CN114685953A - Modified polyester material, composite sandwich board prepared from modified polyester material and preparation method of composite sandwich board - Google Patents
Modified polyester material, composite sandwich board prepared from modified polyester material and preparation method of composite sandwich board Download PDFInfo
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- CN114685953A CN114685953A CN202210220474.1A CN202210220474A CN114685953A CN 114685953 A CN114685953 A CN 114685953A CN 202210220474 A CN202210220474 A CN 202210220474A CN 114685953 A CN114685953 A CN 114685953A
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a modified polyester material, which comprises the following raw materials: polyester, coupling agent; the polyester is a mixture of a group A polyester and a group B polyester; the A type polyester is crystalline polyester, and the B type polyester is non-crystalline polyester; the glass transition temperature of the modified polyester material is 67-81 ℃, the melting point is 210-265 ℃, and the crystallization temperature is 120-220 ℃; the invention has the beneficial effects that: the continuous fiber reinforced polyester composite sandwich panel provided by the invention is characterized in that the upper skin layer and the lower skin layer are made of a continuous fiber reinforced modified polyester material, the crystallization ability of the polyester of the continuous fiber reinforced modified polyester material obtained by soaking the modified polyester in the continuous fiber or a continuous fiber product is reduced, and the polyester material with the reduced crystallization ability has stronger toughness and tear resistance, namely the continuous fiber reinforced polyester composite sandwich panel provided by the invention has stronger mechanical property advantages and dimensional stability advantages.
Description
The application is a divisional application with the application number of 202010366376.X, which is filed on 30.4.2020/4.2020 and is named as a modified polyester material, a composite sandwich board made of the modified polyester material and a preparation method of the composite sandwich board.
Technical Field
The invention belongs to the technical field of composite sandwich panel preparation, and particularly relates to a modified polyester material, a preparation method thereof and application thereof in a composite sandwich panel.
Background
The sandwich board is a board formed by gluing a surface layer material with high strength and a core material with light volume weight and low strength, has the advantages of high strength, light weight, fire resistance, heat preservation, heat insulation, convenient installation and the like, and has wide application in a plurality of fields such as automobile industry, household appliances, building engineering and the like.
The polyester composite sandwich board has higher rigidity, mechanical strength and impact strength, so that the polyester composite sandwich board is more widely concerned by people. The polyester is a generic name of a polymer obtained by polycondensation of a polyhydric alcohol and a polybasic acid. Common polyesters include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT), are engineering plastics with excellent performance and wide application, and are widely applied to the fields of instruments and meters, automobile industry, fibers, films, extrusion molding products, buildings and the like.
Among them, PET is available as a polyester material which is the earliest to be industrially produced, but at the beginning, PET is almost used for synthetic fibers, and after a nucleating agent and a crystallization promoter are successively developed and disclosed, PET is gradually used as an engineering plastic and is used as a thermoplastic polyester together with polybutylene terephthalate (PBT), and becomes one of five major engineering plastics.
The PET has good mechanical property, the long-term use temperature can reach 120 ℃, and the PET also has insulativity, creep resistance, fatigue resistance, friction resistance and dimensional stability, so the polyester composite sandwich board prepared by the PET is widely favored by people, but the impact resistance is poor, the PET is easy to crystallize in the hot pressing process, the toughness is obviously reduced, the use range is limited, and therefore, how to reduce the crystallization capacity of the polyester is one of effective ways for improving the application range of the composite sandwich board.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a modified polyester material, a composite sandwich board made of the modified polyester material and a preparation method of the composite sandwich board.
The raw material polyester adopted by the modified polyester material has lower crystallinity after being modified, so that the processing temperature of the modified polyester material is reduced, and the toughness and the tear resistance of the composite sandwich board are improved.
The continuous fiber reinforced polyester composite sandwich board is formed by compounding a continuous fiber reinforced modified polyester serving as a skin material and a folded hexagonal honeycomb prepared from the modified polyester serving as a core material. The continuous fiber reinforced polyester composite sandwich panel has higher toughness and tear resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a modified polyester material, which comprises the following raw materials, by weight, 75-85 parts of polyester and 0.1-1.5 parts of a coupling agent; the polyester is a mixture of a group A polyester and a group B polyester; the A type polyester is crystalline polyester, and the B type polyester is non-crystalline polyester;
the class A polyester is
R is as follows: a linear, branched or cyclic C4-C12 alkyl group;
the B-type polyester is at least one of polyethylene terephthalate-neopentyl glycol ester and polyethylene terephthalate-1, 4-cyclohexanedimethanol ester; the amount of group B polyester in the polyester is from 40 to 80 wt% (e.g., 60 wt%, 70 wt%, 80 wt%) of the total amount of polyester.
