阅读说明：本技术 聚丙烯改性剂及其制备方法和聚丙烯组合物和聚丙烯材料及其制备方法 (Polypropylene modifier and preparation method thereof, polypropylene composition, polypropylene material and preparation method thereof ) 是由 于芳 梁文斌 马伊 刘国刚 张春波 于 2019-10-21 设计创作，主要内容包括：本发明涉及聚丙烯材料领域,公开了一种聚丙烯改性剂及其制备方法和聚丙烯组合物和聚丙烯材料及其制备方法。所述聚丙烯改性剂的制备方法包括：将配方(1)或配方(2)中的极性单体接枝聚丙烯与组分A接触进行反应挤出造粒,然后进行干燥；所述极性单体接枝聚丙烯中的极性单体能够与组分A发生化学反应；配方(1)中,所述极性单体选自马来酸酐、丙烯酸、丙烯酸酯等；且所述组分A选自多异氰酸酯等；配方(2)中,所述极性单体选自甲基丙烯酸二甲氨基酯、丙烯酸环氧酯等；且所述组分A选自多异氰酸酯、聚环氧乙烷等。所述聚丙烯改性剂引入到普通线性聚丙烯中,能够明显提高聚丙烯的熔体强度以及力学性能。(The invention relates to the field of polypropylene materials, and discloses a polypropylene modifier and a preparation method thereof, a polypropylene composition, a polypropylene material and a preparation method thereof. The preparation method of the polypropylene modifier comprises the following steps: contacting polar monomer grafted polypropylene in the formula (1) or the formula (2) with the component A for reaction, extruding and granulating, and then drying; the polar monomer in the polar monomer grafted polypropylene can chemically react with the component A; in the formula (1), the polar monomer is selected from maleic anhydride, acrylic acid, acrylate and the like; and said component A is selected from polyisocyanates and the like; in the formula (2), the polar monomer is selected from dimethylamino methacrylate, epoxy acrylate and the like; and said component A is selected from polyisocyanates, polyethylene oxides, and the like. The polypropylene modifier is introduced into common linear polypropylene, so that the melt strength and the mechanical property of the polypropylene can be obviously improved.)

1. A method for preparing a polypropylene modifier, which is characterized by comprising the following steps:

contacting polar monomer grafted polypropylene in the formula (1) or the formula (2) with the component A for reaction, extruding and granulating, and then drying; the polar monomer in the polar monomer grafted polypropylene can chemically react with the component A;

in the formula (1), the polar monomer is at least one of maleic anhydride, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, vinyl versatate, glycidyl methacrylate, dimethylamino methacrylate, epoxy acrylate, isocyanurate triacrylate and acrylamide; and said component A is selected from at least one of polyisocyanate and polyethylene oxide;

in the formula (2), the polar monomer is at least one selected from dimethylamino methacrylate, epoxy acrylate, isocyanurate triacrylate and acrylamide; and the component A is selected from at least one of polyisocyanate, polyethylene oxide and amine group-containing substances; the amine-containing substance is at least one selected from a compound I and a compound II, wherein the compound I is an organic substance containing an amine group, an ether bond and an aryl group, and the compound II is polyamine;

based on the total weight of the polar monomer grafted polypropylene and the component A in each formula, the dosage of the polar monomer grafted polypropylene is 95-99.8 wt%, and the content of the component A is 0.2-5 wt%.

2. The production method according to claim 1, wherein the polyisocyanate is selected from one or more of diphenylmethane diisocyanate, 2, 4-xylylene diisocyanate, 2, 6-xylylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, and 4,4, 4-triphenylmethane triisocyanate.

