used as the bumper material for automobiles, and a coating is usually applied on the modified polypropylene bumper for the purpose of providing decoration and protection.

At present, polypropylene resin can be well sprayed only by treatment, two treatment methods are generally adopted to improve the spraying effect, and the first method is to oxidize the surface of a polypropylene plastic part before spraying. The common methods include flame treatment, corona treatment and plasma treatment to form carbonyl, carboxyl and other oxidized polar groups on the surface of polypropylene to improve the spraying performance. The method needs multi-step off-line treatment on a production line, has high personnel, material and equipment cost and low efficiency, and cannot realize the high-speed production of injection molding and spraying collineation. The second method is resin matrix modification, which increases the surface activity of the material by adding polypropylene graft or other polar auxiliary agents. For example, chinese patent (CN96195344.6) discloses a polyetheramine modified polypropylene material, which is prepared by introducing polyetheramine, elastomer, EP rubber, etc. into polypropylene resin, so that the prepared composite material can be used for preparing sprayable car body parts. The polyether amine is an oily substance, which brings inconvenience to processing, and meanwhile, the polyether amine has a large molecular weight and low mobility, has a limited effect on improving surface wetting, and is not favorable for paint film spreading.

Disclosure of Invention

The invention provides a polypropylene composition for overcoming the defects of insufficient adhesive force and no long-acting adhesive force.

It is another object of the present invention to provide a process for the preparation of said polypropylene composition.

It is another object of the present invention to provide the use of said polypropylene composition.

In order to achieve the purpose, the invention adopts the technical scheme that:

a polypropylene composition comprises the following components in parts by weight:

the modified chlorinated polypropylene is grafted with polar functional groups.

In the prior art, chlorinated polypropylene and other substances are mixed as a component to be added into coatings and paints for improving the adhesive force of polypropylene resin. However, the inventor finds that if chlorinated polypropylene is directly added into polypropylene resin to prepare the polypropylene composition, the effect of improving the adhesive force between the coating and the polypropylene resin is not obvious, probably because the chlorinated polypropylene and the polypropylene have similar molecular chain conformations and the effective content of polar group chlorine on the surface of the material is low, so that the adhesive force cannot be improved; on the other hand, especially in some harsh environments, such as high temperature, high humidity or oily stain wiping, the long-acting performance of the paint film needs to be improved.

Through further research, the chlorinated polypropylene grafted with the polar functional group and the polar ethylene block copolymer are blended to prepare the polypropylene resin composition, and the polypropylene resin composition has better adhesive force strength with the coating. On one hand, the modified chlorinated polypropylene has more polar groups and has higher bonding effect with the conventional acrylate/epoxy resin paint; on the other hand, the polar ethylene block copolymer can be used as a bridge between the modified chlorinated polypropylene and the polypropylene matrix, so that the compatibility of the modified chlorinated polypropylene and the polypropylene matrix is increased, the size uniformity of a disperse phase is ensured, and excessive phase separation is avoided; in addition, the polar ethylene block copolymer is beneficial to reducing the crystallization of the surface of the material, the rubber phase is beneficial to the penetration and the adhesion of paint and enters the material body, the adhesive force of a paint film is further improved, and the formed paint film is more durable in adhesion.

The inventors further investigated and found that the mass ratio of the modified chlorinated polypropylene to the polar ethylene-based block copolymer has an influence on the adhesion, and therefore, preferably, the mass ratio of the modified chlorinated polypropylene to the polar ethylene-based block copolymer is 1: (0.25-2).

Preferably, the modified chlorinated polypropylene grafted with polar functional groups is one or more of methyl methacrylate modified chlorinated polypropylene, maleic anhydride modified chlorinated polypropylene or methacrylic acid modified chlorinated polypropylene.

The chlorine content in the modified chlorinated polypropylene accounts for 5-8% of the total mass.

The grafting rate of the polar functional group has influence on the effect of the adhesive force, and the adhesive force improving effect is weak when the grafting rate is too low; too high grafting ratio may cause degradation of molecular chains and decrease of strength, and therefore, preferably, the grafting ratio of the polar functional group is 0.6 to 1.5%. The polar functional group does not contain chlorine.

Preferably, the polar ethylene block copolymer is one or more of an acrylic acid-ethylene block copolymer, a vinyl acetate-ethylene block copolymer or a vinyl alcohol-ethylene block copolymer.