The B-type polyester is non-crystalline polyester, but the B-type polyester is expensive, and the low-cost A-type polyester and the B-type polyester are mixed for ester exchange reaction, so that the crystallization property of the A-type polyester is reduced, the processing temperature of the modified polyester material is reduced, and the toughness and the tear resistance of the composite sandwich board are improved.
In the modified polyester material, as a preferred embodiment, the number of straight-chain and branched carbon atoms in R is 2 to 12.
In the modified polyester material, as a preferred embodiment, the group a polyester is at least one of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate.
In the above modified polyester material, as a preferable embodiment, the intrinsic viscosity of the group A polyester is 0.6 to 1.0dl/g, and the intrinsic viscosity of the group B polyester is 0.7 to 0.8 dl/g.
In the above-mentioned modified polyester material, as a preferred embodiment, the modified polyester material has a glass transition temperature of 67 to 81 ℃ (e.g., 68 ℃, 70 ℃, 72 ℃, 76 ℃, 80 ℃), a melting point of 210-.
In the above modified polyester material, as a preferred embodiment, the modified polyester material further comprises the following raw materials in parts by weight: 0.5-4 parts of lubricant, 0.1-0.5 part of antioxidant, 13-18 parts of flame retardant, 0.0001-0.0005 part of colorant and 0.5-5 parts of toughening agent.
In the modified polyester material of the invention, the functions of each auxiliary material component are as follows:
lubricant: besides improving fluidity, the polyester resin can also play a role of a melting promoter, an anti-adhesion and anti-static agent, a slipping agent and the like.
Antioxidant: the oxidation process of the polymer is retarded. Thereby enabling the polymer to be processed smoothly and prolonging the service life.
Flame retardant: functional additives for imparting flame retardancy to flammable polymers.
Colorant: substances that can change the color of an object, or that can dye a colorless object with color.
In the above modified polyester material, as a preferred embodiment, the coupling agent is a silane coupling agent KH-560, the lubricant is a high temperature resistant lubricant TA-401, the antioxidant is an antioxidant 1010, the flame retardant is polybrominated styrene, the colorant is a blue-degree agent, and the toughening agent is a toughening agent AX 8900.
The second aspect of the present invention provides a method for preparing the modified polyester material, comprising: all raw materials (such as polyester, coupling agent, lubricant, antioxidant, flame retardant, colorant and toughening agent) are banburying homogenized in a double screw extruder at the temperature of 230-300 ℃ (such as 240 ℃, 250 ℃, 260 ℃, 270 ℃ and 280 ℃) to obtain the modified polyester. If the banburying homogenization temperature is lower than 230 ℃, the polyester is not melted and cannot be processed; if the temperature is higher than 300 ℃, degradation is easily caused, so the banburying homogenization temperature is controlled at 230 ℃ to 300 ℃, preferably 230 ℃ to 260 ℃ (such as 240 ℃, 250 ℃, 260 ℃).
A third aspect of the present invention provides a continuous fiber reinforced modified polyester material comprising: the modified polyester material and continuous fibers distributed in the modified polyester material.
In the above modified polyester material reinforced by continuous fibers, as a preferred embodiment, the modified polyester material reinforced by continuous fibers is obtained by impregnating continuous fibers or continuous fiber products with the modified polyester.
The fourth aspect of the invention provides a continuous fiber reinforced polyester composite sandwich board, which comprises an upper skin layer, a core layer and a lower skin layer which are sequentially overlapped;
the upper skin layer and the lower skin layer are made of a continuous fiber reinforced modified polyester material;
the core layer is a honeycomb core layer and is made of modified polyester materials.
The continuous fiber reinforced polyester composite sandwich board provided by the invention is characterized in that an upper skin layer and a lower skin layer are prepared from a continuous fiber reinforced modified polyester material. The continuous fiber reinforced modified polyester material is obtained by infiltrating continuous fibers or continuous fiber products with modified polyester, and the modified polyester effectively reduces the crystallinity of the polyester due to the ester exchange reaction of the A-type polyester and the B-type polyester, improves the toughness of the composite sandwich board, and enlarges the application range of the composite sandwich board.