3. The production method according to claim 1, wherein the polyethylene oxide has a molecular weight of 50 x 10⁴-200×10⁴g/mol。

4. The preparation method according to claim 1, wherein the compound I is one or more of 4,4 '-diaminodiphenyl ether, phenoxyaniline, 3, 4' -diaminodiphenyl ether, and 3,3 ', 4,4' -tetraaminodiphenyl ether;

the compound II is one or more of alkyl diamine, alkylene triamine, alkylene tetramine, alkylene pentamine and aryl diamine;

preferably, the compound II is one or more of C2-12 alkyl diamine, C2-12 alkylene diamine, C2-C12 alkylene triamine, C2-C12 alkylene tetramine, C2-C12 alkylene pentamine and C6-C18 aryl diamine;

more preferably, the compound II is one or more of tetraethylenepentamine, triethylenediamine, diethylenetriamine, triethylenetetramine, p-phenylenediamine, m-phenylenediamine, 1, 9-diaminononane and 1, 12-diaminododecane.

5. The method according to any one of claims 1 to 4, wherein the polar monomer-grafted polypropylene is used in an amount of 97 to 99.5 wt% and the component A is contained in an amount of 0.5 to 3 wt%, based on the total weight of the polar monomer-grafted polypropylene and the component A in each formulation.

6. The production method according to claim 1, wherein the acrylic ester is selected from at least one of ethyl acrylate, butyl acrylate, and isooctyl acrylate; the methacrylate is selected from at least one of ethyl methacrylate, propyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate;

preferably, the polar monomer grafted polypropylene has a grafting ratio of 0.1 to 3%, preferably 0.5 to 2%.

7. The production method according to any one of claims 1 to 6, wherein the temperature of the reaction and extrusion is 150-220 ℃.

8. A polypropylene modifier prepared by the preparation method of any one of claims 1 to 7.

9. A polypropylene composition comprising the polypropylene modifier of claim 8 and a polypropylene; preferably, the polypropylene modifier is present in an amount of from 2 to 20%, more preferably from 5 to 10%, based on the total weight of the composition.

10. A method of preparing a polypropylene material, the method comprising: blending the polypropylene modifier of claim 8 and polypropylene at 220 ℃, extruding and pelletizing, and then drying, wherein the content of the polypropylene modifier is preferably 2-20%, more preferably 5-10% by weight based on the total weight of the polypropylene modifier and the polypropylene.

11. The polypropylene material produced by the production method according to claim 10.

Technical Field

The invention relates to the field of polypropylene materials, in particular to a preparation method of a polypropylene modifier, the polypropylene modifier prepared by the preparation method, a polypropylene composition, a method for preparing a polypropylene material and the polypropylene material prepared by the method.

Background

The polypropylene is a general plastic and has the advantages of rich raw material sources, low price, small density, high melting point, no toxicity, chemical corrosion resistance, easy recovery, easy degradation and the like. Has become an indispensable raw material in the industries of packaging, light industry, building, electronics, electrical appliances, automobiles and the like, and is one of the thermoplastic resins which are developed at the fastest speed at present. The majority of the polypropylenes currently marketed are semicrystalline linear polymers. Because of having soft long-chain macromolecular structure and higher crystallization tendency, the softening point is very close to the melting point, the melt viscosity is rapidly reduced after reaching the melting crystallization temperature, and a large amount of crystallization heat is released in the crystallization process, so that the melt viscosity and the melt strength are further reduced. Therefore, the common polypropylene has small melt strength, poor toughness, poor sag resistance, poor thermal formability and foaming performance, and limits the application field thereof.

The high melt strength polypropylene can be applied to high added value fields such as foaming, thermoforming, extrusion coating and the like, has wider market application prospect, and has remarkable economic and social benefits in research and development. Therefore, the development of polypropylene with higher melt strength is a hot research focus in materials science in recent years. The existing methods for improving the melt strength of polypropylene include crosslinking initiated on polypropylene, grafting modification, blending modification with other resins, and the like.

Blending modification is a simple way for improving the melt strength of common polypropylene products. The common polypropylene is mainly in a straight-chain structure, each molecular structure contains methyl, and basically has no branching or crosslinking. The melting point and rigidity of polypropylene are reduced by adding high melt strength polymers, elastomers or low melting point copolymers, thereby achieving good processability. CN105037952A, CN105153546A, CN104987588A, USP4940736, etc. disclose such methods.