Preferably, the polar small molecular auxiliary agent is one or more of stearic acid ethoxy amide, erucic acid ethoxy amide, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, triglycerol monooleate, triglycerol fatty acid ester, triglycerol laurate or triglycerol myristate.

Preferably, the toughening agent is one or more of ethylene-octene copolymer, ethylene propylene diene monomer, and styrene-ethylene-butylene-styrene copolymer.

Preferably, the polypropylene resin is a co-polypropylene and/or a homo-polypropylene.

Preferably, the antioxidant is selected from one or more of antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) ], antioxidant 168 (tris (2, 4-di-tert-butylphenyl) phosphite), antioxidant 1790(1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione), or antioxidant 412S (pentaerythritol tetrakis 3-laurylthiopropionate).

Preferably, the lubricant is selected from one or more of erucamide, oleamide, EBS amides, PE wax or stearate.

Preferably, the filler is one or more of calcium carbonate, talcum powder, barium sulfate, mica powder, wollastonite or magnesium silicate;

the preparation method of the polypropylene composition comprises the following steps:

s1, uniformly blending polypropylene resin, modified chlorinated polypropylene, a polar ethylene block copolymer, a polar small molecular auxiliary agent, a toughening agent, an antioxidant, a lubricant and a filler to obtain a premix;

s2, melting, extruding and granulating the premix obtained in the step S1 to obtain the polypropylene composition.

Preferably, the processing temperature of the extrusion in the step S2 is 200-240 ℃.

An easy-spraying product is prepared from the composition. The prepared easy-spraying product can have high adhesive force with a paint film and also has the function of long-acting maintenance.

Compared with the prior art, the invention has the beneficial effects that:

the polypropylene resin composition prepared by blending the chlorinated polypropylene grafted with the polar functional group and the polar ethylene block copolymer has obvious adhesive force effect with the coating; the reason is that the polar ethylene block copolymer can promote the dispersibility of the chlorinated polypropylene grafted with the polar functional group and improve the content of the chlorinated polypropylene grafted with the polar functional group on the surface of the polypropylene resin, so that the prepared polypropylene composition has high adhesion and long-acting adhesion with the coating.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.

The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.

The following examples and comparative examples employ the following starting materials:

polypropylene resin a: copolypropylene, EP548R, zhonghai shell petrochemical company, ltd;

polypropylene resin B: homo-polypropylene, HP500N, linadebo industries ltd;

modified chlorinated polypropylene A: methyl methacrylate modified chlorinated polypropylene with grafting rate of 0.6-1.5% is prepared by self;

modified chlorinated polypropylene B: maleic anhydride modified chlorinated polypropylene with grafting rate of 0.6-1.5% is prepared by self;

modified chlorinated polypropylene C1: methacrylic acid modified chlorinated polypropylene with grafting rate of 0.6-1.5% is prepared by self;

modified chlorinated polypropylene C2: methacrylic acid modified chlorinated polypropylene with grafting rate less than 0.6 percent is self-made;

modified chlorinated polypropylene C3: methacrylic acid modified chlorinated polypropylene with grafting rate of more than 1.5 percent is self-made;

the preparation method of the modified chlorinated polypropylene comprises the following steps:

1. chlorinated polypropylene according to the following mass ratio: methyl methacrylate/maleic anhydride/methacrylic acid: BPO: 20, weighing the materials, putting the raw materials into a three-neck bottle at one time, slowly heating to 100 ℃, keeping the temperature for 2 hours, and purifying the reactant after the reaction is finished; the grafting rate of the material can be regulated and controlled by properly regulating the content of the initiator BPO, so that the modified chlorinated polypropylene with different grafting rates can be obtained;

2. the purification method comprises the following steps: and pouring the reaction product into acetone, filtering, extracting the precipitate by using a Soxhlet extractor for 24 hours, removing unreacted monomers and byproducts, and drying the obtained sample under vacuum to constant weight.

