CN116970287A - Modified LCP material and preparation method and application thereof - Google Patents
Modified LCP material and preparation method and application thereof Download PDFInfo
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- CN116970287A CN116970287A CN202310843908.8A CN202310843908A CN116970287A CN 116970287 A CN116970287 A CN 116970287A CN 202310843908 A CN202310843908 A CN 202310843908A CN 116970287 A CN116970287 A CN 116970287A
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004970 Chain extender Substances 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 131
- 238000001125 extrusion Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000004891 communication Methods 0.000 claims description 10
- 238000003475 lamination Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 20
- 238000012986 modification Methods 0.000 abstract description 14
- 230000004048 modification Effects 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 11
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 121
- 238000002156 mixing Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 17
- 238000010096 film blowing Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012768 molten material Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000429 assembly Methods 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101000596046 Homo sapiens Plastin-2 Proteins 0.000 description 1
- 101000762938 Homo sapiens TOX high mobility group box family member 4 Proteins 0.000 description 1
- 239000004976 Lyotropic liquid crystal Substances 0.000 description 1
- 102100026749 TOX high mobility group box family member 4 Human genes 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- -1 anhydride compound Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 125000006159 dianhydride group Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention discloses a modified LCP material, a preparation method and application thereof, and belongs to the technical field of modification of high polymer materials. The modified LCP material provided by the invention comprises the following preparation raw materials: chain extenders, LCP resins; the chain extender is selected from epoxy chain extenders, and the epoxy chain extender contains two or more alicyclic epoxy groups. The invention adopts the specific chain extender to modify the LCP resin, improves the viscosity of the LCP material even under the condition of no compatibilizer, and solves the problems of poor compatibility and uneven dispersion of the chain extender and matrix resin, and the modified LCP material has better film forming property.
Description
Technical Field
The invention belongs to the technical field of polymer material modification, and particularly relates to a modified LCP material and a preparation method and application thereof.
Background
The Liquid Crystal Polymer (LCP) has the characteristics of high temperature resistance, high mechanical strength, good chemical stability, low thermal expansion coefficient, low water absorption, low dielectric constant, low dielectric loss and the like, and has wide application prospect in the fields of electronic appliances, communication, aerospace and the like. At present, the processing characteristics of domestic film-grade LCP resin cannot be compared with those of film-grade LCP resin of Talbond, sila Niles in the United states, meanwhile, the melt strength of the LCP body is lower due to the low viscosity and good fluidity of the LCP body in a molten state, the unstable condition of film bubbles easily occurs in the blow molding processing process, and special equipment is required for processing due to the molecular chain orientation characteristics of the LCP.
In the modification technology of the polymer material, according to whether new and old chemical bonds are formed and broken, chemical modification and physical blending modification are classified, wherein the common chemical modification includes grafting modification and block modification, and the physical modification includes filling modification and reinforcing modification. At present, the LCP modification technology is more focused on the aspects of LCP enhancement modification, such as enhancing the mechanical property and the heat conduction property of the LCP by using the white graphene, improving the wear resistance of the LCP by utilizing glass fiber woven cloth to fill and modify, and aiming at improving the film blowing property of the LCP, the LCP is subjected to grafting modification by adopting polyphenyl ether (PPE) and maleic anhydride grafted polyphenyl ether (PPE-g-MAH), but the problems of poor compatibility and uneven dispersion still exist.
Even though the PPE is under the action of compatibilizer PPE-g-MAH, the compatibility of the PPE and matrix resin LCP is still poor, and the modified sample can clearly distinguish two substances in a macroscopic sense; meanwhile, the film forming property of the modified LCP is poor due to poor compatibility and uneven dispersion, and in the film blowing process, holes are easily broken in the film bubble, so that the film cannot be continuously blown.
Therefore, there is a need for a method of continuously forming films of modified LCPs that can solve the problems of poor compatibility and uneven dispersion of chain extenders, compatibilizers and matrix resin LCPs while increasing the viscosity of LCPs.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes of the present invention is to provide a modified LCP material, wherein the LCP resin is modified by a specific chain extender, and the obtained modified LCP material has high viscosity, good compatibility and good film forming property.
It is a second object of the present invention to provide an apparatus for preparing the above-mentioned modified LCP material.
The invention also aims to provide a preparation method of the modified LCP material.
The fourth object of the invention is to provide an application of the modified LCP material in the fields of electronics, communication or aerospace.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a modified LCP material comprising the following preparation raw materials: chain extenders, LCP resins; the chain extender is selected from epoxy chain extenders, and the epoxy chain extender contains two or more alicyclic epoxy groups.
Preferably, the weight percentage of the chain extender in the preparation raw materials of the modified LCP material is 0.1-2%; more preferably 0.2 to 1.5%; more preferably 0.3 to 1%.
