CN116001401A - Multilayer composite pipeline material and preparation method thereof - Google Patents
Multilayer composite pipeline material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of multilayer pipes, and particularly relates to a multilayer composite pipeline material and a preparation method thereof, wherein the pipeline material comprises the following layers: I. an outer layer made of a polyamide composition (a) comprising at least one semi-crystalline polyamide (A1); II. An inner layer made of a polyolefin composition (B) comprising at least one copolymerized polyethylene (B1); III, modified polyolefin material (C) is used as an adhesive layer, which is an olefin polymer modified by polar groups and used for bonding the outer layer I and the inner layer II. The multilayer composite pipeline has excellent high temperature resistance, long-term use performance, better strength and low temperature toughness and good medium resistance, can be processed into pipelines with different shapes, and widens the application range of the pipeline.
Description
Technical Field
The invention belongs to the technical field of multilayer pipes, and particularly relates to a multilayer composite pipeline material and a preparation method thereof.
Background
At present, materials applied to cooling pipes on automobiles generally use EPDM (ethylene-propylene-diene monomer), TPV (thermoplastic polyurethane) materials and nylon 12 materials, the wall thickness of the cooling pipe made of rubber materials is generally more than 4mm, the cooling pipe is applied to automobiles, the weight of the whole pipeline system is increased, the cooling pipe is easy to age after long-term use, the oil consumption and the power consumption of the automobile by hundred kilometers are seriously increased, meanwhile, the cooling pipe occupies a large space, the layout of cooling pipes is not facilitated, a certain problem exists in hydrolysis resistance of the cooling pipe made of single-layer nylon 12, water vapor permeation is high, and a certain hidden danger exists on new energy automobiles.
Some improvements have also been attempted in the art with respect to the existing drawbacks. For example:
patent document CN1906022a discloses a pipeline with a multilayer structure, wherein the inner layer is made of polypropylene material, the middle layer is made of an adhesive layer, the outer layer is made of polyamide material, the pipeline structure has good hydrolysis resistance, but the polypropylene material has poor low-temperature brittleness resistance, which can lead to poor low-temperature resistance of the pipeline material with the multilayer structure, and meanwhile, after the PP material is resistant to medium, a workpiece can generate microscopic cracks, which is easy to cause pipeline failure.
Patent document CN108343790a discloses a pipeline of a multilayer structure, in which ethylene propylene diene monomer is used as an inner layer, polypropylene-based modified ethylene propylene diene monomer is used as an intermediate layer, and modified nylon 12 is used as an outer layer, the structure can improve the wall thickness of the pipeline, and simultaneously greatly lighten the weight of the original rubber pipeline, but the bursting pressure of the pipeline of the multilayer structure is not high, and meanwhile, the heat resistance of the rubber material is not high, so that the application is limited.
In view of the foregoing, there is a need to develop a multi-layer pipeline for a (e.g. automobile) cooling system, which solves the problems of low and high temperature resistance, poor hydrolysis resistance and high explosion.
Disclosure of Invention
The invention aims to provide a multilayer composite pipeline material and a preparation method thereof, aiming at the problems of the existing multilayer pipeline used for (such as an automobile) cooling system; the three-layer pipeline structure is obtained by taking the copolymerized polyethylene with wide molecular weight distribution, high comonomer content and multiple macromolecular chain segments as an inner layer, so that the high temperature resistance and long-term use performance of the pipeline can be improved, and the outer layer polyamide material endows the pipeline with better strength, low temperature toughness and good medium resistance; more importantly, the method can also ensure that the elongation at break and the internal stress of the pipeline are relatively high, the pipeline with different shapes can be processed, and the application range of pipeline materials is widened.
In order to achieve the above object, the present invention provides the following technical solutions:
in a first aspect, a multilayer composite piping material is provided, comprising the following layers:
I. an outer layer made of a polyamide composition (a) comprising at least one semi-crystalline polyamide (A1) having an average number Nc of carbon atoms per nitrogen atom comprised between 8 and 18 (for example, 10, 11, 14, 16), preferably between 9 and 12;
II. An inner layer made of a polyolefin composition (B) comprising at least one copolymerized polyethylene (B1);
III, modified polyolefin material (C) is used as an adhesive layer, which is an olefin polymer modified by polar groups and is used for bonding the outer layer I and the inner layer II.
