阅读说明：本技术 一种用于pp增强改性的相容料及其制备方法和应用 (Compatible material for PP (polypropylene) reinforcement modification and preparation method and application thereof ) 是由 曹贵平 方学锋 于 2021-08-17 设计创作，主要内容包括：本发明公开了一种用于PP增强改性的相容料及其制备方法和应用,相容料由PP主料、接枝改性第一单体、接枝改性第二单体、引发剂、抗氧母料和润滑剂组成。本发明的相容料利于纤维增强聚丙烯的加工,增强聚丙烯热塑性树脂的综合性能,适用于玻璃纤维增强聚丙烯热塑性树脂的制备。(The invention discloses a compatible material for PP (polypropylene) reinforcement modification and a preparation method and application thereof. The compatible material of the invention is beneficial to the processing of fiber reinforced polypropylene, enhances the comprehensive performance of polypropylene thermoplastic resin, and is suitable for the preparation of glass fiber reinforced polypropylene thermoplastic resin.)

1. A compatible material for PP enhancement modification is a mixture composed of a PP main material, a first graft modification monomer, a second graft modification monomer, an initiator, an antioxidant master batch and a lubricant, and is characterized in that:

the PP in the mixture is a mixture prepared from one or more of isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene and copolymerized polypropylene according to a certain proportion;

the grafting modification first monomer in the mixture is vinyl silane coupling agent or methacryloxy silane coupling agent, the dosage of the grafting modification first monomer is 0.2-15% of the mass of the polypropylene main material, and the vinyl silane coupling agent has the following structure:

CH₂＝CHSiR₁Cl_xwherein R is₁＝-H、-CH₃、-CH₂CH₃X is 2, 3 CH₂＝CHSi(OR₂)₃Wherein R is₂＝-CH₃、-CH₂CH₃(ii) a The structure of the methacryloxy silane coupling agent is as follows:

CH₂＝C(CH₃)COO(CH₂)₃Si(OR₃)₃or CH₂＝C(CH₃)COO(CH₂)₃Si(CH₃)(OR₃)₂Wherein R is₃＝-CH₃、-CH₂CH₃；

The grafting modified second monomer in the mixture is one or a mixture of more of itaconic anhydride and maleic anhydride which are prepared according to a certain proportion, and the using amount of the grafting modified second monomer is 0.0001-12% of the mass of the polypropylene;

the initiator in the mixture is one or a mixture of two of cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile, and the dosage of the initiator is 0.15 to 6.5 percent of the mass of the polypropylene main material;

the using amount of the antioxidant master batch in the mixture is 0.25-12% of the mass of the polypropylene;

the lubricant in the mixture is stearic acid, sodium oleate, butyl laurate or calcium stearate, and the dosage of the lubricant is 0.12-7% of the mass of the polypropylene main material.

2. A compatibilizer for enhancing and modifying PP according to claim 1 wherein:

the PP in the mixture is a mixture prepared from any two of isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene and copolymerized polypropylene according to a certain proportion, and the proportion of the two is 5-96: 95-4 calculated by 100 parts of the total weight.

3. A compatibilizer for enhancing and modifying PP according to claim 1 wherein:

the second grafting monomer in the mixture is itaconic anhydride and maleic anhydride, and the total amount of the amine of the mixture prepared from any two of the itaconic anhydride and the maleic anhydride according to a certain proportion is 100 parts, and the proportion of the amine and the amine is 0.01-100.

4. A compatibilizer for enhancing and modifying PP according to claim 1 wherein:

the dosage of the first grafting monomer in the mixture is 1.0-12% of the mass of the polypropylene main material;

the dosage of the second grafting monomer is 0.5-11% of the mass of the polypropylene main material;

the dosage of the initiator is 0.5 to 5.5 percent of the mass of the polypropylene main material;

the dosage of the antioxidant master batch is 1.5 to 9 percent of the mass of the polypropylene;

the dosage of the lubricant is 0.25-6% of the mass of the polypropylene main material.

5. A compatibilizer for enhancing and modifying PP according to claim 1 wherein:

the dosage of the first grafting monomer in the mixture is 1.5-9% of the mass of the polypropylene main material;

the dosage of the second grafting monomer is 1.2-7.5% of the mass of the polypropylene main material;

the dosage of the initiator is 1.0 to 3.5 percent of the mass of the polypropylene main material;

the dosage of the antioxidant master batch is 2.5 to 6.5 percent of the mass of the polypropylene;

the dosage of the lubricant is 0.5-4.5% of the mass of the polypropylene main material.