The linear PP can generate long-chain branch by crosslinking modification, thereby achieving the purpose of improving the melt strength. USP5047446, USP5414027, USP5541236 and the like are all techniques for preparing high melt strength polypropylene by irradiation crosslinking of Himont company.

CN101125947A discloses a high melt strength polypropylene containing a long branched chain structure and a preparation method thereof. The preparation method of the high melt strength polypropylene containing the long branched chain structure disclosed by the technology comprises the following steps: fully mixing the component A, the antioxidant and the heat stabilizer in a mixing kettle, adding the mixture into a reactive double-screw extruder from a feeding port at the speed of 60-200g/min, adding the component B organic solution into the extruder from one side of the double-screw extruder, and adding the supercritical carbon dioxide fluid into the extruder from the other side of the double-screw extruder. The first heating area of the double-screw extruder is 180-220 ℃, and the other heating areas are 140-220 ℃; and extruding and granulating to obtain the high-melt-strength polypropylene resin. The component A is polar monomer melt grafting polypropylene polymer with grafting rate more than 0.3%, and the component B is amine or alcohol compound. The technology utilizes the reaction of amino or hydroxyl in amine and alcohol compounds and functional groups on polypropylene graft to generate a long branched chain structure, thereby achieving the purpose of improving the melt strength. The technology measures the mechanical property and the melt flow rate of a sample, and does not give measurement data of melt strength.

In addition, the blending of the high melt strength polypropylene of the prior art with the ordinary linear polypropylene can improve the melt strength of the latter to some extent, but the mechanical property of the linear polypropylene is reduced, which limits the application of the modified polypropylene material. Therefore, a new polypropylene modifier which can improve the melt strength of polypropylene and ensure the mechanical property thereof is needed.

Disclosure of Invention

The invention aims to provide a polypropylene modifier, a preparation method and application thereof, a polypropylene composition, a polypropylene material and a preparation method thereof.

According to a first aspect of the present invention, there is provided a process for the preparation of a polypropylene modifier, the process comprising: contacting polar monomer grafted polypropylene in the formula (1) or the formula (2) with the component A for reaction, extruding and granulating, and then drying; contacting polar monomer grafted polypropylene in the formula (1) or the formula (2) with the component A for reaction, extruding and granulating, and then drying; the polar monomer in the polar monomer grafted polypropylene can chemically react with the component A;

in the formula (1), the polar monomer is at least one of maleic anhydride, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, vinyl versatate, glycidyl methacrylate, dimethylamino methacrylate, epoxy acrylate, isocyanurate triacrylate and acrylamide; the component A is selected from at least one of polyisocyanate and polyethylene oxide;

in the formula (2), the polar monomer is at least one selected from dimethylamino methacrylate, epoxy acrylate, isocyanurate triacrylate and acrylamide; and the component A is selected from at least one of polyisocyanate, polyethylene oxide and amine group-containing substances; the amine-containing substance is at least one selected from a compound I and a compound II, wherein the compound I is an organic substance containing an amine group, an ether bond and an aryl group, and the compound II is polyamine;

based on the total weight of the polar monomer grafted polypropylene and the component A in each formula, the dosage of the polar monomer grafted polypropylene is 95-99.8 wt%, and the content of the component A is 0.2-5 wt%.

According to a second aspect of the present invention, the present invention provides a polypropylene modifier prepared by the preparation method.

According to a third aspect of the present invention, there is provided a polypropylene composition, wherein the composition comprises the polypropylene modifier of the present invention and polypropylene.

According to a fourth aspect of the present invention, there is provided a process for the preparation of a polypropylene material, the process comprising: the polypropylene modifier and polypropylene are blended at the temperature of 180-220 ℃, extruded and granulated, and then dried.

According to a fifth aspect of the present invention there is provided a polypropylene material obtainable by the process according to the present invention.

The polypropylene modifier can modify polypropylene with a small addition amount by a physical blending method, simultaneously realizes the improvement of the melt strength and the mechanical property of the polypropylene material, and has the characteristics of simple composition and preparation process of the polypropylene material and low cost.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

According to a first aspect of the present invention, there is provided a process for the preparation of a polypropylene modifier, the process comprising: and (3) contacting the polar monomer grafted polypropylene in the formula (1) or the formula (2) with the component A for reaction, extruding and granulating, and then drying.