According to the multilayer composite piping material provided by the present invention, in some embodiments, the molecular weight (Mw) of the copolymerized polyethylene (B1) is 150000 ～ 400000 (e.g., 160000, 180000, 200000, 250000, 300000, 350000) and the molecular weight distribution is 10 to 25 (e.g., 11, 12, 14, 16, 18, 20, 22, 24).
In some embodiments, the copolymerized polyethylene (B1) has a melt index of 0.2 to 1.5g/10min, e.g., 0.3g/10min, 0.4g/10min, 0.5g/10min, 0.8g/10min, 1.0g/10min, 1.2g/10min, and a density of 0.93 to 0.97g/cm at 190℃and 5kg 3 (e.g., 0.94 g/cm) 3 、0.95g/cm 3 、0.96g/cm 3 ) The crystallinity is < 70% (e.g., 10%, 20%, 30%, 50%, 60%, 65%), and the melting point is 120-140 ℃ (e.g., 125 ℃, 130 ℃).
In some embodiments, the copolymerized polyethylene (B1) is a copolymer of ethylene and one or more of alpha-olefins. The entanglement of the material segments is enhanced by the introduction of the comonomer, promoting lacing molecule formation.
In some embodiments, the alpha-olefin is selected from the group consisting of C2 to C12 olefin monomers, preferably from the group consisting of C4 to C8 olefin monomers (e.g., 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene).
The long-term service properties of the copolymerized polyethylene material are determined by both the amorphous and crystalline domains, while from a microscopic point of view, avoiding property degradation mainly from entanglement of the crystalline and amorphous domains, the long-term properties of which are also more excellent when the entangled network formed by branched molecules in the crystalline and amorphous domains becomes intact. In the long-term use process, the lamella crystal and the lamella crystal are connected by the lacing molecular chain of the amorphous area, when two adjacent lamella crystals are subjected to external stretching action, the lacing molecular chain generates enough internal stress to resist the external force applied to the lamella crystal, so that deformation and further decomposition of the lamella crystal are blocked, and at the moment, the material is not easy to break due to the fact that the molecular chain is disentangled. In the process that the copolymer polyethylene material is expanded into cracks from silver grains, internal stress generated by lacing molecular chains resists external stress born by the platelet, the platelet and the lacing molecular chains form a macromolecular network under the action of continuous external stress to resist integral deformation and damage, and finally, the macromolecular network is relaxed beyond the stress bearing range, so that the mechanical property is reduced; therefore, the key to the long-term performance of the copolymerized polyethylene material is the molecular connection between the lamellar crystals.
The bonds between the platelets are dependent on the lacing molecules, and the amount of stress that the lacing molecular chains can withstand is related to its number and distribution, i.e., the molecular weight and the width of the molecular weight distribution of the material as a whole. Compared with the conventional polyethylene or polypropylene, the inventor selects the copolymerized polyethylene and utilizes the characteristic of wide molecular weight distribution, the copolymerized polyethylene contains a macromolecule and a micromolecule chain segment part, the micromolecule chain segment serves as the fluidity of the macromolecule chain segment, and the processability of the polymer can be improved while the mechanical property is considered, namely, the material performance and the processability are improved when the material is processed, and the molecular weight distribution shows typical double-peak or triple-peak distribution.
In some embodiments, the comonomer content of the copolymerized polyethylene (B1) is 1 to 5wt% (e.g., 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 4.0wt%, 4.5 wt%) based on the total weight of the copolymerized polyethylene (B1).
In some embodiments, the copolymerized polyethylene (B1) is present in an amount ranging from 80 to 99wt%, e.g., 82wt%, 85wt%, 90wt%, 95wt%, 98wt%, based on the total weight of the polyolefin composition (B).
In some embodiments, the polyolefin composition (B) further comprises the following components:
0.3 to 1.2wt percent (e.g., 0.4wt percent, 0.6wt percent, 0.8wt percent, 1.0wt percent) of antioxidant (B2);
0 to 0.5wt% (e.g., 0.1wt%, 0.2wt%, 0.3wt%, 0.4 wt%);
0 to 15wt% (e.g., 0.5wt%, 1wt%, 4wt%, 6wt%, 8wt%, 10wt%, 12 wt%) of filler (B4);
0 to 15wt% (e.g., 0.5wt%, 1wt%, 4wt%, 8wt%, 12 wt%) of other auxiliary agent (B5).
