CN111690206B

CN111690206B - Polar polypropylene composite material and preparation method thereof

Info

Publication number: CN111690206B
Application number: CN202010701875.XA
Authority: CN
Inventors: 李保印; 陆佳伟; 杨峰; 吴志超; 张文勇; 孙嘉慧; 姚威宇
Original assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd; Wanhua Chemical Sichuan Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd; Wanhua Chemical Sichuan Co Ltd
Priority date: 2020-07-18
Filing date: 2020-07-18
Publication date: 2022-07-12
Anticipated expiration: 2040-07-18
Also published as: CN111690206A

Abstract

The invention provides a polar polypropylene composite material and a preparation method thereof. The polar polypropylene composite comprises: polypropylene, chlorinated polyolefin, polyolefin elastomer, hyperbranched multiphase polymer, filler and auxiliary agent. The preparation method of the hyperbranched multiphase polymer comprises the following steps: firstly blending polypropylene and polyethylene, then chloridizing the modified polypropylene-polyethylene blend, then adding unsaturated polar monomer, heating to initiate in-situ self-polymerization of the unsaturated polar monomer, and obtaining the hyperbranched multiphase polymer after treatment. The method of the invention greatly improves the polarity of the material and improves the compatibility and mechanical property of the material.

Description

Polar polypropylene composite material and preparation method thereof

Technical Field

The invention relates to the field of polypropylene composite materials, in particular to a polar polypropylene composite material and a preparation method thereof.

Background

The polypropylene plastic is a thermoplastic resin prepared by polymerizing propylene, has rich raw material sources, good chemical resistance, easy molding and processing and low price, and can be recycled for multiple times. Most importantly, the polypropylene material can be modified by means of blending, reinforcing, filling and the like, so that the engineering and high performance of the general plastic of the polypropylene material are realized, and the requirements of the polypropylene material in the application fields of household appliances, automobile interior and exterior trimming parts, body building, office supplies, sanitary wares and the like are met. However, the non-polarity of polypropylene surface makes it have poor hydrophilicity, dyeing property, antistatic property and compatibility with polar materials, and these disadvantages limit the application of polypropylene in many fields.

The commonly used methods for improving the polarity of polypropylene include a surface grafting method, a surface crosslinking method, a surface coating modification method, a blending method by adding polar substances and the like. The above modification methods can effectively improve the polarity of the polypropylene material, but except the blending method of directly adding polar substances, other modification methods all have the problems of complex processing technology or overhigh modification cost.

Patent CN101717548A discloses a method for preparing polar polypropylene composite material by directly adding polar substances such as Thermoplastic Polyurethane (TPU), maleic anhydride grafted polypropylene, epoxy resin, ethylene acrylate (EEA), Ethylene Vinyl Acetate (EVA) and the like, but adding a large amount of polar substances results in poor material compatibility, low composite material comprehensive performance and incapability of meeting use requirements. Patent CN101768394A discloses a method for preparing a high-polarity polypropylene material by adding maleic anhydride grafted polypropylene, but the maleic anhydride grafting rate is low, the addition amount is high, and the improvement effect of the material polarity is not obvious. Patent CN101768394A discloses a method for effectively improving polarity of polypropylene composite material by adding polyvinyl chloride, which can effectively improve polarity of polypropylene material, and adopts hyperbranched polyesteramide as a compatibilizer to modify compatibility of the material to a certain extent, but the compatibilizer has large molecular weight and is difficult to disperse, and in addition, compatibility with matrix resin is limited, thereby limiting performance improvement of the material. Patent CN1408732A discloses a method for performing graft copolymerization reaction by using polymer or organic low molecular compound during chlorination reaction, which directly uses chlorine gas to perform substitution reaction, and the whole reaction process has low activity, high chlorination reaction temperature and serious material degradation; on the other hand, when chlorine and vinyl monomer coexist, addition reaction is easy to occur, and the reaction activity of copolymerization grafting is reduced.

Disclosure of Invention

The invention aims to provide a high-polarity polypropylene composite material aiming at the problem that the improvement range of the polarity of the material obtained by the prior preparation technology is limited, the polarity of the material is greatly improved, and the compatibility and the mechanical property of the material are improved.

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

a polar polypropylene composite comprising the following components:

35-83.2 parts of polypropylene, preferably 47-73 parts;

8-25 parts of chlorine-containing polyolefin, preferably 10-20 parts;

3-12 parts of polyolefin elastomer, preferably 5-10 parts;

0.8-8 parts of hyperbranched multiphase polymer, preferably 2-6 parts;

5-20 parts of filler, preferably 10-17 parts;

wherein the hyperbranched heterogeneous polymer is formed by introducing unsaturated polar monomers into modified olefin; preferably, the substrate of the modified olefin is a blend of polypropylene and polyethylene; preferably the unsaturated polar monomer is a fatty acid containing at least 2 unsaturated bonds.