The core layer of the continuous fiber reinforced polyester composite sandwich board is made of folded hexagonal honeycombs made of modified polyester. Compared with the traditional circular tube core layer, the contact area of the core layer and the skin layer is larger, and the tear strength of the composite sandwich board can be effectively improved. The core layer is made of modified polyester materials, and the crystallinity of the modified polyester is lower than that of unmodified polyester, so that the toughness resistance of the core layer is improved to a certain extent.
The fifth aspect of the present invention provides a method for preparing the above continuous fiber reinforced polyester composite sandwich panel, comprising the following steps:
(1) evenly and flatly infiltrating the continuous fiber or the continuous fiber product with the modified polyester to prepare a continuous fiber reinforced modified polyester material;
(2) heating, curing, cooling and rolling the continuous fiber reinforced modified polyester material obtained in the step (1) to obtain an upper leather layer and a lower leather layer;
(3) preparing thermoplastic half-hexagon from modified polyester, and stacking and hot-pressing the obtained thermoplastic half-hexagon to obtain a folded hexagonal honeycomb core layer;
(4) and overlapping the obtained upper skin layer, core layer and lower skin layer, and hot-pressing to form the continuous fiber reinforced polyester composite sandwich board.
In the step (1) of the preparation method of the fifth aspect, as a preferred embodiment, before the infiltrating, the method further comprises the steps of flattening, eliminating static electricity and preheating the continuous fiber or the continuous fiber product; preferably, the continuous fiber or continuous fiber product has a glass fiber content of 45 wt% to 65 wt% (e.g., 50 wt%, 55 wt%, 60 wt%). When the glass fiber content is lower than 45 wt%, the performance is low, and no practical application value exists, and when the glass fiber content is higher than 65 wt%, the mass production process is greatly affected, so that normal production cannot be realized.
Preferably, the continuous fiber is one of polymer synthetic fiber and inorganic fiber or a mixture thereof; preferably, the polymer synthetic fiber is at least one of polyamide fiber, ultra-high molecular weight polyethylene fiber, aramid fiber and carbon fiber; the inorganic fiber is at least one of glass fiber, basalt fiber and boron fiber; preferably, the ultra-high molecular weight polyethylene fibers are unbranched linear polyethylene fibers having a molecular weight of 150 ten thousand or more.
In the step (2) of the production method of the above fifth aspect, as a preferred embodiment, the temperature of the heating and aging is 180 ℃ to 210 ℃ (185 ℃, 190 ℃, 200 ℃). If the temperature is lower than 180 ℃, the resin is easy to cool to influence the infiltration effect, and if the temperature is too high, the resin is easy to stick to the roller to influence the production effect.
Compared with the prior art, the invention has the beneficial effects that: compared with the traditional circular tube honeycomb sandwich board, the continuous fiber reinforced polyester composite sandwich board has stronger tear strength because the core layer is a folded hexagonal honeycomb layer.
The continuous fiber reinforced polyester composite sandwich board provided by the invention has the advantages that the upper skin layer and the lower skin layer are prepared from the continuous fiber reinforced modified polyester material, the polyester crystallization capacity of the continuous fiber reinforced modified polyester material obtained by soaking the modified polyester in the continuous fiber or a continuous fiber product is reduced, the crystallization of the polyester material is an important factor influencing the fiber reinforced polyester composite material, and the polyester material with the reduced crystallization capacity has stronger toughness and tear resistance, namely, the continuous fiber reinforced polyester composite sandwich board provided by the invention has stronger mechanical property advantages and dimensional stability advantages.
The continuous fiber reinforced polyester composite sandwich board has wider application range. Can be applied to a plurality of fields such as automobile industry, household electrical appliances, environmental protection machinery, building engineering, aviation, aerospace and the like.
Drawings
FIG. 1 is a schematic structural view of a core layer of a continuous fiber reinforced polyester composite sandwich panel according to the present invention;
FIG. 2 is a cross-sectional view of a continuous fiber reinforced polyester composite sandwich panel in accordance with the present invention;
in the figure: 1. a half hexagon; 2. hexagonal honeycomb; 3. an epithelial layer; 4. folding the hexagonal honeycomb core layer; 5. lower cortex
Detailed Description
The following examples further illustrate the present invention in detail, and the scope of the present invention includes, but is not limited to, the following examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated.