6. The method for preparing the compatibilizer for PP enhancement modification according to claim 1, comprising the following steps:

1) feeding the materials

Weighing a PP main material, a graft modification first monomer, a graft modification second monomer, an initiator, an antioxidant master batch and a lubricant according to a certain proportion, and putting the materials into a mixer to be uniformly stirred;

2) screw extrusion

And adding the mixture into a screw extruder, heating the screw extruder at multiple zones under controlled temperature, carrying out grafting reaction in the screw extruder, extruding from the head of the screw extruder after the reaction is finished, and carrying out spinning, cooling and grain cutting to obtain the required compatible material.

7. The method for preparing the compatibilizer for PP enhancement modification according to claim 6, wherein the method comprises the following steps:

the temperature setting of screw extruder divide into 3 ~ 9 districts, and each district temperature setting value is respectively: the setting value of the 1-3 area is 165-175 ℃, the setting value of the 4-6 area is 180-190 ℃, and the setting value of the 7-9 area is 195-210 ℃.

8. The use of the compatibilizer for PP enhancement modification according to claim 1 in a glass fiber reinforced polypropylene thermoplastic resin.

Technical Field

The invention belongs to the technical field of production of compatible materials for processing polypropylene thermoplastic composite materials, and particularly relates to a reinforced modified polypropylene material compatible material and a preparation method and application thereof.

Background

Polypropylene is a thermoplastic high-molecular resin with large output, wide application and good comprehensive performance, and other components are required to be added in the production process of a plurality of products to increaseThe performance of strong polypropylene, such as common glass fiber reinforced polypropylene thermoplastic resin (usually abbreviated as LFT, CFT, GFT and the like), is that glass fiber is added into polypropylene resin, various special-shaped structural members, semi-structural members and non-structural members are obtained through formula optimization, process optimization, extrusion, stamping/die pressing, and the addition of the glass fiber endows the material with excellent comprehensive properties of light weight, impact resistance, bending resistance, tensile strength, temperature resistance and the like, is widely applied to the fields of automobiles, subways, high-speed rails, airplanes, spaceflight, buildings, traffic and the like, and is suitable for low-carbon and green development of society and economy. However, polypropylene is a nonpolar organic high molecular polymer, and the main component of the glass fiber is SiO₂The polypropylene fiber is an inorganic fiber material with certain polarity, and when the glass fiber is simply added into polypropylene, the compatibility of the surface interface of the polypropylene and the glass fiber is poor, so that the structure and the performance of the material can not meet the actual requirements.

Therefore, there is a need to improve the compatibility between the glass fiber and the surface interface of polypropylene and improve the overall performance of LFT materials and related materials. The more common method is to add a material to the system that is compatible with both the glass fiber and the polypropylene during processing. There are many reports disclosing the technology, such as maleic anhydride, acrylate, etc., grafted on the surface of polypropylene. In order to facilitate the processing of the fiber reinforced polypropylene, the polypropylene graft-modified material is often prepared into a compatibilizer (also called "compatibilizer", "master batch", etc.), and is generally mixed with the polypropylene main material in a particle form during processing and fed into a forming device.

The invention discloses a compatible material for polypropylene processing and a preparation method thereof, in order to better obtain reinforced polypropylene thermoplastic resin with excellent comprehensive performance.

Disclosure of Invention

The invention aims to provide a method for preparing a mixture according to a certain process formula, feeding the mixture of a PP main material, a modifier, an initiator and an auxiliary agent into a screw extruder through a screw extruder reactor, extruding and granulating at a certain temperature to obtain a compatible material, and the obtained compatible material is mainly used for enhancing and modifying polypropylene.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the compatible material is a mixture consisting of a PP main material, a grafting modification first monomer, a grafting modification second monomer, an initiator, an antioxidant master batch and a lubricant, and is prepared by weighing the mixture according to a certain proportion, adding the mixture into a mixer, uniformly stirring the mixture, and adding the mixture into a hopper of a screw extruder according to a certain flow through an automatic feeding unit. The screw extruder is heated by multi-zone temperature control, after the temperature of each zone reaches a set value, a screw motor is started, a screw rotates at a certain rotating speed, an automatic feeding unit is started, the mixture in a hopper enters the screw extruder at a certain flow rate, grafting reaction occurs in the screw extruder, after the reaction is finished, the mixture is extruded from the head of the screw extruder, and the required compatible material is obtained after spinning, cooling and grain cutting.