In the formula (1), the polar monomer in the polar monomer grafted polypropylene is at least one of maleic anhydride, acrylic acid, acrylate, methacrylic acid, methacrylate, vinyl versatate, glycidyl methacrylate, dimethylamino methacrylate, epoxy acrylate, isocyanurate triacrylate and acrylamide; the component A is selected from at least one of polyisocyanate and polyethylene oxide, and the selected polar monomer when used in combination with the selected component A undergoes a chemical reaction during the reactive extrusion process.

Preferably, the acrylate is at least one selected from the group consisting of ethyl acrylate, butyl acrylate, and isooctyl acrylate; the methacrylate is at least one selected from the group consisting of ethyl methacrylate, propyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate.

In the formula (2), the polar monomer in the polar monomer grafted polypropylene is selected from one or more of dimethylamino methacrylate, epoxy acrylate, isocyanurate triacrylate and acrylamide, the component A is selected from at least one of polyisocyanate, polyethylene oxide and an amine group-containing substance, and the selected polar monomer and the selected component A are subjected to chemical reaction in the reaction extrusion process when being matched for use.

In the formula (2), under the condition that the component A is an amino-containing substance, the component A is matched with at least one polar monomer, and the formula (1) can realize the effects of ensuring the higher melt strength of the polypropylene and improving the mechanical property of the polypropylene.

According to the preparation method, the dosage of the polar monomer grafted polypropylene is 95-99.8 wt% and the content of the component A is 0.2-5 wt% based on the total weight of the polar monomer grafted polypropylene and the component A in each formula.

Preferably, the polar monomer grafted polypropylene is used in an amount of 97 to 99.5 wt% and the component a is present in an amount of 0.5 to 3 wt%, based on the total weight of the polar monomer grafted polypropylene and the component a in each formulation.

According to the preparation method of the present invention, the polyisocyanate may be any polyisocyanate that can chemically react with the polar monomer. Typically, the polyisocyanate is selected from one or more of diphenylmethane diisocyanate, 2, 4-xylylene diisocyanate, 2, 6-xylylene diisocyanate, p-phenyl diisocyanate, hexamethylene diisocyanate and 4,4, 4-triphenylmethane triisocyanate. The diphenylmethane diisocyanate is preferably 4, 4-diphenylmethane diisocyanate.

According to the preparation method of the invention, the molecular weight of the polyethylene oxide is 50 multiplied by 10⁴-200×10⁴ g/mol。

According to the preparation method of the invention, the amine group-containing substance is selected from at least one of the compound I and the compound II, preferably at least one of the compound I or at least one of the compound II. The compound I is an organic matter containing an amino group, an ether bond and an aryl group, and the compound II is polyamine. And said compound I and said compound II are different.

According to a particular embodiment, the compound I is one or more of 4,4 '-diaminodiphenyl ether, phenoxyaniline, 3, 4' -diaminodiphenyl ether and 3,3 ', 4,4' -tetraaminodiphenyl ether, preferably phenoxyaniline and/or 3,3 ', 4,4' -tetraaminodiphenyl ether.

The compound II can be one or more of alkyl diamine, alkylene triamine, alkylene tetramine, alkylene pentamine and aryl diamine, such as one or more of C2-12 alkyl diamine, C2-12 alkylene diamine, C2-C12 alkylene triamine, C2-C12 alkylene tetramine, C2-C12 alkylene pentamine and C6-C18 aryl diamine.

According to a specific embodiment, the compound II is one or more of tetraethylenepentamine, triethylenediamine, diethylenetriamine, triethylenetetramine, p-phenylenediamine, m-phenylenediamine, 1, 8-octanediamine, 1, 9-diaminononane, 1, 10-diaminodecane and 1, 12-diaminododecane; preferably diethylenetriamine and/or 1, 9-diaminononane.