In the invention, the polypropylene is selected from one or more of homo-polypropylene, block co-polypropylene and random co-polypropylene; preferably, the polypropylene has a melt index of 8 to 35g/10min (230 ℃, 2.16 kg).

In the invention, the chlorine-containing polyolefin comprises one or more of polyvinyl chloride, vinylidene chloride, chlorinated polyethylene and chlorinated polypropylene; preferably, the chlorine-containing polyolefin has a molecular weight of 40,000-120,000. The chlorine-containing polyolefin is a high-polarity polymer, has the advantages of high strength, strong corrosion resistance, flame retardance, low price and the like, can effectively increase the polarity of a polypropylene material when being introduced into a polypropylene material system, can effectively migrate to the surface of the material when being polymerized, and greatly improves the polarity of the polypropylene composite material by cooperating with the chlorine-containing olefin, and effectively solves the problem of surface polarity reduction caused by polar molecule migration due to the action of the multiphase branched structure rivet fixation, thereby effectively improving the performances of spraying property, adhesion property and the like of a polypropylene product, which are related to the surface polarity.

In the present invention, the polyolefin elastomer is selected from one or more of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, and polystyrene-butadiene copolymer.

In one embodiment, the filler is preferably talc.

In another embodiment, the polar polypropylene composite is added with some auxiliary agents commonly used in the art, such as 0.3-1.1 parts of antioxidant, preferably 0.5-0.9 parts; 0.1-0.5 parts of hydrotalcite, preferably 0.2-0.4 parts; 0.1 to 0.5 part of calcium stearate, preferably 0.2 to 0.4 part.

In the invention, the hyperbranched heterogeneous polymer is prepared by the following method:

s1: extruding and granulating the polypropylene, the polyethylene and the antioxidant;

s2: placing the granules of S1 in a fluorine gas-chlorine gas mixed gas atmosphere, heating for activation modification treatment to obtain chlorinated modified polypropylene-polyethylene;

s3: adding unsaturated polar monomer into chlorinated modified polypropylene-polyethylene, heating to initiate in-situ self-polymerization of the unsaturated polar monomer to obtain an in-situ polymerization modified chlorinated polyolefin material;

s4: and (3) putting the in-situ polymerization modified chlorinated polyolefin material in the S3 into a solvent, and heating, dissolving, separating, washing and drying to obtain the hyperbranched multiphase polymer.

The unsaturated polar monomer is grafted by the free radical generated by heating and cracking after the carbon-chlorine bond, and the grafted unsaturated polar monomer is subjected to polymerization or chain extension reaction under the heating condition to form a hyperbranched structure as shown in the attached drawing 1, wherein the unsaturated polar monomer in the structure in the attached drawing 1 takes linoleic acid as an example.

According to the method, firstly, the bridging between polypropylene and polyethylene mixture molecular chains is realized through the coupling of active free radicals generated in the chlorination process, the problem of layering caused by different crystallization temperatures of polypropylene and polyethylene is solved, and the polyolefin material simultaneously containing the block structures of polyethylene and polypropylene long chains is obtained. And chlorinated polyolefin containing chlorinated ethylene and chlorinated propylene structures is obtained by introducing carbon-chlorine bonds. Meanwhile, free radicals (such as alkyl peroxy radicals) generated in the chlorination modification process and free radicals generated by heating and cracking after carbon-chlorine bonds are used as active sites to initiate the self-polymerization of flexible long-chain and polyunsaturated polar monomers, and finally the hyperbranched multiphase polymer with multiphase and multi-component chemical structures is obtained. In the melt extrusion process, the hyperbranched multiphase polymer is used as a compatilizer to effectively improve the compatibility of polypropylene and polyvinyl chloride, and meanwhile, flexible long-chain polar groups introduced by self polymerization can be migrated to the surface of the material to greatly improve the polarity of the polypropylene material in cooperation with chlorinated olefin, and the hyperbranched multiphase structure effectively avoids the problem of short timeliness caused by migration of directly mixed polar molecules.

In the invention, the raw materials in the S1 comprise:

35-75 parts, preferably 40-65 parts,

25 to 65 parts of polyethylene, preferably 35 to 60 parts,

0.2-0.3 part of antioxidant 1010 and 0.2-0.3 part of antioxidant 168.

In the present invention, the polyethylene is selected from one or more of high density polyethylene, low density polyethylene and linear low density polyethylene; preferably, the polyethylene has a melt index of 6 to 25g/10min (190 ℃, 2.16 kg).

In the invention, the pressure of the fluorine-chlorine mixed gas in the S2 is 10-80KPa, preferably 30-60 KPa; the proportion of fluorine gas is 0.5vol% to 3.0vol%, preferably 0.8vol% to 2.0vol%, based on the total volume of the mixed gas; the treatment time is 0.5-3h, preferably 0.8-2 h; the reaction temperature is 40-110 ℃, preferably 60-100 ℃.