The PP in the mixture is a mixture prepared from one or more of isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene and copolymerized polypropylene according to a certain proportion. The dosage is 100 parts, when the polypropylene is a single polypropylene model, the dosage is 100, when the polypropylene is a mixture of two polypropylenes, the two polypropylenes are mixed according to a certain proportion, the total amount is 100 parts, and the concrete formula is as follows: 5-96: 95-4 of isotactic polypropylene and syndiotactic polypropylene, 7-95: 93-5 of isotactic polypropylene and atactic polypropylene, 11.5-92.5: 88.5-7.5 of isotactic polypropylene and copolymerized polypropylene, 11.5-93: 88.5-7 of syndiotactic polypropylene and atactic polypropylene, 13.5-77.5: 86.5-22.5 of syndiotactic polypropylene and 86-96: 82-4 of atactic polypropylene and copolymerized polypropylene. The melt index of the obtained melt is 15-90, preferably 20-70, and most preferably 30-70. These polypropylene materials are commercially available.

The grafting modified first monomer in the mixture is vinyl silane coupling agent, methacryloxy silane coupling agent and the like. Typical vinyl silane coupling agents have the structure:

CH₂＝CHSiR₁Cl_xwherein R is₁＝-H、-CH₃、-CH₂CH₃X is 2, 3 CH₂＝CHSi(OR₂)₃Wherein R is₂＝-CH₃、-CH₂CH₃. Typical methacryloyloxyalkyl silane coupling agents have the structure:

CH₂＝C(CH₃)COO(CH₂)₃Si(OR₃)₃or CH₂＝C(CH₃)COO(CH₂)₃Si(CH₃)(OR₃)₂Wherein R is₃＝-CH₃、-CH₂CH₃。

The dosage of the first grafting monomer is 0.2-15% of the mass of the polypropylene main material, the preferred range is 1.0-12%, and the best dosage range is 1.5-9%.

The grafting modified second monomer in the mixture is itaconic anhydride and maleic anhydride, the itaconic anhydride and the maleic anhydride can be used independently or mixed according to a certain proportion, and when the two are mixed for use, the proportion of the two is 0.01-100. The dosage of the polypropylene is 0.0001-12% of the mass of the polypropylene, preferably 0.5-11%, and most preferably 1.2-7.5%, regardless of single use or mixed use. The second monomer itaconic anhydride, maleic anhydride and the first monomer play a good synergistic role, and the performance of the compatilizer is superior to that of the compatilizer obtained by only adding the first monomer, not adding itaconic anhydride/maleic anhydride, or not adding the first monomer and only adding itaconic anhydride/maleic anhydride.

The initiator in the mixture is one or a mixture of two of cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile. The dosage of the initiator is 0.15-6.5% of the mass of the polypropylene main material, the preferred range is 0.5-5.5%, and the best dosage range is 1.0-3.5%.

The dosage of the antioxidant master batch in the mixture is 0.25-12% of the mass of the polypropylene, the preferred range is 1.5-9%, and the best range is 2.5-6.5%. The antioxidant master batch can be purchased in the market, is suitable for enhancing the multi-aspect performance index requirements of PP, is preferably special antioxidant master batch for PP, and is most preferably PP antioxidant master batch produced by Changzhou Lefeite new material science and technology company Limited. The invention focuses on the production method of the compatible material, and the patent does not describe the production of the special antioxidant master batch for PP, and other application patents are described.

The lubricant in the mixture is higher fatty acid and ester or salt thereof, typically stearic acid, sodium oleate, butyl laurate and calcium stearate. The dosage of the lubricant is 0.12-7% of the mass of the polypropylene main material, the preferred range is 0.25-6%, and the best dosage range is 0.5-4.5%.