In one embodiment of the present invention, the polyester resin refers to a high molecular product formed by polymerization or transesterification of an alcohol and a carboxylic acid. Specifically, the A-type polyester is linear homopolyester formed by the polycondensation of dihydric alcohol and dibasic acid, for example, the linear homopolyester formed by the polycondensation of ethylene glycol and terephthalic acid is PET polyester; the group B polyester is a copolyester, such as polyethylene terephthalate-neopentyl glycol ester with comonomers of terephthalic acid, ethylene glycol and neopentyl glycol and polyethylene terephthalate-1, 4-cyclohexanedimethanol ester with comonomers of terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol.
The materials, methods, and examples herein are illustrative only and, unless otherwise specified, should not be construed as limiting. Only suitable methods and materials are described herein, and methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
The reagents and starting materials used in the following examples are all commercially available products.
Wherein the polyester B, polyethylene terephthalate-neopentyl glycol ester and polyethylene terephthalate-1, 4-cyclohexanedimethanol ester are directly purchased slice particles, the viscosity is 0.7-0.8dl/g, and GS3 type resin of Issman company; continuous glass fiber was purchased from owens corning under the brand name: SE4805-1200 tex.
Through tests, the melting point of the modified polyester material prepared in the following examples is 200-280 ℃, and the crystallization temperature is 120-220 ℃.
Example 1
(1) Eliminating static electricity and heating: continuous fibers having a glass fiber content of 50 wt.% were placed on rollers in a spinning frame, and then the continuous glass fibers were passed through a pretensioning roller, then through an antistatic device, and then through a heated oven set at 80 ℃.
(2) Dipping: fully drying the raw materials of the modified polyester material respectively before twin-screw honey refining, and then preparing the modified polyester material into PET polyester: polyethylene terephthalate-neopentyl glycol ester: coupling agent KH-560: high-temperature-resistant lubricant TA-401: antioxidant 1010: flame retardant poly brominated styrene: colorant blueness agent: the materials of toughening agent AX 8900: 40:0.3:0.8:0.1:14:0.0001:1 were weighed accurately and mixed well before being fed into the twin screw extruder. The rotation speed of the twin-screw extruder is adjusted to 200 r/min, the vacuum degree is adjusted to 99KPa, and the temperature is set to 260 ℃. The ester composition flows through a metering pump and then through an open die and a melt impregnation die where the glass fibers are combined with the polyester composition for further impregnation within the melt impregnation die. Further, the glass fiber impregnated with the polyester composition was further impregnated with a pair of rollers spaced 0.3mm apart to form a smooth surface.
(3) Heating and curing: and (3) passing the glass fiber soaked by the polyester in the step (2) through a heating roller, and soaking the glass fiber by resin better.
(4) Cooling and rolling: and (4) feeding the heated and cured composite fabric obtained in the step (3) into 2 groups of cooling press rolls, reducing the temperature of the material to be below the glass transition temperature, simultaneously enabling the cooling rolls to have certain pressure to enable the fiber-reinforced polyester composite material to have a smooth surface, and then rolling the fiber-reinforced polyester composite material by using a rolling roll to form an upper skin layer 3 and a lower skin layer 5 of the composite sandwich board.
(5) Fully drying the raw materials of the modified polyester material respectively before twin-screw honey refining, wherein the raw materials are prepared from the following raw materials in percentage by weight: polyethylene terephthalate-neopentyl glycol ester: coupling agent KH-560: high-temperature-resistant lubricant TA-401: antioxidant 1010: flame retardant poly brominated styrene: colorant bluing agent: the materials of toughener AX 8900: 40:0.3:4:0.1:14:0.0001:1 were weighed accurately and mixed well before being fed into a twin screw extruder. The rotation speed of the twin-screw extruder is adjusted to 200 r/min, the vacuum degree is adjusted to 99KPa, and the temperature is set to 260 ℃. The resin is extruded from the casting die to form a polyester film, and the thermoplastic hemihexagonal body 1 is formed by a plastic sucking mode, and the figure 1 is shown. Thermoplastic half-hexagons (also referred to as half-hexagons, i.e. having a structure in which the hexagonal cylinders are equally divided in the height direction) are stacked, hot-pressed and skin-bonded to form a folded hexagonal honeycomb core 4 (also referred to as a honeycomb plate) in which a plurality of hexagonal honeycombs 2 are formed, and referring to fig. 2, two half-hexagons 1 are butted to form one hexagonal honeycomb 2 (i.e. a hollow hexagonal cylinder).
