CN1100087C - Stuffing mother particle for toughening polyolefine and preparation process and usage thereof - Google Patents

Abstract

A kind of filler masterbatch for toughening polyolefin and its preparation method and application belong to the field of inorganic particle toughened polyolefin materials, the filler masterbatch includes inorganic filler with a particle diameter of 0.5 μm-40 μm, surface treatment agent, functionalized thermoplastic Elastomer, thermoplastic resin and their mixture, processing aids, the above-mentioned components are uniformly mixed, extruded by a twin-screw extruder or kneaded by a twin-roller kneader, and granulated. The filler masterbatch for toughened polyolefin of the present invention has inorganic filler uniformly dispersed in the masterbatch carrier, and when compounded with polyolefin materials, it can be regenerated in the form of "core-shell" structure particles with the inorganic filler as the core carrier as the shell. Distributed in the polyolefin matrix, its composite material has achieved high rigidity and high toughness.

Description

A preparation method of filler masterbatch for toughened polyolefin

The invention relates to a filler masterbatch capable of strengthening and toughening polyolefin materials, in particular to a filler masterbatch for polyolefin with low price, increased rigidity and high toughness.

Usually, in the process of plastic processing, the added additives and additives such as stabilizers, flame retardants, pigments, etc. are concentrated on the carrier resin to make masterbatches. It has many advantages, such as good performance stability of plastic products, It is easy to dosing and blending operations, clean the working environment, etc., so the functional research of filler masterbatches, such as the development of filler masterbatches with strengthening and toughening functions, has become a hot spot.

Xu Shengxiu reported a highly dispersed plastic filling masterbatch in the Chinese invention patent "Plastic Filling Masterbatch" (Notice No. 1021857), which is made of calcium carbonate filler as the main body and chelated titanate as the filler. Surface treatment agent, petroleum resin, ethylene-propylene rubber, etc. are prepared as carriers. This kind of filling masterbatch is characterized by excellent dispersion performance in the polymer matrix, and can improve plastic products under a large filling amount. If 20% (wt%) of the filler masterbatch is added to make polypropylene packing tape, the tensile strength of the product can be increased from >160kg/cm ² to 329kg/cm ² according to the departmental standard, and the elongation is determined by the departmental standard The <25% of the plastic is reduced to 17%, but the plastic product does not obtain high toughness.

In Sun Shaoxuan's Chinese invention patent "Universal plastic filler masterbatch and its preparation method" (publication number 1061028A), it involves a filler masterbatch for general-purpose plastics, which is made of fillers that have been ultrafinely pulverized to 1-20μ Zeolite and white carbon black, carrier polyethylene with a molecular weight of 1000-6000, and regulator turpentine and white oil or hexapentylthritol methyl ester are kneaded and granulated. The filler masterbatch is characterized by a wide range of applications and can be used in large Among most thermoplastics, since the masterbatch is based on low molecular weight polyethylene, the strengthening and toughening effect of the masterbatch on plastic products cannot be very significant.

Zhang Yuncan, Pan Enli, etc. in the Chinese invention patents "Toughening Masterbatch for Polyolefin Plastics and Its Manufacturing Method" (Notice No. 1124747) and "Super Tough Masterbatch for Polypropylene Plastics and Its Manufacturing Method" (Notice No. 1131165) , reported the method of using multifunctional coupling agent and co-coupling agent to couple masterbatch carrier resin and inorganic filler to prepare toughened masterbatch and super tough masterbatch. This filler masterbatch has good effect on polyolefin plastics The toughening effect, the best toughening effect can increase the notched impact strength of polypropylene material from 7.3KJ/m ² to 70-80KJ/m ² , but this method is due to the connection between the inorganic filler and the masterbatch carrier. There is a chemical bond between the inorganic filler and the coupling agent, and only the physical entanglement of molecular chains between the auxiliary coupling agent and the carrier. Therefore, it is difficult to obtain high strength and high Rigidity, such as when the above-mentioned masterbatch filled polypropylene material obtains the best toughness, the tensile strength of the polypropylene material decreases from 33.2MPa to 17-18MPa.

In order to overcome the above-mentioned shortcomings in the prior art that polyolefin composite materials with high rigidity and high toughness cannot be obtained at the same time, the present invention provides a preparation method using inorganic fillers as the main body and thermoplastic elastomers, thermoplastic resins, polymer emulsions and mixtures thereof as carriers. The easily dispersible, reinforced, and highly toughened filler masterbatch, when the filler masterbatch is compounded with polyolefin materials, can obtain low-cost, high rigidity of "core-shell" structure particles with inorganic filler as the core carrier as the shell , High toughness polyolefin composite material.

