CN115232423B - Manufacturing method of metal embedded PMMA composite board and metal embedded PMMA composite board - Google Patents
Manufacturing method of metal embedded PMMA composite board and metal embedded PMMA composite board Download PDFInfo
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- CN115232423B CN115232423B CN202210815700.0A CN202210815700A CN115232423B CN 115232423 B CN115232423 B CN 115232423B CN 202210815700 A CN202210815700 A CN 202210815700A CN 115232423 B CN115232423 B CN 115232423B
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- Prior art keywords
- wire harness
- metal wire
- pmma
- release agent
- composite board
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- 239000002184 metal Substances 0.000 title claims abstract description 128
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 95
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 9
- 238000013268 sustained release Methods 0.000 claims description 8
- 239000012730 sustained-release form Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 6
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- YDZIJQXINJLRLL-UHFFFAOYSA-N 2-hydroxydodecanoic acid Chemical compound CCCCCCCCCCC(O)C(O)=O YDZIJQXINJLRLL-UHFFFAOYSA-N 0.000 claims description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Abstract
The application relates to a manufacturing method of a metal embedded PMMA composite board, which comprises the following steps: fixing the wire harness coated with the interface slow release agent in a casting mold; casting a liquid phase material for forming a PMMA matrix in the casting mold; and polymerizing to obtain the metal embedded PMMA composite board. The metal embedded PMMA composite board is manufactured by the manufacturing method. According to the application, the interface slow release agent is coated on the surface of the metal wire harness, so that the isolation state between the metal wire harness and a polymerization product can be slowly changed in the liquid phase material polymerization process until mechanical occlusion is formed, the original space position of the metal wire harness is basically not changed in the polymerization process, and the problem of bending of the composite board caused by mismatching of volume shrinkage and volume change of the metal wire harness in the liquid phase material polymerization process and phase interface occlusion in advance is avoided.
Description
Technical Field
The application relates to the technical field of composite materials, in particular to a manufacturing method of a metal embedded PMMA composite board and the metal embedded PMMA composite board.
Background
Polymethyl methacrylate (Polymethyl methacrylate, PMMA) is widely applied to the fields of traffic sound insulation barriers, building transparent/heat insulation curtain walls, aircraft portholes, super bridge windshields and the like as a transparent high polymer material with excellent comprehensive performance. Specifically, taking a high-speed rail or a urban rail noise reduction facility as an example, if PMMA (polymethyl methacrylate) plates with preset thickness are used as the sound barrier main body materials, double hidden hazards in traffic safety and ecological environment exist, and the two hidden hazards are mainly characterized in that after the PMMA materials are impacted due to the hard brittleness, a large amount of flying fragments are easily generated, so that the safety of pedestrians and vehicles on the nearby roads or below (such as an overhead road) is endangered; the latter mainly considers that birds have difficulty in recognizing transparent PMMA plates and risk of false collision in the flying process.
In the prior art, a PMMA composite material with a wire bundle is generally formed by embedding black nylon wire bundles at proper intervals in the PMMA manufacturing process, so that the impact resistance is moderately improved, a certain dragging effect is formed, the splashing or falling of fragments is reduced, birds are easy to recognize, and the hidden danger is solved. Nevertheless, nylon materials still have great difference in tensile strength and impact resistance compared with metal, namely under the same condition, after the nylon is replaced by the metal wire harness, the falling risk after collision of the corresponding PMMA composite board is obviously improved, however, when the metal embedded PMMA composite board is manufactured, the difference between volume shrinkage caused by monomer polymerization of PMMA and volume change of the metal wire harness and phase interface occlusion in advance cannot be solved all the time, the obtained composite board is bent, and the technical barrier in the field of PMMA composite board manufacturing is formed, so that the break-through is difficult.
Disclosure of Invention
The application provides a manufacturing method of a metal embedded PMMA composite board and the metal embedded PMMA composite board, aiming at the technical problems that the composite board is bent due to mismatching of volume shrinkage and volume change of a metal wire bundle in the polymerization process of liquid phase materials and phase interface occlusion in advance.
In order to solve the technical problems, the application provides a manufacturing method of a metal embedded PMMA composite board, which comprises the following steps:
step S1, fixing a metal wire bundle coated with an interface slow-release agent in a casting mold;
step S2, pouring liquid phase materials for forming PMMA matrix in the pouring mold;
and S3, polymerizing to obtain the metal embedded PMMA composite board.
Alternatively, the interfacial slow release agent has a solubility in MMA (Methyl methacrylate ) solvent of 0.01g/100g MMA-10 g/100g MMA at 20℃and 1 standard atmospheric pressure.