And stacking the continuous fiber reinforced polyester composite material and the polyester hexagonal honeycomb plate into an ABA form, wherein the A layer is the continuous fiber reinforced polyester composite material, namely an upper skin layer 3 and a lower skin layer 5, the B layer is a folding hexagonal honeycomb core layer 4, and hot-pressing the composite material and the polyester hexagonal honeycomb plate by using a Teflon belt press to form the continuous fiber reinforced polyester composite sandwich plate. The specifications and mechanical properties of the composite sandwich panels prepared in this example are shown in table 1.
Example 2
(1) Eliminating static electricity and heating: continuous fibers having a glass fiber content of 50 wt.% were placed on rollers in a spinning frame, and then the continuous glass fibers were passed through a pretensioning roller, then through an antistatic device, and then through a heated oven set at 80 ℃.
(2) Dipping: fully drying the raw materials of the modified polyester material respectively before twin-screw honey refining, and then preparing the modified polyester material into PET polyester: polyethylene terephthalate-neopentyl glycol ester: coupling agent KH-560: high-temperature-resistant lubricant TA-401: antioxidant 1010: flame retardant poly brominated styrene: colorant blueness agent: the materials of toughening agent AX8900 ═ 20:60:0.3:0.8:0.1:14:0.0001:1 were weighed accurately and mixed well before being fed into the twin screw extruder. The rotation speed of the twin-screw extruder is adjusted to 200 r/min, the vacuum degree is adjusted to 99KPa, and the temperature is set to 260 ℃. The ester composition flows through a metering pump and then through an open die and a melt impregnation die where the glass fibers are combined with the polyester composition for further impregnation within the melt impregnation die. Further, the glass fiber impregnated with the polyester composition was further impregnated with a pair of rollers spaced 0.3mm apart to form a smooth surface.
(3) Heating and curing: and (3) passing the glass fiber soaked by the polyester in the step (2) through a heating roller, and soaking the glass fiber by resin better.
(4) Cooling and rolling: and (3) heating the cured composite fabric at 185 ℃ in the step (3) and putting the heated composite fabric into 2 groups of cooling press rolls, reducing the temperature of the material to be below the glass transition temperature, and simultaneously, enabling the cooling rolls to have certain pressure so that the fiber reinforced polyester composite material has a smooth surface. And then the core is wound by a winding roller to be used as an upper skin layer 3 and a lower skin layer 5 of the composite sandwich board.
(5) Fully drying the components in the polyester mixture respectively before twin-screw honey refining, and mixing the components in the proportion of polybutylene terephthalate: polyethylene terephthalate-1, 4-cyclohexanedimethanol ester: coupling agent KH-560: high-temperature-resistant lubricant TA-401: antioxidant 1010: flame retardant poly (brominated styrene): colorant blueness agent: the materials of toughening agent AX8900 ═ 20:60:0.3:0.8:0.1:14:0.0001:1 were weighed accurately and mixed well before being fed into the twin screw extruder. The rotation speed of the twin-screw extruder is regulated to 200 r/min, the vacuum degree is regulated to 99KPa, and the temperature is set to 250 ℃. And extruding the resin from a casting die to form a polyester film, and forming the thermoplastic hemihexagon through a plastic suction mode. The thermoplastic half-hexagons are stacked, hot pressed and skin bonded to form a honeycomb panel.
The continuous fiber reinforced polyester composite material and the polyester hexagonal honeycomb plate are stacked into an ABA form, wherein the layer A is the continuous fiber reinforced polyester composite material, namely an upper skin layer 3 and a lower skin layer 5, the layer B is a folding hexagonal honeycomb core layer 4, and the continuous fiber reinforced polyester composite sandwich plate is formed by hot pressing through a Teflon belt press. The specifications and mechanical properties of the composite sandwich panels prepared in this example are shown in table 1.