The multilayer composite pipeline material can be used in various environments (such as long-term aging resistance, water resistance, alcohol resistance and the like), the selection of the thermal aging agent needs to be capable of meeting the characteristic of continuously playing the role for a long time, and the multilayer composite pipeline material is not separated out in a medium (such as cooling liquid), so that the excellent long-term use performance is achieved. Although antioxidants may be added to the polyolefin matrix as conventional adjuvants, not all antioxidants achieve the objects of the invention.
In some embodiments, the antioxidant (B2) is a precipitation-resistant antioxidant, preferably one or more selected from aromatic amine antioxidants, sterically hindered phenol antioxidants, sulphur-containing synergists and hydroxylamine benzofuranone derivatives. For example, antioxidant 1330, antioxidant 1790, irganox1098, irganox 168 may be mentioned.
In some embodiments, the lubricant (B3) is selected from one or more of titanate, stearic acid, erucamide, oleamide, and silicone.
In some embodiments, the filler (B4) is selected from inorganic or organic fillers, preferably one or more selected from silica, talc, wollastonite and calcium carbonate.
Other adjuvants (B5) may include, but are not limited to, one or more of flame retardants, uv absorbers, pigments, leveling agents, chain extenders, heat conductive agents, conductive performance additives, and toughening agents (such as POE, etc.). These adjuvants are all conventional in the art and will not be described in detail herein. In some embodiments, the other auxiliary agent (B5) is selected from one or more of a photo-aging agent, a leveling agent, and a toughening agent.
For example, the ultraviolet absorber mainly comprises one or more of benzoic acid, benzophenone derivative and benzotriazole, the light stabilizer mainly comprises hindered amine stabilizer, and the weight ratio of the two is (0.5-2): 1 are compounded in proportion.
The semi-crystalline polyamide in layer I may be prepared from diamines and dicarboxylic acids or from aminocarboxylic acids or the corresponding lactams. The semi-crystalline polyamide resins produced by lactams have at least 8 carbon atoms per nitrogen atom, and in the case of combinations of diamines and dicarboxylic acids the arithmetic average of the carbon atoms in the mixed components of diamines and dicarboxylic acids is at least 8.
Examples of suitable semi-crystalline polyamides include, but are not limited to: PA1012 (prepared from 10 carbon atoms decanediamine and 12 carbon atoms dodecanedioic acid), PA12 (dodecalactam polycondensation), PA612, PA610, PA614, PA12, PA11, PA1212, PA614, PA616, PA618, and the like. For example, wanamid L3000, wanamid L2000.
According to the multilayer composite piping material provided herein, in some embodiments, the semi-crystalline polyamide (A1) is selected from one or more of PA1012, PA12, PA612, PA610, PA614, PA12, PA1212, PA614, PA616, and PA 618.
In some embodiments, the semi-crystalline polyamide (A1) is present in an amount of 50wt% (e.g., 55wt%, 60wt%, 75wt%, 85wt%, 95 wt%), preferably 70 to 99wt%, more preferably 80 to 99wt%, based on the total weight of the polyamide composition (A).
In some embodiments, the polyamide composition (a) further comprises: one or more of impact modifier (A2), plasticizer (A3) and additive component (A4).
In some embodiments, based on the total weight of the polyamide composition (a), wherein:
the impact modifier (A2) is contained in an amount of 0 to 25wt% (e.g., 0.5wt%, 1wt%, 4wt%, 5wt%, 10wt%, 12wt%, 15 wt%), preferably 3 to 20wt%, more preferably 3 to 10wt%;
the plasticizer (A3) is contained in an amount of 0 to 20wt% (e.g., 0.5wt%, 1wt%, 4wt%, 10wt%, 18 wt%), preferably 1 to 15wt%, more preferably 2 to 12wt%;
the content of the additive component (A4) is 0 to 5% by weight (for example, 0.5% by weight, 1.5% by weight, 2% by weight, 4% by weight), preferably 1 to 3% by weight.
In some embodiments, the impact modifier (A2) is an elastomeric copolymer, preferably one or more selected from the group consisting of ethylene/butene copolymers, ethylene/hexene copolymers, ethylene/octene copolymers, ethylene/alkyl (meth) acrylate copolymers, ethylene/styrene/butadiene copolymers, styrene/butadiene and ethylene-propylene two/three block copolymers.