In the present invention, the gas replacement is performed after the treatment of S2, the replacement gas is a mixed gas of an inert gas and oxygen, and the proportion of oxygen in the mixed gas is 1vol% to 10vol%, preferably 3vol% to 8vol%, based on the total volume of the mixed gas.

In the invention, the unsaturated polar monomer in S3 is selected from one or more of eleostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA) and docosahexaenoic acid.

The S3 initiates the self-polymerization of flexible long-chain and polyunsaturated polar monomers by taking free radicals generated in the chlorination process and free radicals generated by thermal cracking as active sites on the basis of chlorinated polyolefin materials, effectively adjusts the activity of the self-polymerization reaction through the reaction temperature under the condition of vacuum pumping, and provides multi-direction polymerization growth for multi-double bonds, thereby finally obtaining the hyperbranched multi-phase polymer with multi-phase and multi-chemical structures, wherein the multi-phase comprises polyethylene, polypropylene, chlorinated polyethylene, chlorinated polypropylene and multi-unsaturated polyolefin copolymer, and the multi-chemical structures comprise olefin structures, chlorine grafting structures, carboxyl groups and other chemical structures.

In the invention, the temperature of the S3 self-polymerization reaction is 100-150 ℃, and the reaction time is 1-4 h.

In the invention, the heating temperature in the S4 is 130-140 ℃.

It is another object of the present invention to provide a method for preparing the polar polypropylene composite.

A method for preparing the polar polypropylene composite material comprises the following steps: uniformly mixing polypropylene, chlorinated polyolefin, a polyolefin elastomer, a hyperbranched multiphase polymer, a filler and an auxiliary agent, adding the mixture into a double-screw extruder through a main feeding port, performing melt extrusion granulation, cooling and granulating to obtain the polar polypropylene composite material; preferably, the rotation speed of the double-screw extruder is 150-300 r/min, the reaction temperature is 170-220 ℃, and preferably 180-210 ℃.

The mixed gas pressure is gauge pressure, and the pressure in the kettle under the vacuum pumping condition is absolute pressure.

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

(1) the flexible long-chain polar group introduced by the hyperbranched structure can be effectively migrated to the surface of the material, the polarity of the polypropylene composite material is greatly improved by cooperating with chlorinated olefin, and the problem of surface polarity reduction caused by polar molecule migration is effectively solved by the rivet fixing effect of the multiphase branched structure.

(2) The chlorinated polyolefin copolymer with multiphase and diversified chemical structures is used as a compatilizer, so that the compatibility of nonpolar polypropylene, polyolefin elastomer and high-polarity polyvinyl chloride in the melt extrusion process is effectively improved, and the problems of layering and difficult dispersion of two-phase materials are solved, thereby obtaining the polypropylene composite material with excellent mechanical properties, wherein the tensile strength reaches 20-23MPa, and the flexural modulus reaches 1450-2200 MPa.

Drawings

FIG. 1 is a schematic structural diagram of a hyperbranched heterogeneous polymer.

Detailed Description

The invention is further described in the following with reference to examples, but the scope of protection of the invention is not limited to the examples only, but also includes any other known variations within the scope of the claims of the invention.

The main raw materials and equipment are as follows:

block copolymer polypropylene: medium sand petrochemical, EP548RQ, with a melt index of 28-32g/10min (230 ℃ C., 2.16 kg).

Homo-polypropylene: zhonghai Shell, HP500N, melt index 8-12g/10min (230 ℃, 2.16 kg).

High density polyethylene: the oil-in-water type polyester resin is prepared from Dioscorea villosa petrochemical, DMDA8008, and the melt index of 7-8g/10min (190 ℃, 2.16 kg).

Linear low density polyethylene: the oil-in-water type polyurethane resin is prepared from the raw materials of the kadsura oil, DNDA8320 and the melt index of 18-22g/10min (190 ℃, 2.16 kg).

Polyvinyl chloride: wanhua homemade, molecular weight 60,000.

Polyvinylidene chloride: wanhua homemade, molecular weight 100,000.

Ethylene-octene polyolefin elastomer: dow chemical, Engage 8100, ethylene-octene copolymer, melt index 1g/10min (190 ℃, 2.16 kg).

Ethylene-butene polyolefin elastomer: dow chemical, Engage 7467, ethylene-butene copolymer, melt index 1g/10min (190 ℃, 2.16 kg).

Linolenic acid: wuhanhao Biotechnology Limited, the purity is more than or equal to 99 percent.

Talc powder: aihai AH51210L, Leonian Ehai Talcum powder Co., Ltd, 2000 meshes 3000.

Antioxidant: cia Saba Seisakusho, antioxidant 1010, antioxidant 168.

Hydrotalcite: DHT-4A, manufactured by Nippon Kagaku Kogyo Co., Ltd.

Fluorine gas: hubei Zuoxi fluorinated Co., Ltd, at a concentration of 10 vol%.

Chlorine gas: wanhua chemical self-production, the purity is 99.9%.

