Reinforced polyethylene pipe material and preparation method thereof
阅读说明：本技术 一种增强聚乙烯管材料及其制备方法 (Reinforced polyethylene pipe material and preparation method thereof ) 是由 梁丽 叶林 吴步永 孔令举 梁恒远 赵晓文 于 2020-12-21 设计创作，主要内容包括：本发明提供一种增强聚乙烯管材料及其制备方法,其特点是利用超高分子量聚乙烯(UHMWPE)极高的分子缠结密度及强韧性,通过分别在PE管材料及UHMWPE分子上接枝反应性基团,采用简便高效的反应性熔融加工方法实现两相分子在界面上的反应,并引入较低分子量UHMWPE(L-UHMWPE)构建聚乙烯管材料与UHMWPE相匹配的粘度梯度,从而构筑两相界面分子间强相互作用,促使界面分子间扩散,形成界面高度分子缠结,获得良好界面相容性,实现UHMWPE在聚乙烯管材料基体中的良好分散,显著提升聚乙烯管材料的强韧性。(The invention provides a reinforced polyethylene pipe material and a preparation method thereof, which is characterized in that the ultrahigh molecular weight polyethylene (UHMWPE) is utilized to achieve extremely high molecular entanglement density and toughness, reactive groups are grafted on the PE pipe material and UHMWPE molecules respectively, a simple and efficient reactive melt processing method is adopted to achieve reaction of two-phase molecules on an interface, UHMWPE (L-UHMWPE) with lower molecular weight is introduced to construct a viscosity gradient matched with the UHMWPE, so that strong interaction between the two-phase interface molecules is constructed, diffusion between the interface molecules is promoted, high-level molecular entanglement of the interface is formed, good interface compatibility is obtained, good dispersion of the UHMWPE in a polyethylene pipe material matrix is achieved, and the toughness of the polyethylene pipe material is remarkably improved.)
1. A reinforced polyethylene pipe material is characterized in that the material comprises the following raw material formula components by weight:
wherein the molecular weight of the UHMWPE is 500-1100 ten thousand, and the molecular weight of the L-UHMWPE is 40-500 ten thousand;
the reactive monomer 1 is any one of Maleic Anhydride (MA), styrene-maleic anhydride copolymer (SMA), maleic anhydride (BA), Glycidyl Methacrylate (GMA) and Allyl Glycidyl Ether (AGE);
the reactive monomer 2 is any one of Acrylamide (AM), Allylamine (AP), Acrylic Acid (AA), and methacrylic acid (MAA);
the initiator 1 is any one of dibenzoyl peroxide, azobisisobutyronitrile and dicumyl peroxide;
the initiator 2 is any one of benzophenone, 2, 4-dihydroxy benzophenone, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone and (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide;
the antioxidant is any one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (namely: Irganox1010), N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine (namely: Irganox 1098), octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (namely: Irganox 1076) and 2, 6-di-tert-butyl-4-methylphenol (namely: BHT (264));
the preparation method of the reinforced polyethylene pipe material comprises the following steps:
preparation of polyethylene pipe Material-g-reactive monomer 1
Adding 100 parts of polyethylene pipe material into an internal mixer for plasticizing and melting at the temperature of 180-250 ℃, wherein the rotating speed is 40-100rpm, then sequentially adding 0.05-5 parts of antioxidant, 0.1-20 parts of reactive monomer 1 and 0.1-10 parts of initiator 1, and reacting for 10-100min to obtain polyethylene pipe material-g-reactive monomer 1;
preparation of UHMWPE-g-reactive monomer 2
1-50 parts of UHMWPE, 0.1-10 parts of initiator 2, 0.1-20 parts of reactive monomer 2 and 10-200 parts of acetone are stirred and mixed evenly at the temperature of 30-60 ℃, N is introduced2Then, an ultraviolet lamp is adopted for processing for 10-60min, the power of the ultraviolet lamp is 200-;
preparation of reinforced polyethylene pipe material:
adding 100 parts of polyethylene pipe material-g-reactive monomer 1, 1-50 parts of UHMWPE-g-reactive monomer 2, 1-50 parts of L-UHMWPE and 0.05-5 parts of antioxidant into a high-speed mixer, uniformly mixing, then melting and mixing by using a double-screw extruder, extruding and granulating, wherein the rotating speed of a screw is 50-200 r/min, and the temperature of a charging barrel is 180-250 ℃, so as to obtain the reinforced polyethylene pipe material.
Technical Field
The invention relates to a reinforced polyethylene pipe material and a preparation method thereof, belonging to the field of polymer processing.