The impact modifier (A2) is a modified copolymer, and the optional modifying functional groups include one or more of acid anhydride, epoxy group, halogen, carboxyl group, amino group and hydroxyl group and derivatives thereof. Suitable examples include, but are not limited to, N493 (grafted maleic anhydride), SOG-03 (grafted polymer containing GMA functionality, grafted epoxy), MD715 (grafted maleic anhydride). In some embodiments, the elastomeric polymer contains polar functional groups therein, preferably selected from one or more of anhydride, epoxy, halogen, carboxyl, amino and hydroxyl groups and derivatives thereof.
The plasticizer (A3) may be a C1-C20 ester of P-hydroxybenzoic acid or an amide formed from an aryl sulfonic acid with a C2-C12 amine, and suitable examples include, but are not limited to, one or more of P-benzenesulfonamide, N-butylbenzenesulfonamide (BBSA), methyl P-hydroxybenzoate, N-methylbenzenesulfonamide, ethyl P-hydroxybenzoate, octyl P-hydroxybenzoate, isocetyl P-hydroxybenzoate, N-octylamide toluene sulfonic acid, N-butylamide benzene sulfonic acid, and 2-ethylhexyl benzenesulfonate.
The additive component (A4) may include, but is not limited to, one or more of antioxidants, ultraviolet absorbers, light stabilizers, lubricants, flame retardants, pigments, leveling agents, chain extenders, heat conductors, conductive property additives, and other thermoplastics.
For example, the ultraviolet absorber mainly comprises one or more of benzoic acids, benzophenone derivatives and benzotriazole; the light stabilizer mainly comprises a hindered amine stabilizer, and the weight ratio of the hindered amine stabilizer to the light stabilizer is 0.5-2: 1 are compounded in proportion.
For example, the lubricant may be one or more of calcium stearate, zinc stearate, polyethylene wax, ethylene distearate.
For example, the antioxidants may include antioxidants used alone or in combination with one another; as a specific embodiment, the antioxidant may include one or more of phenolic antioxidants, phosphites, cuprous iodide (CuI), potassium iodide (KI).
According to the multilayer composite piping material provided by the present invention, in some embodiments, the polar group as the modified functional group in the modified polyolefin material (C) is selected from one or more of acid anhydride, carboxyl group, amino group and hydroxyl group and derivatives thereof.
In some embodiments, the polar group is present in an amount ranging from 0.1 to 2.0wt% (e.g., 0.15wt%, 0.3wt%, 0.5wt%, 1.0wt%, 1.5wt%, 1.8 wt%).
The layer III is a modified polyolefin material (C) which is modified based on C2 to C12 olefins in branched or unbranched form or a mixture thereof, and can be selected from polyethylene, polypropylene and the like, and the modified polyolefin material can be prepared by modifying at least one monomer selected from the following: maleic anhydride, glycidyl acrylate, glycidyl methacrylate, acrylic acid, methacrylic acid and vinyl acetate. The polar monomer modified polyolefin material is used as a bonding layer, the bonding property of the inner layer and the outer layer is considered, the inner layer realizes the bonding action of chemical bonds through chain segment entanglement between the modified polyolefin materials and the common polarity of the olefin polymer, and the outer layer material realizes the bonding action of chemical bonds between grafted polar functional groups and the polyamide composition, so that the bonding of three-layer materials is realized, and the formability of the multilayer composite pipeline is improved.
According to the multilayer composite piping material provided by the present invention, in some embodiments, the multilayer composite piping material has an outer diameter of 4 to 30mm (e.g., 5mm, 10mm, 15mm, 20mm, 25 mm), preferably 8 to 24mm; the wall thickness is 0.6 to 3mm (e.g., 0.8mm, 1.2mm, 1.5mm, 2.2mm, 2.5 mm), preferably 1 to 2mm; wherein:
an outer layer I made of the polyamide composition (a) having a wall thickness of not more than 80% (e.g., 10%, 25%, 40%, 60%, 75%) of the total wall thickness of the multilayer composite piping material, preferably 20 to 70% of the total wall thickness of the multilayer composite piping material, more preferably 30 to 50% of the total wall thickness of the multilayer composite piping material;
the modified polyolefin material (C) acts as a tie layer III having a wall thickness of not more than 20% (e.g., 1%, 4%, 8%, 12%, 15%, 18%) of the total wall thickness of the multilayer composite piping material, preferably 10 to 20% of the total wall thickness of the multilayer composite piping material.