Optionally, the interface sustained release agent comprises one or more of n-octane, n-nonane, n-decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, n-octanol, n-nonanol, n-decanol, dodecanol, 1-tridecanol, tetradecanol, 1-pentadecanol, hexadecanol, heptadecanol, octadecanol, butyl ether, n-amyl ether, hexyl ether, heptyl ether, n-octyl ether, n-octanoic acid, nonanoic acid, n-decanoic acid, undecanoic acid, phenyl dodecanoate, 2-hydroxydodecanoate, 3-hydroxydodecanoate, 12-hydroxydodecanoate, methyl dodecanoate, stearic acid, palm wax, slice paraffin and liquid paraffin.
Optionally, the step S1 includes:
providing a casting mold, wherein a positioning bracket is arranged in the casting mold, and is provided with a positioning through hole for passing through the metal wire harness;
passing the metal wire harness through a positioning through hole on the positioning bracket;
and coating an interface slow release agent on the surface of the metal wire harness.
Optionally, the positioning support is made of PMMA, and the positioning through holes are in clearance fit with the metal wire bundles.
Optionally, the casting mold comprises an annular adhesive tape, an upper template and a lower template, wherein the annular adhesive tape is clamped between the upper template and the lower template, and forms a cavity together with the upper template and the lower template, the positioning support is positioned in the cavity, mounting through holes are formed in the portions, positioned on two sides of the length direction of the positioning support, of the annular adhesive tape, and the end portions of the metal wire harnesses penetrate through the mounting through holes.
Optionally, the installation through hole with interference fit between the wire harness, the wire harness adopts one-way locking buckle to fix, one-way locking buckle with the side of cope match-plate pattern and lower bolster offsets.
Optionally, the step S3 includes:
low temperature stage: heating at 45-65 deg.c for 2-72 hr;
high temperature stage: heating at 95-125 deg.c for 1-12 hr.
Optionally, the miscibility of the interfacial slow release agent and MMA meets the following conditions:
at the end of the low-temperature stage, the interface slow release agent on the surface of the wire harness is not diffused;
and at the end of the high-temperature stage, the diffusion of the interface slow release agent on the surface of the metal wire bundle is completed.
The application also provides a metal embedded PMMA composite board, which is manufactured by adopting the manufacturing method of the metal embedded PMMA composite board.
The manufacturing method of the metal embedded PMMA composite board comprises the following steps: fixing the wire harness coated with the interface slow release agent in a casting mold; casting a liquid phase material for forming a PMMA matrix in the casting mold; and polymerizing to obtain the metal embedded PMMA composite board. The metal embedded PMMA composite board is manufactured by the manufacturing method. According to the application, the interface slow release agent is coated on the surface of the metal wire harness, so that the isolation state between the metal wire harness and a polymerization product can be slowly changed in the liquid phase material polymerization process until mechanical occlusion is formed, the original space position of the metal wire harness is basically not changed in the polymerization process, and the problem of bending of the composite board caused by mismatching of volume shrinkage and volume change of the metal wire harness in the liquid phase material polymerization process and phase interface occlusion in advance is avoided.
Drawings
FIG. 1 is an oblique view of a metal embedded PMMA composite sheet material as shown according to a first embodiment;
fig. 2 is a schematic view showing an internal construction of a metal-embedded PMMA composite sheet according to a first embodiment;
FIG. 3 is a schematic cross-sectional partial structure of a metal embedded PMMA composite sheet material according to the first embodiment;
fig. 4 is a flow chart illustrating a method of manufacturing a metal embedded PMMA composite sheet according to a second embodiment;
FIG. 5 is a schematic view showing the diffusion process of the interfacial slow release agent involved in the manufacturing method of the metal embedded PMMA composite board according to the second embodiment;
FIG. 6 is a top view of a locating bracket and its spatial relationship with a wire harness involved in a method of manufacturing a metal embedded PMMA composite sheet material according to a second embodiment;
FIG. 7 is a schematic view of a one-way locking clasp according to a second embodiment;
fig. 8 is a schematic diagram of the working principle of the unidirectional locking buckle according to the second embodiment;
FIG. 9 is a graph comparing the effects of the metal embedded PMMA composite plate obtained in the prior art and the second embodiment;
fig. 10 is a comparison of impact strength data for corresponding composite boards according to process 1, process 2, and process 3.
Detailed Description
Further advantages and effects of the present application will become apparent to those skilled in the art from the disclosure of the present application, which is described by the following specific examples.
In the following description, reference is made to the accompanying drawings which describe several embodiments of the application. It is to be understood that other embodiments may be utilized and that mechanical, structural, electrical, and operational changes may be made without departing from the spirit and scope of the present application. The following detailed description is not to be taken in a limiting sense, and the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Although the terms first, second, etc. may be used herein to describe various elements in some examples, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element.