In the present invention, the polar monomer-grafted polypropylene (also referred to as poly (propylene-graft-polar monomer)) may be obtained commercially or may be prepared by methods well known in the art, for example, by solution grafting, melt grafting, solid phase grafting, radiation grafting, and the like. According to one embodiment, the polar monomer grafted polypropylene is prepared by the melt grafting process comprising: uniformly mixing the polar monomer (1-10%), polypropylene (90-99%) and an initiator (0.1-3%), adding the mixture into a double-screw extruder, carrying out melt extrusion, setting the temperature of the extruder at 230 ℃, the rotating speed of the extruder at 400r/min and the feeding speed at 5-15Hz, cooling the mixture by a water tank, granulating, and drying the product to obtain the polar monomer grafted polypropylene. The initiator may be selected from at least one of benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyisopropyl benzene, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.

According to one embodiment, the polar monomer grafted polypropylene has a grafting degree of 0.1 to 3% by weight, preferably 0.5 to 2% by weight. The polar monomer-grafted polypropylene may have a Melt Index (MI) of 30 to 600g/10min, preferably 45 to 350g/10min at 230 ℃ under 2.16 kg.

According to the preparation method of the invention, the reaction extrusion mode can be carried out according to conventional operation, and for the invention, the reaction extrusion temperature is preferably 150-220 ℃. The rotational speed of the extruder can be, for example, 50 to 100r/min, and the feed rotational speed can be, for example, 3 to 8 Hz. The reactive extrusion can be carried out in various twin-screw extruders. After extrusion granulation, the product may be dried at 80-95 ℃ for 30-120 min.

According to a second aspect of the present invention, there is provided a polypropylene modifier obtainable by the process of the first aspect of the present invention. The polypropylene modifier can be physically blended with common polypropylene in a lower proportion, so that the high melt strength of the polypropylene can be ensured, and the mechanical property of the polypropylene is improved, thereby widening the application of the polypropylene modifier in high added value fields such as thermal forming, extrusion coating and the like. Therefore, the invention also provides a polypropylene composition containing the polypropylene modifier, a polypropylene material containing the polypropylene modifier and a preparation method thereof.

According to a third aspect of the present invention, there is provided a polypropylene composition, wherein the composition comprises the polymer modifier of the present invention and polypropylene.

Preferably, the polypropylene modifier is present in an amount of 2 to 20%, more preferably 5 to 10%, based on the total weight of the polypropylene composition.

According to a fourth aspect of the present invention, there is provided a process for the preparation of a polypropylene material, the process comprising: the polypropylene modifier and polypropylene are blended at the temperature of 180-220 ℃, extruded and granulated, and then dried.

Preferably, the modifier is present in an amount of 2 to 20%, preferably 5 to 10%, based on the total weight of the polypropylene modifier and the polypropylene.

The polypropylene of the present invention is not particularly limited, and may be any conventional linear polypropylene which is required to improve the melt strength.

The conditions for the co-extrusion according to the process of the present invention may be chosen as is conventional in the art, for example for an extruder speed of 50-100r/min and a feed speed of 3-5 Hz.

According to the method of the invention, the drying conditions comprise: the temperature is 80-95 deg.C, and the time is 30-120 min.

According to a fifth aspect of the invention, there is provided a polypropylene material produced by the method.

The present invention is further described below with reference to specific exemplary embodiments, but the present invention is not limited to these embodiments only.

In the following examples and comparative examples,

(1) main raw materials

The maleic anhydride grafted polypropylene has the grade of PO1020 and is purchased from exxonmobil, the grafting rate is 1.2 percent, and the MI is 348g/10 min;

polyethylene oxide, molecular weight 100 million g/mol, available from Aladdin reagents, Inc.;

the polypropylene L5E89 is common linear polypropylene and is purchased from Baotou coal chemical industry division of Shenhua coal oil chemical industry Co., Ltd;

polypropylene WB130 is a high melt strength polypropylene, purchased from northern european chemical;

PE100, brand 3490, available from northern Europe chemical industry.

(2) Property testing

And performing infrared spectrum analysis on the sample by using an Shimadzu IRPresidge-21 type Fourier transform infrared spectrometer.