In some embodiments, the multilayer composite piping material is an oriented smooth multilayer pipe having a draw ratio in the extrusion direction of less than 1:5 (e.g., 1:1, 1:2, 1:2.5, 1:3, 1:3.5, 1:4.5), preferably a draw ratio in the extrusion direction of from 1:1.5 to 1:4. In the text, the stretching ratio is smaller than 1:5, wherein '1' represents the sectional area of a pipeline port after extrusion molding, and '5' represents the sectional area of a pipeline just extruded at the machine head of the multi-layer co-extrusion equipment.
In a second aspect, there is provided a method for producing the multilayer composite piping material as described above, wherein the multilayer composite piping material is produced by processing the polyamide composition (a) as an outer layer, the polyolefin composition (B) as an inner layer, and the modified polyolefin material (C) as an intermediate layer for bonding the outer layer and the inner layer, and performing piping molding by a multilayer coextrusion apparatus.
In the present invention, the polyamide composition (a) and the polyolefin composition (B) may each be pelletized by a screw extrusion process. The extrusion equipment and extrusion process are all routine choices in the art and will not be described in detail herein. As well as the multilayer coextrusion apparatus and multilayer coextrusion process involved, are also a routine choice in the art and will not be described in detail here.
In the preparation method of the multilayer composite pipeline material, for example, the wall thickness of each layer and the total wall thickness of the multilayer composite pipeline can be controlled by the extrusion amount of the materials of each layer in the extrusion process.
In the extrusion processing process, light pipes, corrugated pipes, special pipes and the like can be extruded according to different application requirements. The multi-layer composite pipeline can be applied to medium-resistant pipelines such as cooling pipes, drain pipes, air brake pipes, oil delivery pipes and the like.
The multilayer composite pipeline material can realize a multilayer structure by a coextrusion method, selects a composition containing a copolymerized polyethylene material as an inner layer of the multilayer structure, and has long-term heat resistance and medium resistance through the structural characteristics of the copolymerized polyethylene material and the improvement of the performance of the copolymerized polyethylene material, so that the multilayer composite pipeline material has the performance advantage under a certain application scene; the outer layer is made of polyamide materials, the semi-crystalline polyamide materials have excellent strength and low-temperature toughness, the whole multi-layer composite pipeline is well protected, meanwhile, the stretching ratio of the pipeline is combined with the optimal stretching ratio, a certain degree of orientation can be achieved through controlling the stretching ratio, the proper stretching ratio is beneficial to the refinement of crystals in a system in the extrusion processing process of the materials, the material performance (such as good performance in the aspects of hydrolysis resistance, long-term temperature resistance and the like) is improved, and meanwhile, the stable extrusion processing process (the key point is the stability of the size and the appearance of the pipeline material) is facilitated.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
through carrying out the setting of layer structure arrangement and selecting the suitable material that is suitable for each layer on this layer structure arrangement basis to combine suitable pipeline stretch ratio, can make the three-layer composite pipeline material who obtains have excellent high temperature resistant, hydrolysis resistance, long-term performance and good resistant medium (coolant liquid) performance, and excellent low temperature resistant toughness.
The polyolefin composition (B) is used as an inner layer of the pipeline, and the polyamide composition (A) is used as an outer layer, so that the polyolefin composition (B) contains a copolymerized polyethylene component with wide molecular weight distribution, high comonomer content and multiple macromolecular chain segments, the long-term service performance of the pipeline material can be improved, and meanwhile, the pipeline material is subjected to a proper stretching ratio in the extrusion process of the pipeline, so that the crystals of the material are thinned, and the overall performance of the material is positively improved;
the outer aliphatic polyamide material has low amide bond density due to the long-chain structure, so that the material has excellent environmental corrosion resistance, salt spray resistance, broken stone impact resistance and other performances, and the prepared pipeline material can meet application requirements in different environments;
the polyolefin material (C) modified by the polar groups is introduced as the bonding layer, and the entanglement of the cooling chain segments of the polymer material and the improvement of the polar functional groups are adopted to improve the microcosmic bonding force between the materials of each layer, so that the effective bonding of the inner layer and the outer layer of the material is realized, and the separation phenomenon in the use process of the pipeline is prevented.
Detailed Description
So that the technical features and content of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
< source of raw materials >
The sources of the main raw materials used in each example are shown in Table 1.
TABLE 1 sources of the main raw materials
Examples of the preparation of the copolymer polyethylene are shown below:
the matrix resin of the copolymerized polyethylene (B1) contained in the polyolefin composition (B) of the present invention can be prepared by a multistage copolymerization method, that is, the reaction product of the previous stage (including the catalyst) is transferred to the reactor of the next stage reaction stage in the corresponding reactors of each stage, and the reaction is continued.