Example 3
(1) Eliminating static electricity and heating: continuous fibers having a glass fiber content of 65 wt.% were placed on rollers in a spinning frame, and then the continuous glass fibers were passed through a pretensioning roller, then through an antistatic device, and then through a heated oven set at 80 ℃.
(2) Dipping: fully drying the raw materials of the modified polyester material respectively before twin-screw honey refining, and then preparing the modified polyester material into polytrimethylene terephthalate according to the weight ratio: polyethylene terephthalate-neopentyl glycol ester: coupling agent KH-560: high-temperature-resistant lubricant TA-401: antioxidant 1010: flame retardant poly brominated styrene: colorant blueness agent: the materials of toughener AX8900 ═ 32:48:0.3:0.8:0.1:14:0.0001:1 were weighed accurately and mixed well before being fed into a twin screw extruder. The rotation speed of the twin-screw extruder is regulated to 200 r/min, the vacuum degree is regulated to 99KPa, and the temperature is set to 300 ℃. The ester composition flows through a metering pump and then through an open die and a melt impregnation die where the glass fibers are combined with the polyester composition for further impregnation within the melt impregnation die. Further, the glass fiber impregnated with the polyester composition was further impregnated with a pair of rollers spaced 0.3mm apart to form a smooth surface.
(3) Heating and curing: and (3) allowing the glass fiber soaked by the polyester in the step (2) to pass through a heating roller, and soaking the glass fiber by resin better.
(4) Cooling and rolling: and (3) heating the cured composite fabric at the temperature of 200 ℃ in the step (3) and putting the heated composite fabric into 2 groups of cooling press rolls, reducing the temperature of the material to be below the glass transition temperature, and simultaneously, enabling the cooling rolls to have certain pressure so that the fiber reinforced polyester composite material has a smooth surface. And then wound by a winding roller.
(5) Fully drying the components in the polyester mixture respectively before twin-screw honey refining, and mixing the components in the proportion of polybutylene terephthalate: polyethylene terephthalate-1, 4-cyclohexanedimethanol ester: high-temperature-resistant lubricant TA-401: antioxidant 1010: flame retardant poly brominated styrene: colorant blueness agent: the materials of toughener AX 8900: 40:0.3:4:0.1:14:0.0001:1 were weighed accurately and mixed well before being fed into a twin screw extruder. The rotation speed of the twin-screw extruder is regulated to 200 r/min, the vacuum degree is regulated to 99KPa, and the temperature is set to 300 ℃. And extruding the resin from a casting die to form a polyester film, and forming the thermoplastic hemihexagon through a plastic suction mode. The thermoplastic half-hexagons are stacked, hot pressed and skin bonded to form a honeycomb panel.
And stacking the continuous fiber reinforced polyester composite material and the polyester hexagonal honeycomb plate into an ABA form, wherein the A layer is the continuous fiber reinforced polyester composite material, namely an upper skin layer 3 and a lower skin layer 5, the B layer is a folding hexagonal honeycomb core layer 4, and hot-pressing the composite material and the polyester hexagonal honeycomb plate by using a Teflon belt press to form the continuous fiber reinforced polyester composite sandwich plate. The specifications and mechanical properties of the composite sandwich panel prepared in this example are shown in table 1.
Example 4
In this example, the raw materials and processes were the same except that the polyesters of group A and group B were used in different amounts from those of example 1, and the composite sandwich panel was prepared with the same specifications and the properties as those shown in Table 1. In the embodiment, the modified polyester obtained in the steps (2) and (5) is prepared from the following raw materials in parts by mass: polyethylene terephthalate-neopentyl glycol ester: coupling agent KH-560: high-temperature-resistant lubricant TA-401: antioxidant 1010: flame retardant poly brominated styrene: colorant bluing agent: the toughening agent AX 8900: 56:24:0.3:0.8:0.1:14:0.0001: 1.