Polar ethylene block copolymer a: acrylic acid-ethylene block copolymer, PRIMACOR 3460, dow chemistry;

polar ethylenic block copolymer B: vinyl acetate-ethylene block copolymer, ELVAX 265, dupont, usa;

polar ethylene block copolymer C: vinyl alcohol-ethylene block copolymer, Eval, kosher;

polar small molecular auxiliary agent A: erucic acid ethoxy amide, purchased from national medicine;

polar small molecular auxiliary agent B: sorbitan monooleate, purchased from national medicine;

polar small molecular assistant C: polyglycerol monooleate, purchased from national medicine;

a toughening agent A: ethylene-octene copolymers, POE 8842, exxonmobil;

a toughening agent B: styrene-ethylene-butylene-styrene copolymer, SEBS G1657 VS, kraton polymers trade ltd;

antioxidant: the antioxidant 1010 and the antioxidant 168 are compounded according to the mass ratio of 1:1, and are purchased from Ridiazuron Co;

lubricant: lubricant EBS B50, CMS inc, indonesia;

filling: ultra-fine wollastonite (AT series), Jiangxi Hua Jie Tai mineral fibre science and technology Limited;

the preparation process of the polypropylene compositions of the examples and comparative examples comprises the following steps:

s1, uniformly blending polypropylene resin, modified chlorinated polypropylene, a polar ethylene block copolymer, a polar small molecular auxiliary agent, a toughening agent, an antioxidant, a lubricant and a filler to obtain a premix;

s2, melting, extruding and granulating the premix obtained in the step S1 to obtain the polypropylene composition. The processing temperature of the extrusion in the step S2 is 200-240 ℃.

Examples 1 to 5

Examples 1-5 provide a series of polypropylene compositions, the specific component amounts are shown in Table 1.

TABLE 1 component contents (parts) of examples 1 to 5

Examples 6 to 12

Examples 6-12 provide a series of polypropylene compositions, with specific component amounts shown in Table 2.

TABLE 2 component contents (parts) of examples 6 to 12

Examples 13 to 17

Examples 13-17 provide a series of polypropylene compositions, with specific component amounts as shown in Table 3.

TABLE 3 component contents (parts) of examples 13 to 17

	Example 13	Example 14	Example 15	Example 16	Example 17
						Polypropylene resin A	70	70	70	70	70
Modified chlorinated polypropylene C1	8	8	8	8	10
						Polar ethylene-based Block copolymer A	2	4	16	20	2
Polar small molecular auxiliary agent A	1	1	1	1	1
						Toughening agent A	5	5	5	5	5
Antioxidant agent	0.2	0.2	0.2	0.2	0.2
						Lubricant agent	0.2	0.2	0.2	0.2	0.2

Comparative examples 1 to 5

Comparative examples 1-5 provide a series of polypropylene compositions, with specific component amounts shown in table 4.

TABLE 4 component contents (parts) of comparative examples 1 to 5

	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
						Polypropylene resin A	70	70	70	70	70
Modified chlorinated polypropylene C1	10	—	10	1	10
						Polar ethylene-based Block copolymer A	—	10	10	10	1
Polar small molecular auxiliary agent A	1	1	—	1	1
						Toughening agent A	5	5	5	5	5
Antioxidant agent	0.2	0.2	0.2	0.2	0.2
						Lubricant agent	0.2	0.2	0.2	0.2	0.2

Performance testing

The adhesion grade test method comprises the following steps: according to the test of GB/T9286-1998 paint and varnish paint film scratch test, the adhesive force is calculated according to the coating percentage, the coating adhesive force is 100 percent of the residual lattice number of the coating pulled off/all the lattice numbers of the whole coating, and the coating grades are divided into 0 grade (optimal), 1 grade, 2 grade, 3 grade, 4 grade and 5 grade (the latest);

adhesion rating (85 ℃, 85% RH, 2 h): after the sprayed workpiece is placed in a humid and hot aging box with 85 ℃ and 85% RH humidity for treatment for 2h, the test is carried out according to the national standard GB/T9286-1998 scratch test of paint films of colored paint and varnish;

adhesion rating (60 ℃, poaching for 2 h): after the sprayed workpiece is boiled in water at 60 ℃ for 2 hours in a bath kettle, testing according to the national standard GB/T9286-1998 scratch test of paint films of colored paint and varnish;

TABLE 5 data for examples and comparative examples

From examples 1 to 5, when the grafting ratio of the polar group is 0.6 to 1.5%, the long-acting adhesion level is high,

from examples 13 to 17, the mass ratio of the modified chlorinated polypropylene to the polar ethylene block copolymer was 1: (0.25-2), the long-acting adhesive force is high in grade and good in effect.

From comparative examples 1-3, the adhesion and the long-acting adhesion can be greatly reduced without adding one of the modified chlorinated polypropylene, the polar ethylene block copolymer or the polar small molecular auxiliary agent, and from comparative examples 4 and 5, the content of the modified chlorinated polypropylene or the polar ethylene block copolymer is too low, and the long-acting adhesion effect is not achieved.

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.