In the reaction of each stage of the reactor, ethylene copolymer containing two or more components is prepared by configuring different reaction conditions, different material adding ratios or material types. Specific reaction materials and reaction conditions are shown in Table 2.
TABLE 2 reaction mass and reaction conditions for copolymerizing polyethylene
The properties of the copolymer polyethylene (B1) produced by the above-described production method are shown in Table 3 below.
Table 3 Properties of the copolymer polyethylene obtained
| Preparation example | Molecular weight | Molecular weight distribution | Comonomer species | Comonomer content, wt% |
| PE-a | 150000 | 10 | Hexene | 1 |
| PE-b | 400000 | 25 | Hexene | 5 |
| PE-c | 250000 | 15 | Hexene | 3 |
| PE-d | 250000 | 15 | Butene (B) | 3 |
| PE-e | 250000 | 15 | Hexene and butene | 3 |
| PE-f | 250000 | 25 | Hexene | 4 |
| PE-g | 250000 | 15 | Without any means for | Without any means for |
Preparation of polyolefin composition (B)
The copolymerized polyethylene (B1) matrix resin obtained by the above preparation method, and other components, raw materials are weighed according to the component types and the amount (weight parts) information shown in table 4, mixed in a high-speed mixer for 5min, and the mixed blend is extruded and granulated by a twin-screw extruder; the twin-screw extruder had a screw diameter of 35mm, an extrusion screw aspect ratio of 48, and an extrusion speed of 450rpm/min.
The polyolefin composition (B) was produced as an inner layer by processing and pelletization by a twin screw extruder, and the products were labeled as PE1# to PE8# respectively.
Table 4 types and proportions (parts by weight) of the respective components in the polyolefin composition (B)
| Category(s) | PE1# | PE2# | PE3# | PE4# | PE5# | PE6# | PE7# | PE8# |
| PE-a | 98 | |||||||
| PE-b | 98 | |||||||
| PE-c | 93 | |||||||
| PE-d | 98 | 98 | ||||||
| PE-e | 98 | |||||||
| PE-f | 90 | |||||||
| PE-g | 98 | |||||||
| Engage 7467 | 8 | |||||||
| SiO 2 | 5 | |||||||
| 1330 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
| 1790 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
| 1010 | 0.3 | |||||||
| UV770 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Irganox 168 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Black matrix | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
Preparation of Polyamide composition (A)
The polyamide composition (a) as the outer layer includes the components shown in table 5 below. Weighing raw materials according to the components and the proportions (parts by weight) in Table 5, mixing for 5min in a high-speed mixer, uniformly mixing the raw materials, extruding and granulating the mixed blend through a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 28mm, the length-diameter ratio of an extruding screw is 40, and the extruding rotating speed is 700rpm/min; the polyamide composition (A) was prepared as an outer layer by extrusion processing, and the products were labeled as PA1# to PA3# respectively.
Table 5 Polyamide composition (A) each component and its amount (parts by weight)
| PA1# | PA2# | PA3# | |
| Wanamid L3000 | 98.3 | 85.3 | |
| DMVO | 87.3 | ||
| Butyl benzene sulfonamide | 8 | 8 | |
| FUSABOND N493 | 5 | 3 | |
| Irganox 1098 | 0.3 | 0.3 | 0.3 |
| Irganox 168 | 0.2 | 0.2 | 0.2 |
| Zinc stearate | 0.2 | 0.2 | 0.2 |
| Black matrix | 1 | 1 | 1 |
Preparation of multilayer composite pipeline
The polyolefin composition (B) obtained as above was used as an inner layer, the polyamide composition (a) was used as an outer layer, and the modified polyolefin material (C) was used as an intermediate layer, and pipeline molding was performed by a multilayer coextrusion apparatus to obtain a multilayer composite pipeline, each layer of which was subjected to structural and performance tests as shown in table 7. The outer diameter of the pipeline is 8mm, and the wall thickness is 1mm.
The extrusion line speed of the multilayer coextrusion apparatus was 12m/min. The processing temperatures for each zone in the multilayer coextrusion apparatus are shown in Table 6 below (in units of. Degree. C):
note that: in the above table, Z represents a screw, and H represents a head.