The technical composition of a filler masterbatch for toughening polyolefins in the present invention is mainly based on inorganic fillers, coupling agents and organic monomers are surface treatment agents for inorganic fillers, thermoplastic elastomers, thermoplastic resins, polymer emulsions and the like. The mixture is the carrier, and the low-molecular polymer, low-molecular oil, fatty acid ester, fatty acid and its salt are the processing aids. The filler masterbatch includes the following components and content (weight percent):

Inorganic filler 47.5-84.5

Surface treatment agent 0.5-2.5

Carrier 10-30

Processing aids 5-18

Antioxidant 0-2

The above-mentioned inorganic fillers are talcum powder, kaolin, calcium carbonate, wollastonite, mica, silicon dioxide, aluminum oxide, aluminum hydroxide, titanium dioxide, pyrophyllite, bentonite, and the particle diameter is 0.5 μm-40 μm, preferably The diameter is 1.5μm-5μm. The above-mentioned surface treatment agent is a silane coupling agent such as γ-aminopropyltriethoxysilane, γ-propylmethacrylate trimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, titanate Coupling agents such as isopropyl triisodecanoyl titanate, cationic, anionic, nonionic surfactants, ethylenic monomers and ester monomers (including initiators) such as styrene and maleic anhydride ( Initiator DTBP) mixture. The above-mentioned carriers are natural rubber, butadiene rubber, butyl rubber, styrene-butadiene rubber, nitrile rubber, neoprene rubber, isoprene rubber, EPDM, EVA, SBS, ethylene-α-olefin copolymer, polyester, polyurethane, Polyolefins such as hydroxyl-terminated polybutadiene, polypropylene, high-density polyethylene, low-density polyethylene and their maleic anhydride, bismaleimide, acrylate, vinyl monomer graft or copolymerization graft modification Thermoplastic elastomers and thermoplastic resins such as bismaleimide graft modified ethylene-propylene-diene copolymer, trimethoxypropane triacrylate modified ethylene-propylene-diene copolymer, maleic anhydride The graft-modified ethylene-propylene rubber has a melt flow rate of 0.5g/10min-50g/10min. The above-mentioned processing aids are petroleum resin, polypropylene wax, polyethylene wax, solid paraffin, liquid paraffin, naphthenic oil, lauric acid ester, oleic acid ester, oleic acid, stearic acid ester, stearic acid and its salts such as Calcium stearate. The above-mentioned antioxidants are domestic phenolic antioxidants and amine antioxidants.

A kind of preparation method of filler masterbatch for toughened polyolefin of the present invention is to carry out according to the following sequence of steps:

(1) By weight percentage, add 0.5-2.5 of the above-mentioned surface treatment agent to the diluent and treat the surface of the inorganic filler 47.5-84.5 in a high-speed mixer,

(2) Knead the treated inorganic filler 48.0-87.0, carrier 10-30, processing aid 5-18, and antioxidant 0-2 in a high-speed mixer, and the kneading time is 5-30 minutes. 10°C-100°C,

(3) The kneaded product is co-extruded and granulated in a twin-screw extruder at a processing temperature of 140°C-200°C.

Another preparation method of a kind of toughened polyolefin filling masterbatch of the present invention is to carry out in the following order of steps:

(1) By weight percentage, add 0.5-2.5 of the above-mentioned surface treatment agent to the diluent and treat the surface of the inorganic filler 47.5-84.5 in a high-speed mixer,

(2) Knead the treated inorganic filler 48.0-87.0, carrier 10-30, processing aid 5-18, and antioxidant 0-2 in a high-speed mixer, and the kneading time is 5-30 minutes. 10°C-100°C,

(3) Knead the kneaded mixture in a kneader at a temperature of 120°C-150°C, form it into flakes, and cut it into pellets.

The purpose of the filler masterbatch for toughening polyolefin of the present invention is to prepare polyolefin composite material. The aforementioned polyolefins are homopolypropylene, copolymerized polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ethylene copolymers.

The purpose of surface treatment of inorganic fillers is to introduce reactive groups or unsaturated bonds on the surface. When the above-mentioned inorganic fillers and carriers or modified carriers with functional There is a carrier or modified carrier that can be copolymerized with the unsaturated bond on the surface of the filler. In the process of kneading and extrusion, it is triggered by heat or an initiator, and the reactive group on the surface of the inorganic filler and the carrier partly contacts and undergoes a chemical reaction. , connect the two with a certain connection strength and exist in the prepared filler masterbatch. When the prepared filler masterbatch is compounded with polyolefin, the filler and masterbatch carrier in the filler masterbatch can be uniformly dispersed in the polyolefin matrix in the form of "hard core-soft shell" structure particles with the inorganic filler as the core carrier as the shell, instead of Pure rubber elastomer toughened polyolefin material.