Table 1 specifications and properties of the composite sandwich panels of examples 1-4
Examples 5 to 8
Examples 5-8 are different from example 3 only in the amount of the coupling agent added during the preparation of the modified polyester material, and are otherwise the same as example 3, and the parameters of the amount of the coupling agent added and the product properties of examples 5-8 are shown in Table 2:
TABLE 2 preparation Process parameters and corresponding Properties of examples 5-8
| Numbering | The amount of the coupling agent added | Compressive strength MPa | Peel strength N/cm |
| Example 5 | 0.1 part by weight | 1.7 | 275 |
| Example 6 | 0.2 part by weight | 1.7 | 291 |
| Example 7 | 1.0 part by weight | 1.7 | 289 |
| Example 8 | 1.2 parts by weight | 1.7 | 284 |
Remarking: the detection method of the compression strength is GB/T1453-
The detection method of the peeling strength is GB/T1457-
Examples 9 to 12
Examples 9-12 compared to example 3, the temperature of the banburying homogenization in steps (2) and (5) was different during the preparation of the modified polyester material only, and the rest was the same as example 3, and the parameters of the banburying homogenization temperature and the product properties in examples 9-12 are shown in Table 3:
TABLE 3 preparation Process parameters and corresponding Properties of examples 9-12
Remarking: the detection method of the compression strength is GB/T1453-
The detection method of the peeling strength is GB/T1457-
Comparative example 1: the hexagonal honeycomb plate of the core layer is replaced by a circular tube honeycomb sandwich plate, and other process conditions are the same as those of the invention.
The performance parameters of the composite sandwich panel of comparative example 1 and the composite sandwich panel of example 1 are shown in table 4:
table 4 performance parameters of the composite sandwich panels obtained in comparative example 1 and example 1
| Detecting items | Detection method | Comparative example 1 | Example 1 |
| Thickness mm | 20 | 20 | |
| Area weight Kg/m2 | 3.74 | 3.74 | |
| Compressive strength MPa | GB/T 1453-2005 | 1.7 | 1.7 |
| Peel strength N/cm | GB/T 1457-2005 | 240 | 310 |
As can be seen from table 4, the peel strength of the composite sandwich panel described in example 1 is higher, that is, the continuous fiber reinforced polyester composite sandwich panel of the present invention has stronger tear strength than the conventional circular tube honeycomb sandwich panel due to the folded hexagonal honeycomb core layer.
Comparative example 2: the preparation process of the composite sandwich panel of comparative example 2 was the same as the preparation process of the continuous fiber reinforced polyester composite sandwich panel of example 1 except that the polyester in the modified polyester material used in steps (2) and (5) was a type a polyester.
Comparative example 3, the continuous fiber reinforced polyester composite sandwich panel of comparative example 3 was the same as the continuous fiber reinforced polyester composite sandwich panel of example 1 except that the polyester of the raw material modified polyester was a mixture of a group a polyester and PBT (polybutylene terephthalate).
The performance parameters of the composite sandwich panels of comparative examples 2-3 and the composite sandwich panel of example 1 are shown in table 5:
TABLE 5 Performance parameters of the composite sandwich panels obtained in comparative examples 2-3 and example 1
| Detecting items | Detection method | Example 1 | Comparative example 2 | Comparative example 3 |
| Thickness mm | 20 | 20 | 20 | |
| Area weight Kg/m2 | 3.74 | 3.74 | 3.74 | |
| Compressive strength MPa | GB/T 1453-2005 | 1.7 | 1.2 | 1.3 |
| Peel strength N/cm | GB/T 1457-2005 | 310 | 150 | 230 |
As can be seen from table 5, since the composite sandwich panel described in example 1 uses the modified polyester material with lower crystallization ability as the raw material, the compressive strength (toughness) and tear resistance of the obtained composite sandwich panel are better than those of the composite sandwich panel using the unmodified polyester material in comparative example 2.
Although the compression resistance and the peel strength of the composite sandwich panel in the comparative example 3 are superior to those of the composite sandwich panel made of unmodified polyester in the comparative example 2, compared with the composite sandwich panel in the example 1, the crystallinity of the obtained polyester is lower than that of the polyester obtained by esterification reaction of the A-type polyester and PBT (polybutylene terephthalate), because the esterification reaction of the B-type polyester and the A-type polyester is adopted in the composite sandwich panel in the example 1, and the composite sandwich panel in the example 1 has stronger toughness and tear strength.
Claims (10)
1. The modified polyester material is characterized by comprising the following raw materials in parts by weight: 75-85 parts of polyester and 0.1-1.5 parts of coupling agent; the polyester is a mixture of a group A polyester and a group B polyester;
the A type polyester is crystalline polyester, and the B type polyester is non-crystalline polyester;
the class A polyester is
R is: a linear, branched or cyclic C4-C12 alkyl group;
the B-type polyester is at least one of polyethylene terephthalate-neopentyl glycol ester and polyethylene terephthalate-1, 4-cyclohexanedimethanol ester;
the content of the B-type polyester in the polyester accounts for 40-80 wt% of the total weight of the polyester.