TABLE 7 Multi-layer composite pipeline Structure and Performance test data
Note that: the low-temperature impact toughness test process is that 10 sampling tubes are randomly taken for ball falling impact experiments. In the table, x/10 represents x pipe failures in 10 pipes; for example, 0/10 represents that 0 of the 10 tubes failed and that all 10 tubes passed the test.
From the results of examples 1-8, it can be seen that the three-layer composite pipeline material (initial performance test of the three-layer composite pipeline material) has better strength and low-temperature impact toughness by arranging the multilayer composite pipeline in a layer structure and selecting the material types applicable to different layers based on the layer structure arrangement and combining the proper pipeline stretch ratio; after 1000 hours of treatment at 100 ℃ in a cooling liquid environment, the tensile strength and impact toughness of the pipeline are still good, the performance degradation is small, and the excellent high temperature resistance, long-term use performance and good medium (cooling liquid) resistance of the multi-layer pipeline material are reflected.
Compared with examples 2 and 4, the comparative examples 1-2 adopt polyethylene components which are not limited by the invention as the inner layer of the pipeline, and under the same processing conditions, the initial tensile property of the prepared multilayer pipeline is lower, and the phenomenon of fracture of part of the pipe fittings is found in a low-temperature toughness experiment; and after long-term treatment experiments of the cooling liquid, the number of broken pipelines in the low-temperature toughness test of the pipelines is further increased; therefore, the multilayer pipeline materials of comparative examples 1-2 are poor in initial tensile strength and low-temperature toughness, and after being treated for 1000 hours at 100 ℃ in a cooling liquid environment, the impact toughness of the pipeline is further reduced, and the multilayer pipeline material does not have high temperature resistance, long-term use performance and good medium (cooling liquid) resistance, so that the advantages of the selected copolymer polyethylene are reflected.
Compared with the embodiment 3, the stretching ratio of the comparative example 3 is 1:6, so that the initial stretching strength of the pipeline is lower, and the attenuation of the stretching strength of the pipeline is more serious after long-term cooling liquid treatment, which proves that the stretching ratio defined by the invention is more beneficial to the maintenance of the mechanical property of the pipeline material, and has better medium resistance and long-term use resistance.
Compared with the pipeline obtained in the example 4, the initial performance of the pipeline obtained in the example 4 is basically equivalent, but the antioxidant 1010 is selected in the example 4, so that the pipeline prepared by the pipeline has great reduction of mechanical properties such as tensile strength, low-temperature toughness and the like after long-term cooling liquid treatment, and the preferred antioxidant type has good advantages for the long-term service performance and good medium (cooling liquid) resistance of the pipeline.
The foregoing description of some embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. A multilayer composite piping material characterized by comprising the following layers:
I. an outer layer made of a polyamide composition (a) comprising at least one semi-crystalline polyamide (A1) having an average number Nc of carbon atoms per nitrogen atom comprised between 8 and 18, preferably between 9 and 12;
II. An inner layer made of a polyolefin composition (B) comprising at least one copolymerized polyethylene (B1);
III, modified polyolefin material (C) is used as an adhesive layer, which is an olefin polymer modified by polar groups and is used for bonding the outer layer I and the inner layer II.
2. The multilayer composite pipe material according to claim 1, wherein the copolymerized polyethylene (B1) has a molecular weight of 150000 ～ 400000 and a molecular weight distribution of 10 to 25; and/or
The melt index of the copolymer polyethylene (B1) is 0.2-1.5 g/10min (190 ℃,5 kg) and the density is 0.93-0.97 g/cm 3 The crystallinity is less than 70 percent, and the melting point is 120-140 ℃; and/or
The copolymer polyethylene (B1) is a copolymer of ethylene with one or more of alpha-olefins, preferably selected from C2 to C12 olefin monomers, more preferably from C4 to C8 olefin monomers; and/or
The content of the comonomer in the copolymer polyethylene (B1) is 1 to 5wt% based on the total weight of the copolymer polyethylene (B1).