Furthermore, as used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context indicates otherwise. It will be further understood that the terms "comprises," "comprising," "includes," and/or "including" specify the presence of stated features, steps, operations, elements, components, items, categories, and/or groups, but do not preclude the presence, presence or addition of one or more other features, steps, operations, elements, components, items, categories, and/or groups. The terms "or" and/or "as used herein are to be construed as inclusive, or meaning any one or any combination. Thus, "A, B or C" or "A, B and/or C" means "any of the following: a, A is as follows; b, a step of preparing a composite material; c, performing operation; a and B; a and C; b and C; A. b and C). An exception to this definition will occur only when a combination of elements, functions, steps or operations are in some way inherently mutually exclusive.
First embodiment
As shown in fig. 1 and 2, the present application provides a metal embedded PMMA composite sheet, comprising a wire harness 100 and a PMMA matrix 120.
Referring to fig. 3, the wire harness sites 100 are arranged in parallel along the length or width direction of the PMMA matrix 120, and preferably are arranged in parallel at a predetermined pitch in the middle position, length or width direction of the PMMA matrix 120 in the thickness direction, that is, b1=b2, a1=a2.
The metal wire harness 100 may be made of one of iron, aluminum and alloys thereof, and has a form including stranded wires or single-stranded bars, a diameter of 0.5-5 mm, and an arrangement interval of 2-20 cm.
In addition, according to the manufacturing method of the second embodiment of the present application, the PMMA matrix 120 of the metal embedded PMMA composite sheet of the present application is further dispersed with an interfacial slow release agent, and the interfacial slow release agent is mainly distributed in the surrounding area of the wire harness 100. In some embodiments, the PMMA matrix 120 may also include positioning brackets for supporting and positioning the wire harness 100. The interfacial slow release agent and the positioning stent will be described in detail in the second embodiment.
Second embodiment
Fig. 4 is a flow chart illustrating a method of manufacturing a metal embedded PMMA composite sheet according to a second embodiment. As shown in fig. 4, the method for manufacturing the metal embedded PMMA composite board of the present application comprises the steps of:
step S1, fixing a metal wire bundle coated with an interface slow-release agent in a casting mold;
s2, pouring liquid phase materials for forming a PMMA matrix in a pouring mold;
and S3, polymerizing to obtain the metal embedded PMMA composite board.
Optionally, the interfacial sustained release agent is a linear saturated fatty chain or a hetero chain, and the specific chemical structure can be as follows:
wherein R is 1 Is CH 3 、COOCH 3 One of the following; r is R 2 Is OH, CH 3 、COOH、NH 2 One of the following; x is X 1 Is NH, O, CH 2 、CH-OH、CH-NH 2 N is a positive integer of 6 to 30. The solubility of the interfacial slow-release agent in MMA solvent is 0.01g/100g MMA-10 g/100g MMA at 20deg.C and 1 standard atmospheric pressure, so that the interfacial slow-release agent does not or hardly diffuse into liquid phase material for forming PMMA matrix at normal temperature.
In this embodiment, the interfacial sustained release agent comprises one or more of n-octane, n-nonane, n-decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, n-octanol, n-nonanol, n-decanol, dodecanol, 1-tridecanol, tetradecanol, 1-pentadecanol, hexadecanol, heptadecanol, octadecanol, butyl ether, n-amyl ether, hexyl ether, heptyl ether, n-octyl ether, n-octanoic acid, nonanoic acid, n-decanoic acid, undecanoic acid, phenyl dodecanoate, 2-hydroxydodecanoic acid, 3-hydroxydodecanoic acid, 12-hydroxydodecanoic acid, methyl dodecanoate, stearic acid, palm wax, slice paraffin, and liquid paraffin.
Optionally, the liquid phase material is composed of a polymer solution for polymerizing to form PMMA and an initiator, which are commonly used in the art, and the present application is not limited in particular, and may be suitably selected according to practical situations, for example, refer to the relevant process of applicant in "blue-phase enhanced PMMA heat resistant sheet manufacturing method and blue-phase enhanced PMMA heat resistant sheet", application No. 202210285151.0: the composition of the liquid phase material for forming the PMMA matrix can comprise polymethyl methacrylate, methyl methacrylate and an initiator, wherein a solution consisting of polymethyl methacrylate and methyl methacrylate is defined as a polymer solution in the application, the polymer solution can be obtained by stopping the bulk polymerization process of the methyl methacrylate in a controlled reaction process mode in a stepwise manner (the stopping point is judged by using a viscosity index, the specific viscosity is preferably the application of the solution at 25 ℃ for 50-135 s), the solution can also be obtained by dissolving a commercially available PMMA resin master batch in the methyl methacrylate to prepare the proper viscosity (preferably the application of the solution at 25 ℃ for 50-135 s), the adding stage of the initiator forms the polymer solution in the two modes and the polymer solution is cooled to room temperature, and the residual initiator content in the original bulk polymerization or the resin master batch is not considered when the adding amount is calculated.