A double-screw extruder: cobaron (Nanjing) machinery, Inc., model CTE35 PLUS.

Melt index meter: INSTRON CEAST (USA), model MF30, tested according to ISO1133 standard.

And (3) testing mechanical properties: the test method is carried out according to ISO 527, ISO 178 and ISO180 standards by using Instron 5966 and INStron CEAST 9050.

Surface energy testing: the American A.shine dyne pen is adopted, and the surface energy range is 25-45 mN/m.

Chemical composition test: the chlorine content and the oxygen content were obtained by analyzing the chemical element composition of the hyperbranched, multiphase polymer by X-ray photoelectron spectroscopy (XPS).

And (3) material compatibility characterization: the compatibility of the material is characterized by the melt index of the material, and the compatibility of the material is realized by improving the compatibility of different materials based on the diversified structural design of the chlorinated polyolefin, so that the polarity of the materials is increased, and the melt index of the material is reduced.

Example 1

1) Weighing 75Kg of block copolymer polypropylene, 25Kg of high density polyethylene, 0.3Kg of antioxidant 1010 and 0.2Kg of antioxidant 168, uniformly mixing by a high-speed mixer, and then melting, extruding and granulating at the temperature of 210 ℃ to obtain the polypropylene/polyethylene blend.

2) After heating and vacuumizing the blend obtained in the step (1) to remove moisture, the blend is heated to 40 ℃ in a fluorine/chlorine mixed gas atmosphere of 10kPa to be activated and modified, the fluorine concentration is 0.5vol%, the chlorine concentration is 99.5 vol%, and the reaction time is 0.5h, and then the mixture is replaced by a nitrogen/oxygen mixed gas (oxygen accounts for 1vol% of the mixed gas), so that a chlorinated modified polypropylene/polyethylene blend is obtained.

3) And (3) adding 40Kg of linoleic acid (in a ratio of 1:0.5) into 80Kg of chlorination modified mixture obtained in the step (2), heating to 100 ℃ under the condition of vacuum pumping (the pressure in the kettle is less than 200Pa) to carry out in-situ polymerization for 1h, and then washing, separating and drying (vacuum drying, 80 ℃) to obtain the linoleic acid modified chlorinated polyolefin material.

4) And (4) putting 60Kg of the linoleic acid modified chlorinated polyolefin product in the step (3) into a xylene solvent, wherein the concentration of a xylene solution of the chlorinated mixture is 10 wt%, heating and stirring the mixture at 130 ℃ for 2h for dissolution, filtering and separating the solution by using a Buchner funnel, washing the solution by using xylene, and drying the solution in a vacuum oven at 80 ℃ for 2h to obtain the hyperbranched multiphase polymer, wherein the chlorine content which is an index of the chlorination rate of the chlorinated polyolefin is 6.5 wt%, and the oxygen content which is an index of the grafting polymerization amount of linoleic acid is 1.8 wt%.

5) 83.2Kg of block copolymerization polypropylene, 8Kg of polyvinyl chloride, 3Kg of ethylene-octene polyolefin elastomer, 0.8Kg of hyperbranched multi-phase polymer, 5Kg of talcum powder, 0.2Kg of antioxidant 1010, 0.2Kg of antioxidant 168, 0.1Kg of hydrotalcite and 0.1Kg of calcium stearate are weighed, mixed for 2 minutes in a high-speed mixer, and stirred and mixed uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of 180 ℃ and 150 r/min of rotating speed, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. Melt index, mechanical properties and surface energy tests were performed and the results are shown in table 1.

Example 2

1) 60Kg of homopolymerized polypropylene, 40Kg of linear low density polyethylene, 0.3Kg of antioxidant 1010 and 0.2Kg of antioxidant 168 are weighed, evenly mixed by a high-speed mixer, melted, extruded and granulated at the temperature of 200 ℃ to obtain the polypropylene/polyethylene blend.

2) Heating and vacuumizing the blend in the step (1) to remove moisture, then heating to 60 ℃ in a fluorine/chlorine mixed gas atmosphere of 30kPa to perform activation modification, wherein the fluorine concentration is 0.8vol%, the chlorine concentration is 99.2 vol%, and the reaction time is 0.8h, and then replacing with a mixed gas of nitrogen/oxygen (the oxygen accounts for 3vol% of the mixed gas), thereby obtaining a chlorinated modified polypropylene/polyethylene blend.

3) And (3) adding 80Kg of linolenic acid (in a ratio of 1:1) into 80Kg of chlorination modified mixture obtained in the step (2), heating to 110 ℃ under the vacuum condition (the pressure in the kettle is less than 200Pa) for in-situ polymerization reaction for 2h, and then washing, separating and drying (vacuum drying, 80 ℃) to obtain the linolenic acid modified chlorinated polyolefin material.