3. The multilayer composite pipe material according to claim 1, wherein the copolymerized polyethylene (B1) is contained in an amount ranging from 80 to 99wt% based on the total weight of the polyolefin composition (B); and/or
The polyolefin composition (B) further comprises the following components:
0.3 to 1.2 weight percent of antioxidant (B2),
0 to 0.5% by weight of a lubricant (B3),
0 to 15% by weight of a filler (B4),
0 to 15wt% of other auxiliary agent (B5);
preferably, the antioxidant (B2) is a precipitation-resistant antioxidant, more preferably one or more selected from aromatic amine antioxidants, sterically hindered phenol antioxidants, sulfur-containing synergists and hydroxylamine benzofuranone derivatives;
preferably, the lubricant (B3) is selected from one or more of titanate, stearic acid, erucamide, oleamide and silicone;
preferably, the filler (B4) is selected from inorganic or organic fillers, more preferably from one or more of silica, talc, wollastonite and calcium carbonate;
preferably, the other auxiliary agent (B5) is selected from one or more of a photo-ageing agent, a leveling agent and a toughening agent.
4. The multilayer composite pipe material according to claim 1, characterized in that the semi-crystalline polyamide (A1) is selected from one or more of PA1012, PA12, PA612, PA610, PA614, PA12, PA1212, PA614, PA616 and PA 618; and/or
The content of the semi-crystalline polyamide (A1) is greater than or equal to 50wt%, preferably 70 to 99wt%, more preferably 80 to 99wt%, based on the total weight of the polyamide composition (A).
5. The multilayer composite pipe material according to claim 1, wherein the polyamide composition (a) further comprises: one or more of an impact modifier (A2), a plasticizer (A3) and an additive component (A4); and/or
Based on the total weight of the polyamide composition (a), wherein:
the impact modifier (A2) is contained in an amount of 0 to 25wt%, preferably 3 to 20wt%, more preferably 3 to 10wt%;
the plasticizer (A3) is contained in an amount of 0 to 20wt%, preferably 1 to 15wt%, more preferably 2 to 12wt%;
the content of the additive component (A4) is 0 to 5% by weight, preferably 1 to 3% by weight.
6. The multilayer composite pipe material according to claim 5, wherein the impact modifier (A2) is an elastomeric copolymer, preferably one or more selected from the group consisting of ethylene/butene copolymers, ethylene/hexene copolymers, ethylene/octene copolymers, ethylene/alkyl (meth) acrylate copolymers, ethylene/styrene/butadiene copolymers, styrene/butadiene and ethylene-propylene two/three block copolymers;
the elastomeric polymer contains polar functional groups therein, preferably selected from one or more of anhydride, epoxy, halogen, carboxyl, amino and hydroxyl groups and derivatives thereof.
7. The multilayer composite piping material according to claim 1, wherein in the modified polyolefin material (C), the polar group as the modified functional group is selected from one or more of acid anhydride, carboxyl group, amino group and hydroxyl group and derivatives thereof; and/or
The content of the polar groups is in the range of 0.1 to 2.0wt%.
8. The multilayer composite pipe material according to claim 1, characterized in that the outer diameter of the multilayer composite pipe material is 4-30 mm, preferably 8-24 mm; the wall thickness is 0.6-3 mm, preferably 1-2 mm; wherein:
the outer layer I made of the polyamide composition (A) has a wall thickness which is not more than 80% of the total wall thickness of the multilayer composite pipeline material, preferably 20-70% of the total wall thickness of the multilayer composite pipeline material, more preferably 30-50% of the total wall thickness of the multilayer composite pipeline material;
the modified polyolefin material (C) is used as a bonding layer III, and the wall thickness of the modified polyolefin material (C) is not more than 20% of the total wall thickness of the multilayer composite pipeline material, preferably 10-20% of the total wall thickness of the multilayer composite pipeline material.
9. The multilayer composite pipe material according to claim 1, characterized in that the multilayer composite pipe material is an oriented smooth multilayer pipe having a stretch ratio in the extrusion direction of less than 1:5, preferably a stretch ratio of 1:1.5 to 1:4.
10. The method for producing a multilayer composite piping material according to any one of claims 1 to 9, wherein the multilayer composite piping material is produced by subjecting the polyamide composition (a) as an outer layer, the polyolefin composition (B) as an inner layer, and the modified polyolefin material (C) as an intermediate layer bonding the outer layer and the inner layer to a piping molding process by a multilayer coextrusion apparatus.
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| CN202211703830.1A CN116001401A (en) | 2022-12-29 | 2022-12-29 | Multilayer composite pipeline material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117734240A (en) * | 2023-11-29 | 2024-03-22 | 会通特种材料科技有限公司 | Three-layer composite pipe and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117734240A (en) * | 2023-11-29 | 2024-03-22 | 会通特种材料科技有限公司 | Three-layer composite pipe and preparation method thereof |
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