The melt strength of the polypropylene material was measured with a melt extensional rheometer model Rheotens 71.97 (Goettfert, germany), and the temperature was determined: at 200 ℃. The diameter of the die head is 2mm, the initial rotating speed of the roller is 20mm/s, the acceleration of the roller is 2.4mm/s, and the distance from the die head to the roller is 65 mm.

The polypropylene material has the following mechanical property test standards:

item	Unit of	Test standard
			Tensile strength	MPa	ISO 527-1
Bending strength	MPa	ISO 178/A
			Flexural modulus	MPa	ISO 178/A

Example 1

(1) Preparation of Polypropylene modifier

98.0 parts of methyl acrylate-grafted polypropylene (grafting ratio of 1.0%, MI of 52g/10min) was weighed and mixed with 2.0 parts of polyethylene oxide thoroughly. And (3) adding the completely mixed raw materials into a HAAKE double-screw extruder, wherein the extrusion temperature is set to 190 ℃, the rotating speed of the extruder is 50r/min, and the feeding rotating speed is 3 Hz. And (4) extruding and granulating, and drying the obtained product at 90 ℃ for 60min to obtain the polypropylene modifier.

Preparing a sample of the polypropylene modifier, and performing infrared analysis on the sample, wherein the infrared spectrogram of the sample is 1722cm^-1Characteristic absorption peaks of carbonyl groups appear at 1145, 1118 and 1090cm^-1The absorption peak is the symmetric and asymmetric stretching vibration peak of the C-O-C group, 3000-2750cm^-1is-CH₂The asymmetric vibration absorption peak of the group shows that the methyl acrylate reacts with the polyethylene oxide, and the prepared product is the target product.

(2) Preparation of Polypropylene Material

And (3) uniformly mixing 10 parts of polypropylene modifier and 90 parts of polypropylene L5E89, adding the mixture into a HAAKE double-screw extruder, and blending and extruding. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 60min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Comparative example 1

A polypropylene modifier and a polypropylene material were produced in the same manner as in example 1, except that in the production of the polypropylene modifier, polyethylene oxide was replaced with 4,4' -diaminodiphenyl ether and tetraethylenepentamine in a mass ratio of 1: 1.

The properties of the prepared polypropylene materials are respectively shown in table 1.

Example 2

(1) Preparation of Polypropylene modifier

98.5 parts of acrylic acid-grafted polypropylene (graft ratio: 1.2% by weight, MI: 67g/10min) was weighed and mixed thoroughly with 1.5 parts of 2, 4-xylene diisocyanate. And (3) adding the completely mixed raw materials into a HAAKE double-screw extruder, wherein the extrusion temperature is set to 190 ℃, the rotating speed of the extruder is 50r/min, and the feeding rotating speed is 3 Hz. And (4) extruding and granulating, and drying the obtained product at 90 ℃ for 60min to obtain the polypropylene modifier.

(2) Preparation of Polypropylene Material

And (3) uniformly mixing 10 parts of polypropylene modifier and 90 parts of polypropylene L5E89, adding the mixture into a HAAKE double-screw extruder, and blending and extruding. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 60min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Example 3

(1) Preparation of Polypropylene modifier

99 parts of acrylamide-grafted polypropylene (graft ratio: 1.0% by weight, MI: 64g/10min) was weighed and mixed thoroughly with 1 part of 4,4' -diphenylmethane diisocyanate. The fully mixed raw materials were added to a HAAKE twin screw extruder with the extrusion temperature set at 180 ℃. The rotating speed of the extruder is 50r/min, and the feeding rotating speed is 3 Hz. And (4) extruding and granulating, and drying the obtained product at 90 ℃ for 30min to obtain the polypropylene modifier.

Sampling the polypropylene modifier, and performing infrared analysis on the sample at 3325cm in an infrared spectrogram^-12937cm at the peak of stretching vibration of N-H bond^-1The absorption peak is the characteristic absorption peak of a saturated alkane C-H bond, and the stretching vibration of-C ═ O in an ester group is 1670cm^-1The deformation vibration is 1560cm^-1Here, the reaction of acrylamide with isocyanate is illustrated, and the product produced is the target product.