4) And (3) putting the chlorinated polyolefin product modified by the linolenic acid in the step (3) into a xylene solvent, heating and stirring the xylene solution of a chlorinated mixture at 130 ℃ for 2h for dissolving, filtering and separating the solution by using a Buchner funnel, washing the solution by using the xylene solvent, and drying the solution in a vacuum oven at 80 ℃ for 2h to obtain the hyperbranched multiphase polymer, wherein the chlorine content of the chlorinated polyolefin is 12.3 wt% and the oxygen content of the linolenic acid graft polymerization amount is 3.2 wt%.

5) 73Kg of homopolymerized polypropylene, 10Kg of polyvinyl chloride, 5Kg of ethylene-octene polyolefin elastomer, 2Kg of hyperbranched multi-phase polymer, 10Kg of talcum powder, 0.3Kg of antioxidant 1010, 0.2Kg of antioxidant 168, 0.2Kg of hydrotalcite and 0.2Kg of calcium stearate are weighed, mixed for 2 minutes in a high-speed mixer, and stirred and mixed uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of the temperature of 190 ℃ and the rotating speed of 170 revolutions per minute, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. Melt index, mechanical properties and surface energy tests were performed and the results are shown in table 1.

Example 3

1) Weighing 50Kg of block copolymer polypropylene, 50Kg of high density polyethylene, 0.3Kg of antioxidant 1010 and 0.2Kg of antioxidant 168, uniformly mixing by a high-speed mixer, and then melting, extruding and granulating at 190 ℃ to obtain the polypropylene/polyethylene blend.

2) After heating and vacuumizing the blend obtained in the step (1) to remove moisture, the blend is heated to 80 ℃ in a fluorine/chlorine mixed gas atmosphere of 50kPa to be activated and modified, the fluorine concentration is 1.2 vol%, the chlorine concentration is 98.8 vol%, and the reaction time is 1.0h, and then the blend is replaced by a mixed gas of nitrogen and oxygen (the oxygen accounts for 5vol% of the mixed gas), so that a chlorinated modified polypropylene/polyethylene mixture is obtained.

3) And (3) adding 160Kg of linolenic acid (the proportion is 1:2) into 80Kg of chlorination modified mixture in the step (2), heating to 120 ℃ under the vacuum condition (the pressure in the kettle is less than 200Pa) to carry out in-situ polymerization for 3h, and then washing, separating and drying (vacuum drying, 80 ℃) to obtain the chlorinated polyolefin material modified by the linolenic acid.

4) And (3) putting the chlorinated polyolefin product modified by the linolenic acid in the step (3) into a xylene solvent, heating and stirring the xylene solution of a chlorinated mixture at 130 ℃ for 2h for dissolving, filtering and separating the solution by using a Buchner funnel, washing the solution by using the xylene solvent, and drying the solution in a vacuum oven at 80 ℃ for 2h to obtain the hyperbranched multiphase polymer, wherein the chlorine content of the chlorinated polyolefin is 18.6 wt%, and the oxygen content of the linolenic acid graft polymerization amount is 5.3 wt%.

5) 58Kg of block copolymer polypropylene, 15Kg of polyvinyl chloride, 8Kg of ethylene-butylene copolymer, 4Kg of hyperbranched multiphase polymer, 15Kg of talcum powder, 0.3Kg of antioxidant 1010, 0.3Kg of antioxidant 168, 0.3Kg of hydrotalcite and 0.3Kg of calcium stearate are weighed, mixed for 2 minutes in a high-speed mixer, and stirred and mixed uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of the temperature of 200 ℃ and the rotating speed of 180 r/min, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. Melt index, mechanical properties and surface energy tests were performed and the results are shown in table 1.

Example 4

1) Weighing 40Kg of block copolymer polypropylene, 60Kg of high density polyethylene, 0.3Kg of antioxidant 1010 and 0.2Kg of antioxidant 168, uniformly mixing by a high-speed mixer, and then melting, extruding and granulating at 190 ℃ to obtain the polypropylene/polyethylene blend.

2) Heating and vacuumizing the blend in the step (1) to remove moisture, then heating to 100 ℃ in a fluorine/chlorine mixed gas atmosphere of 60kPa to activate and modify, wherein the fluorine concentration is 2 vol%, the chlorine concentration is 98 vol%, and the reaction time is 2.0h, and then replacing with a nitrogen/oxygen (oxygen accounts for 7 vol% of the mixed gas) mixed gas to obtain a chlorinated modified polypropylene/polyethylene blend.

3) Adding 240kg of linoleic acid (ratio 1: 3) heating to 130 ℃ under the condition of vacuum pumping (the pressure in the kettle is less than 200Pa) to carry out in-situ polymerization reaction for 3h, and then carrying out separation, washing and drying (vacuum drying, 80 ℃) to obtain the linoleic acid modified chlorinated polyolefin material.