The grafting ratio of the polypropylene is controlled to be 0.1-12%, preferably 0.25-10%, and most preferably 0.5-9%. Carrying out polypropylene chemical grafting in a screw extruder, uniformly mixing polypropylene, a first monomer, a second monomer, an initiator, an antioxidant master batch and a lubricant according to the proportion, and feeding the mixture into the screw extruder with set temperature, wherein the temperature setting of the screw extruder is divided into 3-9 zones, and the temperature setting values of the zones are respectively as follows: setting the setting values of the areas 1-3 to 165-175 ℃, the areas 4-6 to 180-190 ℃ and the areas 7-9 to 195-210 ℃, extruding the grafted polypropylene from a machine head in an extruder, cooling and granulating to obtain the compatible material for the modified polypropylene.

The production capacity of the screw extruder can be adjusted within a large range, and the production capacity is mainly determined by the optimal matching of the throughput area, the screw rotating speed, the feeding speed and the temperatures of all zones of the screw extruder. The rotation speed of the screw can be adjusted within a certain range, the range is 15 rpm-250 rpm, the preferred rotation speed range is 30 rpm-200 rpm, and the most preferred rotation speed range is 40 rpm-120 rpm.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

Example 1

Accurately weighing 100kg of isotactic polypropylene, 12kg of vinyltriethoxysilane, 0.3kg of maleic anhydride, 1.59kg of cumene hydroperoxide, 4.15kg of antioxidant master batch (Leifeite) and 3.18kg of sodium laurate sulfate, adding into a mixer, stirring and mixing uniformly, and adding into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 zones to be 170 ℃, 4-9 zones to be 185 ℃ and 10-12 zones to be 195 ℃, and starting a screw motor and a feeding motor after the temperatures of the zones reach the set temperature, wherein the rotating speed of the screw is 215 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 2

100kg of syndiotactic polypropylene, 8kg of vinyltris (2-methoxyethoxy) silane, 4.2kg of itaconic anhydride, 3.75kg of di-tert-butyl peroxide, 9.35kg of antioxidant masterbatch (Rafeite) and 7.01kg of potassium oleate are accurately weighed, added into a mixer, stirred and mixed uniformly, and added into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 zones to be 175 ℃, 4-9 zones to be 190 ℃ and 10-12 zones to be 205 ℃, and starting a screw motor and a feeding motor after the temperatures of the zones reach the set temperature, wherein the rotating speed of the screw is 165 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 3

100kg of random polypropylene, 5kg of vinylmethyldichlorosilane, 6.8kg of a mixture of itaconic anhydride and maleic anhydride (the mass ratio of itaconic anhydride to maleic anhydride is 0.1), 5.91kg of azobisisobutyronitrile, 0.25kg of antioxidant master batch (commercially available), and 0.12kg of stearic acid were accurately weighed, added to a mixer, stirred, sufficiently and uniformly mixed, and added to a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 areas to be 165 ℃, 4-9 areas to be 185 ℃ and 10-12 areas to be 195 ℃, and starting a screw motor and a feeding motor after the temperatures of the areas reach the set temperature, wherein the rotating speed of the screw is 115 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 4

100kg of polypropylene copolymer, 2.5kg of gamma-methacryloxypropyltrimethoxysilane, 10.7kg of itaconic anhydride, 0.15kg of dibenzoyl peroxide, 5.45kg of antioxidant master batch (commercially available) and 6.24kg of ethyl palmitate were weighed accurately, added into a mixer, stirred and mixed uniformly, and added into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 areas to be 175 ℃, 4-9 areas to be 190 ℃ and 10-12 areas to be 200 ℃, and starting a screw motor and a feeding motor after the temperatures of the areas reach the set temperature, wherein the rotating speed of the screw is 65 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 5

10kg of isotactic polypropylene, 90kg of syndiotactic polypropylene, 7kg of gamma-methacryloxypropylmethyldimethoxysilane, 5.5kg of a mixture of itaconic anhydride and maleic anhydride (the ratio between the two is 1), 2.31kg of tert-butyl hydroperoxide, 10.65kg of antioxidant master batch (commercially available) and 1.65kg of butyl laurate are accurately weighed, added into a mixer, stirred and mixed uniformly, and added into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 areas as 170 ℃, 4-9 areas as 185 ℃ and 10-12 areas as 200 ℃, and starting a screw motor and a feeding motor after the temperatures of the areas reach the set temperature, wherein the rotating speed of the screw is 15 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 6