Optionally, the mass ratio of the polymethyl methacrylate to the initiator is 5-20%, the mass ratio of the initiator is less than or equal to 1%, and the balance is methyl methacrylate, wherein the polymethyl methacrylate and the methyl methacrylate form the polymer solution, the initiator adopts a critical temperature of 45-100 ℃ and has a half-life of 100-10 1 h, specifically comprises at least one of BPO, AIBN, ABVN, methyl vinyl ketone, benzoin, xylene ketone, fluorescein and eosin, wherein a single initiator or a combination of initiators can be selected.
Alternatively, the manner of coating the interfacial slow-release agent on the wire bundle may be one of dip coating, wiping, spraying. Referring to fig. 5, after the interfacial agent is coated on the surface of the wire harness, a coating layer 500 having a d0 thickness is formed. In the casting in step S2, since the diffusion rate of the interfacial agent into the liquid phase material 118 is extremely slight at room temperature, the thickness d1 is not substantially changed (where d1≡d0), and then, in step S3, the interfacial agent gradually and slowly diffuses to the periphery (arrow 600 indicates the diffusion direction of the interfacial agent), and at this time, the thickness of the interfacial agent gradually decreases to d2, and at this time, the liquid phase material 118 is substantially changed to the preliminary solid phase medium 119, and at the end of the polymerization, the thickness of the interfacial agent further decreases to d3 (where d3≡0), and the preliminary solid phase medium 119 becomes the complete or substantially complete solid phase medium 120, thereby completing the whole polymerization process. In the polymerization process, the diffusion rate of the interface slow release agent is a spontaneous process and is controlled by temperature, namely, the diffusion rate is an increasing function taking the temperature as an independent variable, so that the diffusion process of the interface slow release agent is adapted to the polymerization time, a polymerization product and a metal wire bundle are in a non-contact state in the early and middle stages of polymerization, mechanical occlusion is difficult to form on the polymerization product, moderate physical isolation of the metal wire bundle and MMA or PMMA high polymer chains in the polymerization process is ensured, the interface corrosion inhibitor basically has no residue on the surface of the metal wire bundle in the later stage of polymerization, the metal wire bundle is in direct contact with the PMMA substrate which is preliminarily solidified, and the mechanical occlusion is formed by utilizing the polymerization reaction of residual monomer MMA at the interface, so that the original spatial position of the metal wire bundle is basically not changed. Therefore, by reasonably using the interface slow release agent, the isolation state between the metal wire harness and the polymerization product can be slowly changed in the polymerization process of the liquid phase material until mechanical occlusion is formed, the original space position of the metal wire harness is basically not changed in the polymerization process, and the problem that the composite board is bent due to mismatching of volume shrinkage and volume change of the metal wire harness in the polymerization process of the liquid phase material and phase interface occlusion in advance is avoided. Referring to fig. 1 or 2, in the manufactured plate, the metal wire bundles are arranged in parallel in the PMMA matrix, and the surface of the plate is smooth and clean and has no bending visible to naked eyes.
Optionally, in order to better control the polymerization process and the diffusion process of the interfacial sustained release agent, the production efficiency is improved, and step S3 includes:
low temperature stage: heating at 45-65 deg.c for 2-72 hr;
high temperature stage: heating at 95-125 deg.c for 1-12 hr.
Optionally, the interfacial slow release agent meets the following conditions with respect to MMA:
at the end of the low-temperature stage, the interface slow release agent on the surface of the wire harness is not diffused;
and at the end of the high-temperature stage, the diffusion of the interface slow release agent on the surface of the wire harness is completed.
With continued reference to fig. 5, in the polymerization process, in the low-temperature stage, along with the occurrence of the polymerization reaction, the interfacial slow release agent gradually diffuses slowly to the periphery (arrow 600 indicates the diffusion direction of the interfacial slow release agent), the thickness is reduced to d2 (d 2 < d 1) until the low-temperature stage is finished, the polymerization reaction main body is completed, the liquid phase medium 118 becomes the preliminary solid phase medium 119, the volume reduction degree is obvious, at this time, the polymerization product and the metal wire bundle are in a non-contact state, so that mechanical occlusion is difficult to form on the polymerization product, moderate physical isolation of the metal wire bundle and MMA or PMMA polymer chains in the polymerization process is ensured, and bending caused by volume change of the metal wire bundle, volume shrinkage mismatch of the polymerization product and phase interface occlusion occurring in advance is avoided. And then the high-temperature stage is carried out until the polymerization reaction is finished, the thickness is further reduced to d3 (d3 is approximately equal to 0), the preliminary solid phase medium 119 is changed into a complete or basically complete solid phase medium 120, and the whole polymerization process is completed, at this time, the interface corrosion inhibitor basically has no residue on the surface of the metal wire harness, so that the metal wire harness is in direct contact with the PMMA matrix which is preliminarily cured, and the mechanical occlusion is formed by utilizing the polymerization reaction of the residual monomer MMA at the interface, thereby ensuring that the original spatial position of the metal wire harness is basically unchanged. Finally, the obtained metal embedded PMMA composite board basically does not bend. It will be appreciated that step S3 may also include only a low temperature stage, in which case the heating time may be extended until the entire polymerization process is completed.