The filler masterbatch for toughened polyolefin of the present invention has the characteristics that the inorganic filler can be uniformly dispersed in the filler masterbatch carrier, and evenly distributed in the polyolefin matrix in the form of inorganic filler-masterbatch carrier "hard core-soft shell" structure . When the amount of the filler masterbatch is 30-40 wt%, the modulus of the polyolefin composite material can be increased by 0.5-1 times, the notched impact strength can be increased by 1-4 times, and the processing is convenient and the cost is low.

Example 1

774.5 g of talcum powder with a particle size of 5 μm treated with 115 g of γ-propylmethacrylate trimethoxysilane, 91.2 g of ethylene-propylene-diene copolymer modified by bismaleimide grafting, and Melt flow rate is 2.5g/10min, polypropylene 60.8g, its melt flow rate is 30g/10min, polypropylene wax 53.5g, calcium stearate 10g, N-cyclohexyl-N'-phenyl-p-phenylenediamine 10g After kneading in a high-speed mixer at room temperature for 20 minutes, it is extruded through a twin-screw extruder. The barrel temperature of the extruder is 150-160-190-200-190°C from the inlet to the outlet, and water-cooled and cut into pellets.

The talcum powder filled masterbatch and ethylene-propylene copolymerized polypropylene resin are mixed in a high-speed mixer at a ratio of 10:90 (percentage by weight) for 3-5 minutes, and then compounded in a twin-screw extruder, and the barrel of the extruder is The temperature from the inlet to the outlet is 195-205-205-220-195°C, and the mechanical performance test results of the composite materials are shown in Table 1.

Example 2:

The talcum powder filler masterbatch prepared in Example 1 and ethylene-propylene copolymerized polypropylene were compounded in the same method and conditions as in Example 1 at a ratio (percentage by weight) of 20:80.

Example 3:

The talcum powder filler masterbatch prepared in Example 1 and ethylene-propylene copolymerized polypropylene were compounded in the same method and conditions as in Example 1 at a ratio (weight percentage) of 30:70.

Example 4:

The talcum powder filler masterbatch prepared in Example 1 and ethylene-propylene copolymerized polypropylene were compounded in the same method and conditions as in Example 1 at a ratio (weight percentage) of 40:60. Table 1 After the talcum powder filler masterbatch is compounded with the polypropylene copolymer resin, the mechanical properties of the material compound Implementation Implementation Implementation Implementation

Example 1 case 2 cases 3 cases of 3 cases of 4 gap cantilever beams shock 218.0 267.0 308.0 525.0 intensity (J/m) Stretching strength (MPA) 28.5 27.8 26.1 24.7 Fracture and elongation ( %) 1044.8 1020.0 979.2 997.8 Bending strength (MPA) 27.4 26.1 25.0 23.2 Flexural modulus (GPa) 0.7 0.8 0.8 0.9

Embodiment 5 (comparative example):

Talc powder and ethylene-propylene copolymerized polypropylene resin were uniformly mixed at a ratio of 10:90 (percentage by weight), compounded and injection molded under the same processing conditions as in Example 1.

Embodiment 6 (comparative example):

Talc powder and ethylene-propylene copolymerized polypropylene resin were uniformly mixed at a ratio of 20:80 (percentage by weight), compounded and injection molded under the same processing conditions as in Example 1.

Embodiment 7 (comparative example):

Talc powder and ethylene-propylene copolymerized polypropylene resin were uniformly mixed in a ratio (weight percentage) of 30:70, then compounded and injection molded under the same processing conditions as in Example 1.

Embodiment 8 (comparative example):

Talc powder and ethylene-propylene copolymerized polypropylene resin were uniformly mixed at a ratio (weight percentage) of 40:60, then compounded and injection molded under the same processing conditions as in Example 1. Table 2 Mechanical properties of talcum powder and copolymerized polypropylene composites Implementation Implementation Implementation Implementation

In 5 cases in 6 cases and 7 cases of 8 gap cantiles, 181.0 178.0 160.5 129.0 hit strength (J/m) stretching strength (MPA) 29.8 30.5 30.2 29.8 Fracture and elongation rate ( %) 1021.2 1122.4 659.8 389.2 Bending strength (MPA) 34.1 37.9 38.5 40.2 Flexural modulus (GPa) 1.0 1.1 1.2 1.2

Embodiment 9:

704.5 g of talc powder with a particle size of 5 μm, 70 g of titanium dioxide, and 91.2 g of ethylene-α-olefin copolymer treated with 11.5 g of isopropyl triisostearyl titanate, and the melt flow rate is 0.5 g/10 min , polypropylene 60.8g, its melt flow rate is 50g/10min, naphthenic oil 53.5g, calcium stearate 10g, N-cyclohexyl-N'-phenyl-p-phenylenediamine 10g, at 40℃-50℃ The kneading temperature is kneaded in a high-speed mixer for 30 minutes, and then extruded through a twin-screw extruder. The barrel temperature of the extruder is 160-180-190-200-170°C from the inlet to the outlet, and water-cooled and cut into pellets.