Accurately weighing 12kg of isotactic polypropylene, 88kg of atactic polypropylene, 0.1kg of vinyl trichlorosilane, 12kg of maleic anhydride, 4.47kg of tert-butyl peroxybenzoate, 1.55kg of antioxidant master batch (Leifett) and 5.48k of zinc laurate, adding into a mixer, stirring and mixing uniformly, and adding into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 areas to be 175 ℃, 4-9 areas to be 190 ℃ and 10-12 areas to be 190 ℃, and starting a screw motor and a feeding motor after the temperatures of the areas reach the set temperature, wherein the rotating speed of the screw is 250 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 7

Accurately weighing 12.5kg of isotactic polypropylene, 87.5kg of copolymerized polypropylene, 0.25kg of vinyl trimethoxy silane, 9.4kg of itaconic anhydride, 6.63kg of cumene hydroperoxide, 6.75kg of antioxidant master batch (Leifett) and 0.89kg of sodium oleate, adding into a mixer, stirring, mixing fully and uniformly, and adding into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 areas as 170 ℃, 4-9 areas as 185 ℃ and 10-12 areas as 195 ℃, and starting a screw motor and a feeding motor after the temperatures of the areas reach the set temperature, wherein the rotating speed of the screw is 190 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 8

Accurately weighing 11kg of syndiotactic polypropylene, 89kg of atactic polypropylene, 0.5kg of vinyl triacetoxysilane, 8.1kg of a mixture of itaconic anhydride and maleic anhydride (the proportion between the two is 50), 0.87kg of azobisisobutyronitrile, 11.95kg of antioxidant master batch (Leifett) and 4.71kg of titanium stearate, adding into a mixer, stirring fully and uniformly mixing, and adding into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 zones to be 165 ℃, 4-9 zones to be 180 ℃ and 10-12 zones to be 195 ℃, and starting a screw motor and a feeding motor after the temperatures of the zones reach the set temperature, wherein the rotating speed of the screw is 140 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 9

Accurately weighing 16kg of syndiotactic polypropylene, 84kg of copolymerized polypropylene, 1kg of gamma-methacryloxypropyltrichlorosilane, 1.6kg of maleic anhydride, 3.03kg of dicumyl peroxide, 2.85kg of antioxidant master batch (commercially available) and 0.12kg of stearic acid, adding into a mixer, stirring, fully and uniformly mixing, and adding into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperature of 1-3 areas to be 165 ℃, the temperature of 4-9 areas to be 180 ℃ and the temperature of 10-12 areas to be 210 ℃, and starting a screw motor and a feeding motor after the temperature of each area reaches a set temperature, wherein the rotating speed of the screw is 90 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 10

17kg of random polypropylene, 83kg of copolymerized polypropylene, 6kg of gamma-methacryloxypropylmethyldiethoxysilane, 2.9kg of a mixture of itaconic anhydride and maleic anhydride (the ratio between the two is 75), 5.19kg of azobisisoheptonitrile, 8.05kg of antioxidant master batch (commercially available), and 3.95kg of zinc palmitate were weighed accurately, added to a mixer, stirred well and mixed uniformly, and added to a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 areas as 170 ℃, 4-9 areas as 185 ℃ and 10-12 areas as 210 ℃, and starting a screw motor and a feeding motor after the temperatures of the areas reach the set temperature, wherein the rotating speed of the screw is 40 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.

Example 11

100kg of random polypropylene, 2.2kg of vinylmethyldichlorosilane, 9.8kg of a mixture of itaconic anhydride and maleic anhydride (the mass ratio of itaconic anhydride to maleic anhydride is 100), 3.9kg of azobisisobutyronitrile, 3.5kg of antioxidant master batch (commercially available) and 2.6kg of stearic acid are accurately weighed, added into a mixer, stirred, fully mixed and uniformly added into a hopper of a screw extruder. And starting a heating power supply of the screw extruder, setting the temperatures of 1-3 zones to be 175 ℃, 4-9 zones to be 180 ℃ and 10-12 zones to be 200 ℃, and starting a screw motor and a feeding motor after the temperatures of the zones reach the set temperature, wherein the rotating speed of the screw is 220 rpm. Extruding by a screw extruder, spinning, cooling, cutting and granulating to obtain the required compatible material.