Optionally, step S1 may specifically include:
providing a casting mold, wherein a positioning bracket is arranged in the casting mold, and is provided with a positioning through hole for passing through a metal wire harness;
passing the wire harness through a positioning through hole on the positioning bracket;
and coating an interface slow release agent on the surface of the metal wire harness.
Wherein, use the locating support in the casting mould, can increase the reliability of metal wire harness straightening state and space position (centering and parallel arrangement). When the positioning support is used, the positioning support is kept to be arranged in parallel at equal intervals as far as possible and is perpendicular to the arrangement direction of the metal wire bundles. Referring to fig. 6, the positioning through holes of the positioning bracket and the spatial relationship between the positioning through holes and the metal wire harness are divided into two types, namely a mirror circular table 300 and a cylinder 310, when the positioning through holes are the mirror circular table 300, the diameter of the metal wire harness is matched with the diameter of the section 301 at the narrowest section 301 of the positioning through holes when the metal wire harness passes through the positioning through holes, the space between the metal wire harness and the positioning bracket in the vertical direction is in clearance fit, and the distance between the metal wire harness and the positioning bracket is increased along the horizontal direction of the metal wire harness and changes along with the distance of the section 301, so that the liquid phase material is not easy to form bubbles in the overlapping space between the metal wire harness and the positioning bracket in the polymerization process; when the positioning through hole is a cylinder 310, the diameter of the positioning through hole should be slightly larger than that of the wire harness to be used, and the positioning through hole is also in clearance fit in consideration of the infiltration sufficiency of the liquid phase material and the effective discharge of bubbles.
Optionally, the positioning bracket is made of PMMA, so that the positioning bracket can be mutually dissolved with a liquid phase material forming a PMMA matrix to a certain extent in the forming process of the composite board, namely, the surface layer of the positioning bracket can be moderately dissolved by MMA monomer, and an interpenetrating network is formed with PMMA polymer generated by polymerization, so that a liquid-solid interface phase is eliminated. After polymerization, the positioning bracket is formed in the PMMA composite board and forms a transparent whole with the PMMA matrix, and the transparent whole cannot be distinguished by naked eyes. The positioning support can be used or not in the embodiment, and the quantity of the positioning support is positively related to the centering and parallel arrangement effect of the metal wire bundles in the PMMA composite plate finally in use, but the more the quantity is, the longer the operation time is. In practical application, 3 are generally preferred. When the locating support is used, the interface slow release agent is preferably coated on the surface of the metal wire harness after the metal wire harness passes through the locating through hole in the locating support, so that the interface slow release agent is prevented from being scraped in the process that the metal wire harness passes through the locating through hole.
Optionally, the casting mold comprises an annular adhesive tape, an upper template and a lower template, the annular adhesive tape is clamped between the upper template and the lower template, a cavity is formed together with the upper template and the lower template, the positioning support is located in the cavity, mounting through holes are formed in the portions, located on two sides of the length direction of the positioning support, of the annular adhesive tape, the end portions of the metal wire harnesses penetrate out of the mounting through holes, and accordingly the end portions of the metal wire harnesses can be fixed. The casting mold is a glass mold for casting molding, the manufacturing process of the casting mold is described in detail in patent 'mold suitable for high polymer fast casting' (ZL 202120435162.3) and related description in 'fastening mechanism of high polymer casting mold and high polymer casting device' (ZL 202120246569.1), and the main difference is that the part of the annular adhesive tape located at two sides of the length direction of the positioning bracket is provided with mounting through holes for fixing after the end part of the metal wire harness penetrates out of the annular adhesive tape. Optionally, the installation through hole is in interference fit with the metal wire bundle, and the adhesive tape has certain elasticity, so that radial extrusion can be formed on the metal wire bundle in an interference state, the installation through hole is in a closed state, and liquid phase materials in a cavity formed by the adhesive tape and the template cannot overflow through the through hole in the polymerization process. The material of the adhesive tape is not particularly limited, and the general polymer material with moderate elasticity, such as PVC, organic silicon rubber and the like, can be circular, elliptical or rectangular in cross section, and is found in practical use that when the rectangular adhesive tape is perforated, the rectangular adhesive tape is not easy to slide, the hole position precision is higher, and the mounting through hole is always positioned at the parallel center position of the adhesive tape clamped by the glass mold, so that the convenience of the rectangular adhesive tape is more outstanding. In order to improve the compression elasticity of the adhesive tape with the same material, the adhesive tape with a hollow structure can be adopted, and meanwhile, the use cost of raw materials is reduced. The positioning bracket is arranged in a frame surrounded by the adhesive tape of the pouring mold in advance, the adhesive tape is nested and locked with the lower template of the glass mold in the step, then the metal wire bundles coated with the interface slow release agent are sequentially penetrated into the corresponding aligned mounting through holes (the end parts respectively penetrate, and the stretching mode after the non-end penetrates), if the positioning bracket is included, the metal wire bundles also penetrate through the corresponding through holes of the positioning bracket (and the step occurs before penetrating into the mounting through holes), then the upper template is covered, the periphery of the mold is locked by the fastening piece, and the next stage is entered.