4) And (3) putting the chlorinated polyolefin product modified by the linoleic acid in the step (3) into a xylene solvent, heating and stirring the xylene solution of the chlorinated mixture at 130 ℃ for 2h for dissolving, filtering and separating the solution by using a Buchner funnel, washing the solution by using the xylene solvent, and drying the solution in a vacuum oven at 80 ℃ for 2h to obtain the hyperbranched multiphase polymer, wherein the chlorine content of the chlorinated polyolefin is 22.2 wt% as an index, and the oxygen content of the linoleic acid graft polymerization amount is 6.7 wt%.

5) Weighing 47Kg of block copolymer polypropylene, 20Kg of polyvinyl chloride, 10Kg of ethylene-octene copolymer, 6Kg of hyperbranched multi-phase polymer, 17Kg of talcum powder, 0.4Kg of antioxidant 1010, 0.3Kg of antioxidant 168, 0.4Kg of hydrotalcite and 0.4Kg of calcium stearate, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of the temperature of 210 ℃ and the rotating speed of 250 revolutions per minute, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. Melt index, mechanical properties and surface energy tests were performed and the results are shown in table 1.

Example 5

1) Weighing 35Kg of block copolymer polypropylene, 65Kg of high density polyethylene, 0.3Kg of antioxidant 1010 and 0.2Kg of antioxidant 168, uniformly mixing by a high-speed mixer, and then melting, extruding and granulating at the temperature of 180 ℃ to obtain the polypropylene/polyethylene blend.

2) After the blend obtained in the step (1) was heated and evacuated to remove moisture, the blend was heated to 110 ℃ in an atmosphere of a fluorine gas/chlorine gas mixed gas of 80kPa to carry out activation modification, the fluorine gas concentration was 3vol%, the chlorine gas concentration was 97 vol%, and the reaction time was 3.0 hours, and then the mixture was replaced with a nitrogen gas/oxygen gas mixed gas (oxygen gas contained in the mixed gas: 10 vol%), thereby obtaining a chlorinated modified polypropylene/polyethylene blend.

3) And (3) adding 320kg of linolenic acid (the ratio is 1:4) into 80kg of chlorination modified mixture in the step (2), wherein the ratio of the polypropylene/polyethylene mixture to the linolenic acid is 4:1, heating to 150 ℃ under the vacuum condition (the pressure in the kettle is less than 200Pa) to carry out in-situ polymerization for 4h, and then carrying out separation, washing and drying (vacuum drying, 80 ℃) to obtain the chlorinated polyolefin material modified by the linolenic acid.

4) And (3) putting the chlorinated polyolefin product modified by the linolenic acid in the step (3) into a xylene solvent, heating and stirring the xylene solution of a chlorinated mixture at 135 ℃ for 2h for dissolving, filtering and separating the solution, washing the solution with the solvent, and drying the solution in a vacuum oven at 80 ℃ for 2h to obtain the hyperbranched multiphase polymer, wherein the chlorine content of the chlorinated polyolefin is 28.9 wt%, and the oxygen content of the linolenic acid graft polymerization is 8.4 wt%.

5) Weighing 35Kg of block copolymer polypropylene, 25Kg of polyvinylidene chloride, 12Kg of ethylene-octene copolymer, 8Kg of hyperbranched multiphase polymer, 20Kg of talcum powder, 0.4Kg of antioxidant 1010, 0.4Kg of antioxidant 168, 0.5Kg of hydrotalcite and 0.5Kg of calcium stearate, mixing for 2 minutes in a high-speed mixer, and stirring and mixing uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of the temperature of 220 ℃ and the rotating speed of 300 revolutions per minute, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. Melt index, mechanical properties and surface energy tests were performed and the results are shown in table 1.

Comparative example 1

This comparative example is compared to example 1, except that it employs a chlorinated polypropylene/polyethylene comparative reference that is not grafted with linoleic acid.

2) Heating and vacuumizing the mixture obtained in the step (1) to remove moisture, then heating to 40 ℃ in a fluorine/chlorine mixed gas atmosphere of 10kPa to perform activation modification, wherein the fluorine concentration is 0.5vol%, the chlorine concentration is 99.5 vol%, and the reaction time is 0.5h, and then replacing with a mixed gas of nitrogen/oxygen (oxygen accounts for 1vol% of the mixed gas), thereby obtaining a chlorinated modified polypropylene/polyethylene blend.

3) And (3) putting the chlorinated modified mixture obtained in the step (2) into a xylene solvent, heating and stirring the mixture at 130 ℃ for 2 hours for dissolving, wherein the concentration of the xylene solution of the chlorinated mixture is 10 wt%, then separating and washing the solution, and drying the solution in a vacuum oven at 80 ℃ for 2 hours to obtain the chlorinated modified polyolefin, wherein the chlorine content of the chlorinated polyolefin is 8.9 wt%.

4) 83.2Kg of block copolymer polypropylene, 8Kg of polyvinyl chloride, 3Kg of ethylene-octene copolymer, 0.8Kg of chlorinated polyolefin, 5Kg of talcum powder, 0.2Kg of antioxidant 1010, 0.2Kg of antioxidant 168, 0.1Kg of hydrotalcite and 0.1Kg of calcium stearate are weighed, mixed for 2 minutes in a high-speed mixer, and stirred and mixed uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of 180 ℃ and 150 r/min of rotating speed, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. Melt index, mechanical properties and surface energy tests were performed and the results are shown in table 1.