(2) Preparation of Polypropylene Material

5 parts of polypropylene modifier and 95 parts of polypropylene L5E89 are uniformly mixed and then added into a HAAKE double-screw extruder for blending and extrusion. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 60min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Examples 4 to 6

Polypropylene modifiers and polypropylene materials were prepared according to the method of example 3, except that in examples 4 to 6, in the preparation of the polypropylene modifiers, the properties of the polypropylene materials prepared by replacing the acrylamide-grafted polypropylene with equal mass of maleic anhydride-grafted polypropylene, dimethylamino methacrylate-grafted polypropylene (graft ratio of 1.8 wt%, MI of 76g/10min), and epoxy acrylate-grafted polypropylene (graft ratio of 1.4 wt%, MI of 159g/10min, the same applies) were as shown in Table 1.

Example 7

A polypropylene modifier and a polypropylene material were prepared by the method of example 3, except that in the preparation of the polypropylene modifier, the amounts of the acrylamide-grafted polypropylene and 4,4' -diphenylmethane diisocyanate were adjusted to 95 parts and 5 parts, respectively.

The properties of the prepared polypropylene materials are respectively shown in table 1.

Example 8

(1) Preparation of Polypropylene modifier

99.3 parts of isocyanurate-grafted polypropylene (grafting ratio of 1.6 wt%, MI of 78g/10min) was weighed and mixed with 0.7 part of phenoxyaniline. The fully mixed raw materials were added to a HAAKE twin screw extruder with the extrusion temperature set at 200 ℃. The rotating speed of the extruder is 70r/min, and the feeding rotating speed is 3 Hz. And (4) extruding and granulating, and drying the obtained product at 90 ℃ for 70min to obtain the polypropylene modifier.

Sampling the polypropylene modifier, performing infrared analysis, and obtaining 1660cm infrared spectrogram^-1Is the stretching vibration characteristic peak of-C ═ O in urea, 1550cm^-1The peak is the deformation vibration characteristic peak of-C ═ O in urea. 3400cm^-1The peak is the stretching vibration peak of-N-H in urea, which shows that the isocyanate group reacts with amino group to generate urea, and the prepared product is the target product.

(2) Preparation of Polypropylene Material

5 parts of polypropylene modifier and 95 parts of polypropylene L5E89 are uniformly mixed and then added into a HAAKE double-screw extruder for blending and extrusion. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 60min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Comparative example 2

A polypropylene modifier and polypropylene material were prepared as in example 8, except that during the preparation of the polypropylene modifier, the isocyanurate-grafted polypropylene was replaced with equal mass maleic anhydride-grafted polypropylene.

The properties of the polypropylene material prepared are shown in table 1.

Comparative example 3

(1) Preparation of Polypropylene modifier

99.3 parts of maleic anhydride grafted polypropylene is weighed and fully mixed with 0.4 part of phenoxyaniline and 0.3 part of p-phenylenediamine. The fully mixed raw materials were added to a HAAKE twin screw extruder with the extrusion temperature set at 200 ℃. The rotating speed of the extruder is 70r/min, and the feeding rotating speed is 3 Hz. And (4) extruding and granulating, and drying the obtained product at 90 ℃ for 70min to obtain the polypropylene modifier.

(2) Preparation of Polypropylene Material

5 parts of polypropylene modifier and 95 parts of polypropylene L5E89 are uniformly mixed and then added into a HAAKE double-screw extruder for blending and extrusion. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 60min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Example 9

(1) Preparation of Polypropylene modifier

Weighing 98.3 parts of acrylic epoxy ester grafted polypropylene, and fully mixing with 1.7 parts of 1, 9-diaminononane. The fully mixed raw materials were added to a HAAKE twin screw extruder with the extrusion temperature set at 200 ℃. The rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And (4) extruding and granulating, and drying the obtained product at 90 ℃ for 30min to obtain the polypropylene modifier.