Background
The Polyethylene (PE) pipe has excellent comprehensive performance and is widely applied to the fields of building water supply and drainage, gas transportation, electrical and telecommunication protection, agricultural irrigation and the like; in recent years, along with the increase of the conveying pressure of a pipe network, the increase of the caliber of a pipeline and the increasing requirement on the safety of the pipe network, higher requirements are put forward on the compressive strength and the service life of a PE pipe. Therefore, a great deal of work is carried out on the modification research of the mechanical property of the PE pipe material. Ran chong et al, synthetic resins and plastics, 2018, (4),31-33, describe studies of graphene reinforced PE tube materials, indicating that the flexural modulus of the composite material can be increased from 1080MPa for pure PE to 1160 MPa. Wangchun et al, plastics science 2016, (44),32-36, have studied glass fiber modified PE tubing materials and found that when 20 wt% glass fiber is added, the tensile strength of the composite is improved by 10% over pure PE. In the application of engineering plastics, 2016, (44) and 110-. In the modification method, although the mechanical strength of the PE pipe material can be improved to a certain extent by adopting fibers, inorganic nanoparticles and the like, the enhancement effect is limited due to the lack of strong interaction between the filler and the PE matrix, and the toughness of the PE pipe material is obviously reduced.
Disclosure of Invention
The invention aims to provide a reinforced polyethylene pipe material and a preparation method thereof aiming at the defects of the prior art, and is characterized in that the ultrahigh molecular weight polyethylene (UHMWPE) is utilized to achieve extremely high molecular entanglement density and toughness, reactive groups are grafted on the PE pipe material and UHMWPE molecules respectively, a simple, convenient and efficient reactive melting processing method is adopted to achieve the reaction of two-phase molecules on an interface, and UHMWPE (L-UHMWPE) with lower molecular weight is introduced to construct a viscosity gradient matched with the UHMWPE pipe material, so that strong interaction between the two-phase interface molecules is constructed, diffusion between the interface molecules is promoted, high interface molecular entanglement is formed, good interface compatibility is obtained, the UHMWPE is well dispersed in a polyethylene pipe material matrix, and the toughness of the polyethylene pipe material is remarkably improved.
The aim of the invention is achieved by the following technical measures, wherein the raw material fractions are parts by weight except for special specifications.
The reinforced polyethylene pipe material comprises the following raw materials in formula:
wherein the molecular weight of the UHMWPE is 500-1100 ten thousand, and the molecular weight of the L-UHMWPE is 40-500 ten thousand;
the reactive monomer 1 is any one of Maleic Anhydride (MA), styrene-maleic anhydride copolymer (SMA), maleic anhydride (BA), Glycidyl Methacrylate (GMA) and Allyl Glycidyl Ether (AGE);
the reactive monomer 2 is any one of Acrylamide (AM), Allylamine (AP), Acrylic Acid (AA), and methacrylic acid (MAA);
the initiator 1 is any one of dibenzoyl peroxide, azobisisobutyronitrile and dicumyl peroxide;
the initiator 2 is any one of benzophenone, 2, 4-dihydroxy benzophenone, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone and (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide;
the antioxidant is any one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (namely: Irganox1010), N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine (namely: Irganox 1098), octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (namely: Irganox 1076) and 2, 6-di-tert-butyl-4-methylphenol (namely: BHT (264));
the preparation method of the reinforced polyethylene pipe material comprises the following steps:
preparation of polyethylene pipe Material-g-reactive monomer 1
Adding 100 parts of polyethylene pipe material into an internal mixer for plasticizing and melting at the temperature of 180-250 ℃, wherein the rotating speed is 40-100rpm, then sequentially adding 0.05-5 parts of antioxidant, 0.1-20 parts of reactive monomer 1 and 0.1-10 parts of initiator 1, and reacting for 10-100min to obtain polyethylene pipe material-g-reactive monomer 1;
preparation of UHMWPE-g-reactive monomer 2
1-50 parts of UHMWPE, 0.1-10 parts of initiator 2, 0.1-20 parts of reactive monomer 2 and 10-200 parts of acetone are stirred and mixed evenly at the temperature of 30-60 ℃, N is introduced2Then, an ultraviolet lamp is adopted for processing for 10-60min, the power of the ultraviolet lamp is 200-;
preparation of reinforced polyethylene pipe material:
adding 100 parts of polyethylene pipe material-g-reactive monomer 1, 1-50 parts of UHMWPE-g-reactive monomer 2, 1-50 parts of L-UHMWPE and 0.05-5 parts of antioxidant into a high-speed mixer, uniformly mixing, then melting and mixing by using a double-screw extruder, extruding and granulating, wherein the rotating speed of a screw is 50-200 r/min, and the temperature of a charging barrel is 180-250 ℃, so as to obtain the reinforced polyethylene pipe material.
Enhancing the properties of polyethylene pipe materials
Compared with the original polyethylene pipe material, the tensile strength of the reinforced polyethylene pipe material prepared by the invention is improved by 15-30%, and the impact strength is improved by 80-100%.