The above-mentioned filled masterbatch and ethylene-propylene copolymerized polypropylene resin were used in the ratio of 40:60 (weight percent), and the same processing method as in Example 1 was used to obtain a filled copolymerized polypropylene composite material, and its mechanical properties are shown in Table 3.

Example 10:

Treated with 11.5g of γ-aminopropyltriethoxysilane, 774.5g of talcum powder with a particle size of 5 μm, and 152g of ethylene-propylene-diene copolymer modified by trimethoxypropane triacrylate, its melt flow rate is 5g/10min, polypropylene wax 53.5g, calcium stearate 10g, N-cyclohexyl-N'-phenyl-p-phenylenediamine 10g, under the processing method identical with embodiment 1 and processing condition, prepare filler The pellets are compounded with the copolymerized polypropylene resin at a ratio of 40:60 (weight percent) to form a filled composite material.

Embodiment 11 (comparative example):

Ethylene-propylene copolymerized polypropylene resin, the brand name is PP1330, produced by Beijing Yanshan Petrochemical Corporation No. 2 Chemical Factory, pellets, and the processing conditions are the same as in Example 9.

Embodiment 12 (comparative example):

When the copolymerized polypropylene and the ethylene-propylene-diene elastomer are filled with the polyolefin composite material according to the master batch prepared in Example 9, the copolymerized polypropylene matrix and the ethylene-propylene-diene elastomer as the master batch carrier are both the same After the ratio (percentage by weight) of the mixture is uniformly mixed, composite molding is performed, and the molding conditions are the same as in Example 9. Table 3 embodiment 9, embodiment 10 and embodiment 8, embodiment 11, the comparative compound of embodiment 12 results Implementation Implementation Implementation Implementation Implementation Implementation

In 9 cases in 10 cases and 8 cases and 11 cases of 12 gaps. Bending strength 34.7 25.3 40.2 30.7 24.9 degrees (MPa) bending modulus 1.5 1.0 1.2 0.8 0.7 weight (GPa)

Example 13:

With adsorbed initiator DTBP0.1g, styrene monomer 8.0g, maleic anhydride 1.6g, particle size is 750.8g of calcium carbonate of 1.5 μm, propylene-alpha-olefin copolymer 158.0g, and its melt flow rate is 0.5g/ 10min, 39.6g of hydroxyl-terminated polybutadiene, 7.9g of laurate, 42.1g of polyethylene wax, kneaded by a high-speed mixer at room temperature for 10min, kneaded on a double-roller kneader, formed into sheets, and pelletized. The mixing temperature is 120-150°C.

The above-mentioned filling masterbatch and polypropylene resin are formulated according to 40:60 (weight percentage), and the filling polypropylene composite material is obtained by the same processing method as in Example 1.

Embodiment 14 (comparative example):

Table 4 also shows the mechanical properties of the filled polypropylene composite material obtained by using the same processing method and processing conditions as in Example 13 with calcium carbonate and polypropylene matrix in a ratio of 40:60 (weight percent).

Embodiment 15 (comparative example):

Homopolypropylene, the brand name is PP2401, produced by Beijing Yanshan Petrochemical Corporation No. 2 Chemical Factory, the pellets are processed under the same processing conditions as in Example 13 and injection molded into national test standard samples. Table 4 Example 13 and Example 14, the results of Example 15 are compared with the compound

    jib impact   strength   elongation   strength   modulus

Impact Strength (MPa) Rate (%) (MPa) (GPa)

(J/M) Example 13 166.3 29.2 156.0 48.5 2.0 Example 14 47.5 35.0 212.6 52.1 1.7 Example 15 22.5 37.3 381.7 50.3 1.4

Example 16:

679.5g of 2.5μm kaolin treated with 7.5g gamma-glycidyloxypropyltrimethoxysilane, 75.5g of 2.5μm aluminum hydroxide, 47.3g of high-density polyethylene, the melt flow rate of which is 5g/10min, and 47.3g of low-density polyethylene g, its melt flow rate is 50g/min, 94.6g of ethylene-propylene rubber grafted with maleic anhydride, its melt flow rate is 3g/min, liquid paraffin 37.8g, calcium stearate 8g, four [beta-(3, 4g of 5-ditert-butyl-4-hydroxyphenylpropionic acid] pentaerythritol ester, 6g of didodecyl thiodipropionate were kneaded at room temperature for 20min in a high-speed mixer, extruded through a twin-screw extruder, and extruded The temperature of the barrel of the machine is 140-160-180-200-190°C from the inlet to the outlet, and it is water-cooled and cut into pellets.