Comparative example 2

This comparative example is compared to example 1, except that it is directly physically blended with linoleic acid as a comparative reference material.

2) After heating and vacuumizing the mixture obtained in the step (1) to remove moisture, the mixture is placed in a fluorine/chlorine mixed gas atmosphere of 10kPa to be heated to 40 ℃ for activation and modification, the fluorine concentration is 0.5vol%, the chlorine concentration is 99.5 vol%, and the reaction time is 0.5h, and then the mixture is replaced by a nitrogen/oxygen mixed gas (the oxygen accounts for 1vol% of the mixed gas), so that a chlorinated modified polypropylene/polyethylene blend is obtained.

3) And (3) putting the chlorinated modified mixture in the step (2) into a xylene solvent, heating and stirring the mixture at 130 ℃ for 2h for dissolving, separating and washing the solution, and drying the solution in a vacuum oven at 80 ℃ for 2h to obtain the chlorinated modified polyolefin, wherein the chlorine content of the chlorinated polyolefin is 8.9 wt% as an index of the chlorination rate.

4) 83.2Kg of block copolymer polypropylene, 8Kg of polyvinyl chloride, 3Kg of ethylene-octene copolymer, 5Kg of talcum powder, 0.65Kg of chlorinated modified polyolefin, 0.15Kg of linolenic acid, 0.2Kg of antioxidant 1010, 0.2Kg of antioxidant 168, 0.1Kg of hydrotalcite and 0.1Kg of calcium stearate are weighed, mixed for 2 minutes in a high-speed mixer, and stirred and mixed uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of 180 ℃ and 150 r/min of rotating speed, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. Melt index, mechanical properties and surface energy tests were performed and the results are shown in table 1.

Comparative example 3

This comparative example is different from example 1 in that maleic anhydride was used as a comparative reference material.

2) After 90Kg of the blend obtained in the step (1) and 45Kg of maleic anhydride were heated and evacuated to remove moisture, the mixture was heated to 40 ℃ in an atmosphere of 10kPa of fluorine gas/chlorine gas mixed gas to carry out activation modification, the fluorine gas concentration was 0.5vol%, the chlorine gas concentration was 99.5 vol%, and the reaction time was 0.5 hour, and then the mixture was replaced with a nitrogen gas/oxygen gas mixed gas (oxygen gas accounted for 1vol% of the mixed gas), thereby obtaining a maleic anhydride-copolymerized chlorinated modified polypropylene/polyethylene blend.

3) And (3) putting the maleic anhydride copolymerized chlorinated modified polypropylene/polyethylene blend in the step (2) into a xylene solvent, wherein the concentration of the xylene solution of the chlorinated mixture is 10 wt%, heating and stirring at 130 ℃ for 2h for dissolving, filtering, separating, washing the solution with the solvent, and drying in a vacuum oven at 80 ℃ for 2h to obtain the maleic anhydride copolymerized modified chlorinated modified polyolefin (wherein the chlorine content is 3.2 wt% and the oxygen content is 0.4 wt%).

4) 83.2Kg of block copolymerization polypropylene, 5Kg of polyvinyl chloride, 3Kg of ethylene-octene copolymer, 5Kg of talcum powder, 0.8Kg of linoleic acid copolymerization modified chlorinated modified polyolefin, 0.2Kg of antioxidant 1010, 0.2Kg of antioxidant 168, 0.1Kg of hydrotalcite and 0.1Kg of calcium stearate are weighed, mixed for 2 minutes in a high-speed mixer, and stirred and mixed uniformly. Then, the uniformly mixed materials are poured into a feed inlet of a double-screw extruder, melted and extruded under the conditions of 180 ℃ and 150 r/min of rotating speed, extruded into strip-shaped primary materials, cooled in a water tank and air, and cut into plastic particles by a granulator. Melt index, mechanical properties and surface energy tests were performed and the results are shown in table 1.

TABLE 1 physical Properties of Polypropylene materials for examples and comparative examples

As can be seen from the comparison of the above tables, in comparative example 1 and comparative example 1, the hyperbranched multiphase polymer can improve the compatibility, mechanical properties and polarity of the polypropylene composite material, and as the ratio of the hyperbranched multiphase polymer to the polyvinyl chloride is increased, the polarity can be greatly improved while the mechanical properties of the composite material are maintained. Comparing example 1 and comparative example 2, the hyperbranched heterophasic polymer imparts to the material a polarity that does not decay substantially over time; compared with the example 1 and the comparative example 3, the hyperbranched heterogeneous polymer obtained by adopting the method of copolymerization while chlorination has lower chlorination rate and polymerization efficiency.