2. The modified polyester material of claim 1, wherein the number of straight-chain and branched-chain carbon atoms in R is 2-12;
preferably, the A-type polyester is at least one of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate;
more preferably, the intrinsic viscosity of the group A polyester is from 0.6 to 1.0dl/g and the intrinsic viscosity of the group B polyester is from 0.7 to 0.8 dl/g;
preferably, the glass transition temperature of the modified polyester material is 67-81 ℃, the melting point is 210-265 ℃ and the crystallization temperature is 120-220 ℃.
3. The modified polyester material according to claim 1 or 2, further comprising the following raw materials in parts by weight: 0.5-4 parts of lubricant, 0.1-0.5 part of antioxidant, 13-18 parts of flame retardant, 0.0001-0.0005 part of colorant and 0.5-5 parts of toughening agent;
preferably, the coupling agent is a silane coupling agent KH-560, the lubricant is a high-temperature-resistant lubricant TA-401, the antioxidant is an antioxidant 1010, the flame retardant is polybrominated styrene, the colorant is a blueness agent, and the toughening agent is a toughening agent AX 8900.
4. The method for preparing the modified polyester material as claimed in any one of claims 1 to 3, wherein the modified polyester is obtained by banburying and homogenizing all the raw materials in a twin-screw extruder at a temperature of 230 ℃ to 300 ℃, preferably at a banburying and homogenizing temperature of 230 ℃ to 260 ℃.
5. A continuous fiber reinforced modified polyester material, comprising the modified polyester material according to any one of claims 1 to 3 and continuous fibers distributed in the modified polyester material;
preferably, the continuous fiber reinforced modified polyester material is obtained by impregnating continuous fibers or continuous fiber products with the modified polyester.
6. The continuous fiber reinforced polyester composite sandwich board is characterized by comprising an upper skin layer, a core layer and a lower skin layer which are sequentially overlapped;
the upper skin layer and the lower skin layer are made of the continuous fiber-reinforced modified polyester material of claim 5;
the core layer is a folded hexagonal honeycomb core layer, and the core layer is made of the modified polyester material in any one of claims 1-3.
7. The method of making the continuous fiber reinforced polyester composite sandwich panel of claim 6, comprising the steps of:
(1) uniformly and flatly infiltrating the modified polyester material of any one of claims 1-3 into continuous fibers or continuous fiber products to prepare a continuous fiber reinforced modified polyester material;
(2) heating, curing, cooling and rolling the continuous fiber reinforced modified polyester material obtained in the step (1) to obtain an upper skin layer and a lower skin layer;
(3) preparing the modified polyester material as claimed in any one of claims 1 to 3 into a thermoplastic hemihexagonal body, stacking the obtained thermoplastic hemihexagonal body, and carrying out hot pressing treatment to obtain a folded hexagonal honeycomb core layer;
(4) and sequentially overlapping the upper skin layer, the core layer and the lower skin layer, and performing hot pressing to form the continuous fiber reinforced polyester composite sandwich board.
8. The method for preparing the continuous fiber reinforced polyester composite sandwich panel according to claim 7, wherein the step (1) further comprises the steps of flattening, eliminating static electricity and preheating the continuous fiber or the continuous fiber product before infiltration; preferably, the continuous fiber or continuous fiber product has a glass fiber content of 45 wt% to 65 wt%.
9. The method for preparing the continuous fiber reinforced polyester composite sandwich panel according to claim 7 or 8, wherein the continuous fiber is one or a mixture of polymer synthetic fiber and inorganic fiber; preferably, the polymer synthetic fiber is at least one of polyamide fiber, ultra-high molecular weight polyethylene fiber, aramid fiber and carbon fiber; the inorganic fiber is at least one of glass fiber, basalt fiber and boron fiber; more preferably, the ultra-high molecular weight polyethylene fibers are unbranched linear polyethylene fibers having a molecular weight of 150 ten thousand or more.
10. The method for preparing the continuous fiber reinforced polyester composite sandwich panel according to claim 7 or 8, wherein the temperature for heating and curing in the step (2) is 180 ℃ to 210 ℃.
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| CN111363320A (en) | 2020-07-03 |
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