The above-mentioned filling masterbatch and high-density polyethylene resin are mixed according to the formula of 20:80 (weight percentage), and then directly injected into the national test standard sample in the injection machine, the injection temperature is 200 ° C, and the injection pressure is 13.5 MPa, the test results of mechanical properties of its composite materials are shown in Table 5.

Example 17:

High-density polyethylene resin, the trade mark is HDPE DMD7006, and Qilu Petrochemical Company plastic factory produces, pellet, and processing condition is the same with embodiment 16.

Example 18:

With the kaolin and aluminum hydroxide mixed filler and high-density polyethylene resin of the same proportioning ratio as in Example 16, according to the formula of 20:80 (percentage by weight), the filled high-density polyethylene resin obtained with the same processing method and processing conditions as in Example 16 The results of mechanical properties test of polyethylene composites can also be seen in Table 5. Table 5 Example 16 and Example 17, Comparative Compound of Example 18 Results Notch Cantilever Stretch Fracture Bending Bending

Beam Impact Strength Strength Elongation Strength Modulus

Degree (J/M) (MPA) rate ( %) (MPA) (GPA) Example 16 56.0 22.7 72.0 39.8 1.5 Comparison Example 17 34.1 250.0 33.8 0.8 Comparison Example 18 37.6 26.3 136.0 37.6 1.3

Claims (8)

1. a kind of preparation method of toughening polyolefin filler masterbatch, it is characterized in that carrying out in the following order of steps: (1) by weight percentage, treat the surface of inorganic filler 47.5-84.5 with surface treatment agent 0.5-2.5 in high-speed mixer, (2) Knead the treated inorganic filler 48.0-87.0 with carrier 10-30, processing aid 5-18, and antioxidant 0-2 in a high-speed mixer. The kneading time is 20-30 minutes, and the kneading temperature is 25°C-50°C, (3) Extrude the above-mentioned kneaded mixture through a twin-screw extruder at a temperature of 140°C-200°C, and then granulate it. 2. A preparation method for a toughened polyolefin filled masterbatch, characterized in that it is carried out in the following steps: (1) by weight percentage, treat the surface of inorganic filler 47.5-84.5 with surface treatment agent 0.5-2.5 in high-speed mixer, (2) Knead the treated inorganic filler 48.0-87.0 with carrier 10-30, processing aid 5-18, antioxidant 0-2 in a high-speed mixer, (3) The above-mentioned kneaded mixture is kneaded in a kneader at 120°C-150°C, formed into flakes and pelletized. 3. The preparation method of a filler masterbatch for toughened polyolefin according to claim 1 or 2, characterized in that the inorganic filler is talcum powder, kaolin, calcium carbonate, titanium dioxide or aluminum hydroxide. 4. The preparation method of a filler masterbatch for toughened polyolefin according to claim 1 or 2, characterized in that the particle diameter of the inorganic filler is 1.5 μm-5 μm. 5. The preparation method of a kind of toughened polyolefin filling masterbatch according to claim 1 or 2, characterized in that the surface treatment agent is γ-propylmethacrylate trimethoxysilane, γ- Aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, isopropyltriisostearyl titanate or a 5:1 by weight mixture of styrene and maleic anhydride. 6. the preparation method of a kind of toughening polyolefin filling masterbatch according to claim 1 or 2, is characterized in that described carrier is the ethylene-propylene-diene of bismaleimide graft modification Copolymer, ethylene-propylene-diene copolymer grafted with trimethoxypropane triacrylate, ethylene-propylene rubber grafted with maleic anhydride, ethylene-α-olefin copolymer, polypropylene, low-density polyethylene, High density polyethylene or hydroxyl terminated polybutadiene. 7. The preparation method of a filler masterbatch for toughened polyolefin according to claim 6, characterized in that the melt flow rate of the carrier is 0.5g/10min-50g/10min. 8. The preparation method of a kind of toughened polyolefin filler masterbatch according to claim 1 or 2, characterized in that said processing aid is polypropylene wax, polyethylene wax, laurate, stearic acid Calcium, liquid paraffin or naphthenic oil.