With reference to fig. 7 and 8, optionally, after the metal wire harness passes through the annular adhesive tape, the end portion of the metal wire harness is fixed by adopting a unidirectional locking buckle, the unidirectional locking buckle is propped against the outer side of the annular adhesive tape or the edge of the glass mold 800, and the step of fixing the two ends of the metal wire harness can be performed after the casting mold is fastened, so that the metal wire harness can be further ensured to be in a straightened state, and the problem of bending of the composite board caused by factors such as dead weight collapse and displacement of the metal wire harness can be avoided or reduced by combining the metal wire harness with the positioning bracket. The unidirectional locking buckle 700 comprises a radial locking unit 703, a pushing movable unit 702 and an internal channel (not identified in the figure) for a wire harness to pass through, and the use mechanism is as follows: the metal wire harness penetrates into the pushing movable unit 702 end, enters the inner channel until the metal wire harness is exposed, and is pushed forward along the metal wire harness to a required position, and the unidirectional locking function of the unidirectional locking buckle 700 is provided by the radial locking unit 703, for example, the radial locking unit 703 comprises a telescopic spring, a spherical steel ball and a round table cavity channel, so that the metal wire harness can only push forward (the diameter increasing direction of the round table cavity channel, so that the spherical steel ball is in a loose state), and cannot be pulled out in the opposite direction (the diameter decreasing direction of the round table cavity channel, so that the spherical steel ball is in a pressed state). In this embodiment, after the wire harness passes through the unidirectional locking buckle 700, the unidirectional locking buckle 700 is pushed until the front end 701 thereof symmetrically resides at the edge of the glass mold 800 and abuts against the upper and lower templates of the glass mold 800 (as shown in fig. 7 b), thereby locking the wire harness 100 to maintain a straightened state inside the mold. Considering the fracture risk when the mold made of glass material and the unidirectional locking buckle made of metal material are propped against each other, soft material adhesion or cladding, such as rubber, polyurethane and other polymer materials with moderate elasticity, can be properly carried out on the surface of the front end 701 of the unidirectional locking buckle. The related structure or operation mechanism of the unidirectional locking buckle can refer to the existing product, and the description is not repeated here.
The following are different implementation processes of the manufacturing method according to the present embodiment:
process 1
The manufacturing method of the metal embedded PMMA composite board has the thickness of 15mm.
The mass ratio of polymethyl methacrylate to the material composition ratio of the liquid phase material is 5-15%, the mass ratio of the initiator is less than or equal to 1%, and the balance is methyl methacrylate, wherein the polymethyl methacrylate and the methyl methacrylate form the PMMA polymer solution, and the initiator is ABVN. And (3) at the end of the step S1, forming a liquid phase material with the viscosity characteristic of 4-cup coating and the characterization outflow time of 80-120S (25 ℃).
The coating mode adopts wiping, in particular to dipping the interface slow release agent by dust-free cloth and coating the surface of the wire harness. The interfacial sustained release agent is moderately compatible with MMA, and the following conditions are satisfied: at the end of the low temperature stage (water bath) of 45-65 ℃/2-72 h, a small amount of interface slow release agent (d 2 > 0) still exists on the surface of the metal wire harness 100, and at the end of the high temperature stage (air bath) of 95-125 ℃/1-12 h, the interface slow release agent is fully diffused to the PMMA matrix. The interfacial sustained release agent in the process 1 is specifically C 8-20 Alkane, C 8-20 Alcohols, C 8-20 The acid is sequentially and correspondingly provided with alpha 1, alpha 2 and alpha 3, and the metal wire bundles in the other group of alpha 4 are not coated by an interface slow release agent, and the section diameters of the metal wire bundles used in the process 1 are the same.
The positioning bracket is arranged in the adhesive tape frame of the pouring mold in advance, at the moment, the adhesive tape is nested and locked with the lower template of the pouring mold, then the metal wire bundles coated with the interface slow release agent are sequentially penetrated into the corresponding through holes of the positioning bracket, then the metal wire bundles are penetrated into the mounting through holes of the corresponding adhesive tape, and then the upper template is covered on the metal wire bundles, and the periphery of the mold is locked by the fastener. The positioning brackets are always arranged in parallel at equal intervals as far as possible and are perpendicular to the arrangement direction of the metal wire bundles.