The invention has the following advantages
The invention is intended to prepare a reinforced polyethylene pipe material, having the following characteristics:
due to the extremely high molecular weight, the ultra-high molecular weight polyethylene (UHMWPE) has high molecular entanglement density, excellent mechanical strength and toughness and wear resistance, but due to the large and mismatched viscosity difference between the UHMWPE and the Polyethylene (PE), the two-phase separation of the blend is obvious, the compatibility is poor, and the mechanical property is far lower than expected. Therefore, the invention creatively realizes the reaction of two-phase molecules on the interface by grafting reactive groups on the PE pipe material and the UHMWPE molecules respectively and adopting a simple, convenient and efficient reactive melt processing method, so as to construct strong interaction between the interface molecules, obtain good interface compatibility, realize good dispersion of the UHMWPE in the polyethylene pipe material matrix and obviously improve the toughness of the polyethylene pipe material;
and further introducing UHMWPE (L-UHMWPE) with lower molecular weight into the polyethylene pipe material/UHMWPE blending system to construct a viscosity gradient matched with the UHMWPE for the polyethylene pipe material and the UHMWPE, so that the diffusion between two phase interface molecules is promoted, the interface high-degree molecular entanglement is formed, the phase separation phenomenon is reduced, and the mechanical property of the blend can be further improved.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the above disclosure.
Example 1
1kg of polyethylene pipe material is added into an internal mixer to be plasticized and melted at 180 ℃, the rotating speed is 40rpm, then 5g of tetra [ - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (namely Irganox1010), 50g of Maleic Anhydride (MA) and 5g of dibenzoyl peroxide are added according to the above steps, and the mixture reacts for 30min to obtain the polyethylene pipe material-g-MA.
100g of UHMWPE, 3g of benzophenone, 10g of Allylamine (AP) and 300g of propaneThe ketone is stirred and mixed evenly at 30 ℃, and N is introduced2And then treating for 10min by using an ultraviolet lamp with the power of 800W, then washing by using acetone, and drying for 4 hours in vacuum at 90 ℃ to obtain the UHMWPE-g-AP.
1kg of polyethylene pipe material-g-MA, 100g of UHMWPE-g-AP, 50g L-UHMWPE and 5g of Irganox1010 are added into a high-speed mixer to be uniformly mixed, then a double-screw extruder is used for melting and mixing, and extrusion granulation is carried out, wherein the rotating speed of a screw is 50 revolutions per minute, and the temperature of a charging barrel is 180 ℃, so that the reinforced polyethylene pipe material is obtained.
Example 2
1kg of polyethylene pipe material is added into an internal mixer to be plasticized and melted at 220 ℃ at the rotating speed of 70rpm, then 10g N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine (namely Irganox 1098), 100g of Allyl Glycidyl Ether (AGE) and 10g of azobisisobutyronitrile are sequentially added to react for 50min, and the polyethylene pipe material-g-AGE is obtained.
200g UHMWPE, 10g 2, 4-dihydroxy benzophenone, 50g Acrylic Acid (AA) and 500g acetone are stirred and mixed evenly at 45 ℃, N is introduced2And then treating for 30min by using an ultraviolet lamp with the power of 2000W, then washing by using acetone, and drying for 4 hours in vacuum at 90 ℃ to obtain UHMWPE-g-AA.
Adding 1kg of polyethylene pipe material-g-AGE, 200g of UHMWPE-g-AA, 100g L-UHMWPE and 10g of Irganox 1098 into a high-speed mixer, uniformly mixing, then melting and mixing by using a double-screw extruder, extruding and granulating, wherein the rotating speed of a screw is 120 revolutions per minute, and the temperature of a charging barrel is 220 ℃, thus obtaining the reinforced polyethylene pipe material.
Example 3
Adding 1kg of polyethylene pipe material into an internal mixer, plasticizing and melting at 250 ℃ at the rotating speed of 100rpm, then sequentially adding 20g b- (4-hydroxy-3, 5-di-tert-butylphenyl) propionic acid octadecyl ester (namely Irganox 1076), 150g of styrene-maleic anhydride copolymer (SMA) and 20g of dicumyl peroxide, and reacting for 80min to obtain the polyethylene pipe material-g-SMA.
500g UHMWPE, 30g 2-hydroxy-2-methyl-1-phenyl acetone, 100g Acrylamide (AM) and 1000g acetone are stirred and mixed evenly at 60 ℃, N is introduced2Then treated with UV lamp 6After 0min, the power of an ultraviolet lamp is 5000W, and then the UHMWPE-g-AM is obtained by washing with acetone and drying in vacuum for 4 hours at 90 ℃.
1kg of polyethylene pipe material-g-SMA, 500g of UHMWPE-g-AM, 200g L-UHMWPE and 15g of Irganox 1076 are added into a high-speed mixer to be uniformly mixed, then a double-screw extruder is used for melting and mixing, and extrusion granulation is carried out, wherein the screw rotating speed is 200 r/min, and the charging barrel temperature is 250 ℃, so as to obtain the reinforced polyethylene pipe material.