(2) Preparation of Polypropylene Material

6 parts of polypropylene modifier and 94 parts of polypropylene L5E89 are uniformly mixed and then added into a HAAKE double-screw extruder for blending and extrusion. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 60min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Example 10

(1) Preparation of Polypropylene modifier

97.2 parts of dimethylamino methacrylate-grafted polypropylene was weighed out and mixed well with 2.8 parts of diethylenetriamine. The fully mixed raw materials were added to a HAAKE twin screw extruder with the extrusion temperature set at 210 ℃. The rotating speed of the extruder is 50r/min, and the feeding rotating speed is 3 Hz. And (4) extruding and granulating, and drying the obtained product at 90 ℃ for 120min to obtain the amine modified polypropylene.

(2) Preparation of Polypropylene Material

And (3) uniformly mixing 10 parts of polypropylene modifier and 90 parts of polypropylene L5E89, adding the mixture into a HAAKE double-screw extruder, and blending and extruding. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 120min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Comparative example 4

A polypropylene modifier and a polypropylene material were prepared as in example 10, except that the dimethylamino methacrylate-grafted polypropylene was replaced with an equal mass of acrylic acid-grafted polypropylene in the preparation of the polypropylene modifier.

The properties of the polypropylene material prepared are shown in table 1.

Example 11

(1) Preparation of Polypropylene modifier

99.2 parts of acrylamide grafted polypropylene is weighed and fully mixed with 0.8 part of 3,3 ', 4,4' -tetraaminodiphenyl ether. The fully mixed raw materials were added to a HAAKE twin screw extruder with the extrusion temperature set at 210 ℃. The rotating speed of the extruder is 50r/min, and the feeding rotating speed is 3 Hz. And (4) extruding and granulating, and drying the obtained product at 90 ℃ for 120min to obtain the amine modified polypropylene.

(2) Preparation of Polypropylene Material

And (3) uniformly mixing 10 parts of polypropylene modifier and 90 parts of polypropylene L5E89, adding the mixture into a HAAKE double-screw extruder, and blending and extruding. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 120min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Example 12

A polypropylene modifier and a polypropylene material were prepared as in example 11, except that the acrylamide-grafted polypropylene was replaced with isocyanurate-grafted polypropylene during the preparation of the polypropylene modifier.

The properties of the prepared polypropylene materials are respectively shown in table 1.

Example 13

A polypropylene modifier and a polypropylene material were produced as in example 11, except that in the production of the polypropylene modifier, the amounts of the acrylamide-grafted polypropylene and 3,3 ', 4,4' -tetraaminodiphenyl ether were adjusted to 99.7 parts and 0.3 part, respectively.

The properties of the prepared polypropylene materials are respectively shown in table 1.

Comparative example 5

10 parts of PE100 and 90 parts of polypropylene L5E89 are weighed and mixed uniformly, and then the mixture is added into a HAAKE double-screw extruder for blending and extrusion. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 60min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

Comparative example 6

Weighing 10 parts of polypropylene WB130 and 90 parts of polypropylene L5E89, uniformly mixing, adding into a HAAKE double-screw extruder, and blending and extruding. The extrusion temperature is set to 200 ℃, the rotating speed of the extruder is 100r/min, and the feeding rotating speed is 5 Hz. And drying at 90 ℃ for 60min after granulation to obtain the polypropylene material.

The properties of the polypropylene material are shown in table 1.

TABLE 1

As shown in Table 1, the melt strength of the conventional linear polypropylene L5E89 is 8.6cN, and the melt strength of the product is improved and the mechanical properties such as tensile and bending properties of the polypropylene material are improved after the polypropylene modifier of the invention is added in examples 1-13. In comparative examples 2 and 4, although the melt strength values were improved, but significantly lower than those of the polypropylene materials modified with the polypropylene modifier of the invention, comparative examples 1 to 4 all resulted in a decrease in the mechanical properties of linear polypropylene. Therefore, the polypropylene modifier provided by the invention can obviously improve the melt strength value and mechanical property of polypropylene and broaden the application field of the polypropylene.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.