Considering the fracture risk when the die made of glass material and the unidirectional locking buckle made of metal material are propped against each other, the polyurethane elastic material can be properly attached to the surface of the front end 701 of the unidirectional locking buckle.
The polymerization process sequentially comprises a water bath or a blast air bath at 45-65 ℃ in a low-temperature stage for 2-72 h, and a blast air bath at 95-125 ℃ in a high-temperature stage for 1-12 h.
Process 2
Unlike process 1, the wire harness is replaced with a nylon harness of equal diameter, the surface of which is not coated with the interfacial slow-release agent, and the rest are kept consistent.
Process 3
Blank, no wire harness.
Sample preparation and result analysis
In the process 1, the composite plates with the groups of alpha 1, alpha 2 and alpha 3 are respectively arranged in a PMMA matrix in a centered and parallel manner, the surfaces of the plates are flat and smooth, no bending is visible (H in fig. 9), specifically, H1 in fig. 9 represents a cross-section perspective view, H2 in fig. 9 represents a front angle perspective view, and the metal wire bundles 100 are in a centered and parallel state; the composite sheet material of group α4 has a horizontal and vertical bending (D in fig. 9), and is not centered in the cross section (D1 in fig. 9) or is in a non-parallel state at a front view (D2 in fig. 9), that is, the sheet material mainly composed of the PMMA base 120 and the wire harness 100 is curved as a whole, and is difficult to use normally.
The light transmittance test is carried out by a UV-Vis spectrophotometer, the processes 1-3 are cut into samples with the sizes of 50mm multiplied by 15mm, wherein the samples in the process 1 and the process 2 are respectively characterized by transparent areas without metal or nylon wire harnesses, the wavelength range is 250-1100nm, the light transmittance test is carried out according to GB/T7134-2008 casting industrial organic glass plates, and the light transmittance data at the wavelength of 420nm are taken. In the process 1, the light transmittance of alpha 1, alpha 2, alpha 3 and alpha 4 is 92.31%, 92.29%, 92.24% and 92.36% in sequence; in process 2, the light transmittance was 92.28%; in the process 3, the light transmittance was 92.30%. Therefore, the light transmittance of the processes 1 to 3 has higher consistency, which indicates that the interfacial sustained-release agent has no influence on the transparency of the PMMA composite board.
The glass transition temperature (Tg) was measured by DSC equipment, and the heating temperature was selected to be in the range of room temperature to 200℃and the heating rate was 20/min ℃. In the process 1, the composite plates of the groups alpha 1, alpha 2, alpha 3 and alpha 4 have the corresponding Tg of 106 ℃, 103 ℃ and 107 ℃ respectively; the Tg of the composite board in the process 2 is 105 ℃; the Tg of the composite board in Process 3 was 105 ℃. Therefore, the Tg values of the corresponding composite boards in the processes 1-3 have higher consistency, which shows that the interface slow release agent has no influence on the temperature resistance of the PMMA composite board basically.
In addition, the application also tests and characterizes basic physical properties (tensile strength, elongation at break and impact strength without notch of a simply supported beam) according to GB/T7134-2008 casting industrial organic glass plate. In the sample preparation, the impact strength test samples are prepared by taking the area containing the metal or nylon wire harness in the middle in the process 1 and the process 2, and taking the transparent areas from the rest test items. The sample preparation size is carried out according to the national standard requirements of the corresponding test. As apparent from the statistics of the results of the performance characterization shown in Table 1, the notched impact strength index (with reference to FIG. 10) of the simply supported beams is shown, and the samples in the process 1 are 110.3-134.1 kJ/m 2 And the process 2 and the process 3 are greatly reduced to 51.8-64.4 kJ/m in sequence 2 And 20.7-28.4 kJ/m 2 The impact resistance of the wire harness is obviously higher than that of nylon with the same diameter, and the transparent plate without the wire harness is the lowest. In addition to impact properties, the other basic physical properties of processes 1-3 are statistically consistent.
TABLE 1 statistics of Performance characterization results
Remarks: c the impact strength is specifically the impact strength of a simple beam without a notch.
The application also provides a metal embedded PMMA composite board, which is manufactured by adopting the manufacturing method of the metal embedded PMMA composite board in the embodiment.