Although the present invention has been described in detail with reference to preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims

1. A polar polypropylene composite, characterized in that it comprises the following components:

35-83.2 parts of polypropylene;

8-25 parts of chlorine-containing polyolefin;

3-12 parts of polyolefin elastomer;

0.8-8 parts of hyperbranched multiphase polymer;

5-20 parts of a filler;

wherein the hyperbranched heterogeneous polymer is formed by introducing unsaturated polar monomers into modified olefin; the base material of the modified olefin is a blend of polypropylene and polyethylene; the unsaturated polar monomer is fatty acid containing at least 2 unsaturated bonds;

the modified olefin is modified through chlorination, bridging between polypropylene and polyethylene mixture molecular chains is realized through coupling of active free radicals generated in the chlorination process, and meanwhile, the free radicals generated in the chlorination modification process and generated by heating and cracking after carbon-chlorine bonds are generated are used as active sites to initiate self-polymerization of flexible long-chain and polyunsaturated polar monomers, so that the hyperbranched multiphase polymer with multiphase and multi-chemical structures is obtained.

2. The polypropylene composite according to claim 1, wherein the polar polypropylene composite comprises the following components:

47-73 parts of polypropylene;

10-20 parts of chlorine-containing polyolefin;

5-10 parts of polyolefin elastomer;

2-6 parts of a hyperbranched multiphase polymer;

10-17 parts of a filler.

3. The polypropylene composite according to claim 1 or 2, wherein the polypropylene is selected from one or more of homo polypropylene, block co-polypropylene and random co-polypropylene.

4. The polypropylene composite according to claim 3, wherein the polypropylene has a melt index at 230 ℃ and 2.16kg of 8 to 35g/10 min.

5. The polypropylene composite of claim 1, wherein the chlorine-containing polyolefin comprises one or more of polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, and chlorinated polypropylene.

6. The polypropylene composite according to claim 1, wherein the chlorinated polyolefin has a molecular weight of 40,000-120,000.

7. The polypropylene composite of claim 1, wherein the polyolefin elastomer is selected from one or more of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, and polystyrene-butadiene copolymer.

8. The polypropylene composite according to claim 1, wherein the hyperbranched heterophasic polymer is prepared by:

9. The polypropylene composite according to claim 8, wherein the raw material of S1 comprises:

35-75 Parts of Polypropylene (PP),

25-65 parts of polyethylene, namely polyethylene,

0.2-0.3 part of antioxidant 1010, 0.2-0.3 part of antioxidant 168;

and/or the polyethylene is selected from one or more of high density polyethylene, low density polyethylene and linear low density polyethylene.

10. The polypropylene composite according to claim 9, wherein the raw material in S1 comprises:

40-65 parts of polypropylene, namely polypropylene,

35-60 parts of Polyethylene (PE),

0.2-0.3 part of antioxidant 1010, 0.2-0.3 part of antioxidant 168;

the polyethylene has a melt index of 6-25g/10min at 190 ℃ under 2.16 kg.

11. The polypropylene composite material according to claim 8, wherein the pressure of the fluorine-chlorine mixed gas in S2 is 10 to 80 KPa; the proportion of the fluorine gas is 0.5vol% to 3.0vol% based on the total volume of the mixed gas; the treatment time is 0.5-3 h; the reaction temperature is 40-110 ℃;

and/or performing gas replacement after treatment, wherein the replacement gas is a mixed gas of inert gas and oxygen, and the proportion of the oxygen in the mixed gas is 1-10 vol% based on the total volume of the mixed gas.

12. The polypropylene composite material according to claim 11, wherein the pressure of the fluorine-chlorine mixed gas in S2 is 30-60 KPa; the proportion of fluorine gas is 0.8-2.0 vol% based on the total volume of the mixed gas; the treatment time is 0.8-2 h; the reaction temperature is 60-100 ℃;

and/or the proportion of oxygen in the mixed gas is 3vol% to 8vol% based on the total volume of the mixed gas.

13. The polypropylene composite of claim 8, wherein the unsaturated polar monomer in S3 is selected from one or more of eleostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid;

and/or the temperature of the self-polymerization reaction is 100-150 ℃, and the reaction time is 1-4 h.

14. The polypropylene composite according to claim 8, wherein the heating temperature in S4 is 130-140 ℃.

15. A method for preparing the polar polypropylene composite according to any one of claims 1 to 14, wherein the method comprises: uniformly mixing polypropylene, chlorinated polyolefin, polyolefin elastomer, hyperbranched multiphase polymer, filler and auxiliary agent, adding the mixture into a double-screw extruder through a main feeding port, performing melt extrusion granulation, cooling and granulating to obtain the polar polypropylene composite material.

16. The method according to claim 15, wherein the twin-screw extruder has a rotation number of 150 to 300 rpm and a reaction temperature of 170 to 220 ℃.

17. The method as recited in claim 15 wherein the reaction temperature of the twin screw extruder is 180-210 ℃.