The manufacturing method of the metal embedded PMMA composite board comprises the following steps: fixing the wire harness coated with the interface slow release agent in a casting mold; casting a liquid phase material for forming a PMMA matrix in a casting mold; and polymerizing to obtain the metal embedded PMMA composite board. The metal embedded PMMA composite board is manufactured by the manufacturing method. According to the application, the interface slow release agent is coated on the surface of the metal wire harness, so that the isolation state between the metal wire harness and a polymerization product can be slowly changed in the polymerization process of the liquid phase material until mechanical occlusion is formed, the original space position of the metal wire harness is basically not changed in the polymerization process, and the problems of bending of a composite plate caused by mismatching of volume shrinkage and volume change of the metal wire harness in the polymerization process of the liquid phase material and phase interface occlusion in advance are avoided.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. The manufacturing method of the metal embedded PMMA composite board is characterized by comprising the following steps of:
step S1, fixing a metal wire bundle coated with an interface slow-release agent in a casting mold;
step S2, pouring liquid phase materials for forming PMMA matrix in the pouring mold;
step S3, polymerizing to obtain a metal embedded PMMA composite board;
the step S3 includes:
low temperature stage: heating at 45-65 deg.c for 2-72 hr;
high temperature stage: heating at 95-125 deg.c for 1-12 hr;
wherein, the compatibility of the interface slow release agent and MMA meets the following conditions:
when the low-temperature stage is finished, the interface slow release agent on the surface of the wire harness is not completely diffused;
and at the end of the high-temperature stage, the interface slow release agent on the surface of the metal wire bundle is diffused.
2. The method according to claim 1, wherein the interfacial slow-release agent has a solubility in MMA solvent of 0.01g/100g MMA-10 g/100g MMA at 20℃and 1 standard atmospheric pressure.
3. The method according to claim 1, wherein the interfacial sustained release agent comprises one or more of n-octane, n-nonane, n-decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, n-octanol, n-nonanol, n-decanol, dodecanol, 1-tridecanol, tetradecanol, 1-pentadecanol, hexadecanol, heptadecanol, octadecanol, butyl ether, n-amyl ether, hexyl ether, heptyl ether, n-octyl ether, n-octanoic acid, nonanoic acid, n-decanoic acid, undecanoic acid, phenyl dodecanoate, 2-hydroxydodecanoate, 3-hydroxydodecanoate, 12-aminododecanoate, methyl dodecanoate, stearic acid, palm wax, slice paraffin, and liquid paraffin.
4. The method according to claim 1, wherein the step S1 includes:
providing a casting mold, wherein a positioning bracket is arranged in the casting mold, and is provided with a positioning through hole for passing through the metal wire harness;
passing the metal wire harness through a positioning through hole on the positioning bracket;
and coating an interface slow release agent on the surface of the metal wire harness.
5. The method of manufacturing according to claim 4, wherein the positioning bracket is made of PMMA, and the positioning through hole is in clearance fit with the wire harness.
6. The method according to claim 4, wherein the casting mold comprises an annular adhesive tape, an upper die plate and a lower die plate, the annular adhesive tape is clamped between the upper die plate and the lower die plate, a cavity is formed together with the upper die plate and the lower die plate, the positioning bracket is positioned in the cavity, mounting through holes are formed in portions, located on two sides in the length direction, of the positioning bracket, and the end portions of the metal wire bundles penetrate through the mounting through holes.
7. The method of manufacturing according to claim 6, wherein the mounting through hole is in interference fit with the wire harness, the wire harness is fixed by a one-way locking buckle, and the one-way locking buckle abuts against the side surfaces of the upper die plate and the lower die plate.
8. A metal embedded PMMA composite sheet manufactured by the method of any one of claims 1 to 7.
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| CN113524535A (en) * | 2021-07-14 | 2021-10-22 | 汤臣(江苏)材料科技股份有限公司 | Production process of acrylic plate embedded with silk |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3002942B1 (en) * | 2013-03-11 | 2016-01-22 | Arkema France | LIQUID (METH) ACRYLIC SYRUP FOR IMPREGNATING A FIBROUS SUBSTRATE, METHOD FOR IMPREGNATING A FIBROUS SUBSTRATE, COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF SAID PRE-IMPREGNATED SUBSTRATE. |
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| JPH0260496B2 (en) * | 1985-03-29 | 1990-12-17 | Fukubi Kagaku Kogyo Kk | |
| EP0319659A2 (en) * | 1987-12-09 | 1989-06-14 | Basf Engineering Plastics Co., Ltd. | Process for producing composite laminate comprising insert part and injection-molded part |
| CN101184816A (en) * | 2005-05-27 | 2008-05-21 | 卢西特国际英国有限公司 | An embedment casting composition |
| CN113150481A (en) * | 2021-04-26 | 2021-07-23 | 中国电子科技集团公司第三十三研究所 | Acrylic cast wire mesh shielding glass and preparation method thereof |
| CN113524535A (en) * | 2021-07-14 | 2021-10-22 | 汤臣(江苏)材料科技股份有限公司 | Production process of acrylic plate embedded with silk |
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