Preferably, among the chain extenders, the epoxy-based chain extender is selected from ADR chain extenders; further preferably, the ADR chain extender comprises at least one of ADR-4468, ADR-4368CS, ADR-4370, ADR-4385, ADR-4380 or ADR-4300; still more preferably, the ADR chain extender comprises at least one of ADR-4468, ADR-4368CS or ADR-4370.
In some embodiments of the invention, the ADR chain extender is selected from ADR-4468.
The ADR-4468 chain extender has 9 alicyclic epoxy groups, so that the hydroxyl or carboxyl of the main chain of the LCP molecule is easier to react to form a branched chain, the problem of poor compatibility of the LCP resin and the chain extender is solved, and the tackifying modification of the LCP resin is facilitated.
Preferably, in the chain extender, the anhydride compound is selected from dianhydride compounds; further preferably selected from pyromellitic dianhydride.
Preferably, in the chain extender, the isocyanate is selected from diisocyanates; further preferred is from toluene diisocyanate.
The liquid crystal polymer is a polymer which can exist in a liquid crystal phase state under certain conditions, has characteristics of both polymer and liquid crystal, and can be classified into a Thermotropic Liquid Crystal Polymer (TLCP) and a Lyotropic Liquid Crystal Polymer (LLCP) according to the formation conditions of liquid crystal.
Preferably, the LCP resin of the present invention is selected from Thermotropic Liquid Crystalline Polymers (TLCPs); further preferably, the LCP resin is selected from at least one of a950, R8000; still more preferably, the LCP resin is selected from at least one of polyplasics a950, celanesA950, ticonaA950, or golden R8000.
Preferably, the melt index of the modified LCP material is 0.1-1 g/10min at 285 ℃ and 1.2 kg; more preferably 0.2 to 0.8g/10min.
Preferably, the modified LCP material has a viscosity of 10 at 25℃and a frequency of 0.01 to 100/sec 5 ～10 9 mPa.s; further preferably 2X 10 5 ～8×10 8 mPa·s。
A second aspect of the present invention provides an apparatus for preparing a modified LCP material as defined in the first aspect of the present invention, comprising a screw extrusion device comprising a meshing block of 4 or more strips of meshing sheets alternately stacked with each adjacent two of the meshing sheets having an included angle of 30 to 60 degrees
Preferably, the screw extrusion device comprises a twin screw extruder or a single screw extruder; still more preferably a twin screw extruder.
Preferably, the engagement block comprises 4-10 strip-shaped engagement pieces; more preferably 4 to 6.
Preferably, the included angle between two adjacent engaging pieces is 30-60 degrees; more preferably 40 to 50 °.
Preferably, the screw extrusion device comprises 8-12 engagement blocks; more preferably 8 to 10.
Preferably, a threaded conveying element is connected between the engagement blocks; it is further preferred that a threaded conveying element is connected between each adjacent two of the engagement blocks.
In some specific embodiments of the invention, the engagement blocks are formed by overlapping 5 strip-shaped engagement pieces in a crossed mode, the included angle between every two adjacent engagement pieces is 45 degrees, the screw is provided with 9 engagement blocks, and a threaded conveying element is connected between every two engagement blocks. When this embodiment is used, the stream is split into two streams each time it passes one engagement piece, the screw rotates while mixing the streams thoroughly, and the stream passes 9 engagement pieces together in 45 engagement pieces, split into 2 45 The strand material flows are divided and mixed for a plurality of times, so as to achieve good dispersing and mixing effects. In addition, to prevent gel blocking due to excessive residence time of the stream, screw conveyor elements are inserted between the engagement blocks to ensure sufficient reaction time of the chain extender with the LCP resin while allowing forward transport of the melt stream.
A third aspect of the present invention provides a method of preparing a modified LCP material according to the first aspect of the present invention, comprising the steps of: the LCP resin and the chain extender are mixed and then extruded and granulated.
Preferably, in the preparation method, the mixing temperature of the LCP resin and the chain extender is 40-120 ℃; further preferably 50 to 110 ℃.
Preferably, in the preparation method, the mixing time for mixing the LCP resin and the chain extender is 3-40 min; more preferably 5 to 30 minutes.
Preferably, in the preparation method, extrusion granulation is performed in a screw extruder; further preferred is a twin screw extruder.
Preferably, the screw diameter of the screw extruder is 30-40 mm.
Preferably, the screw length-diameter ratio of the screw extruder is 40-50.
Preferably, in the preparation method, the extrusion granulation comprises the following steps: plasticizing, mixing, extruding, bracing, cooling and granulating.
Preferably, in the plasticizing mixing, the temperatures of the regions of the screw extruder are 210-230 ℃, 225-245 ℃, 230-250 ℃, 250-270 ℃, 255-275 ℃, 260-280 ℃, 270-290 ℃, 275-295 ℃ respectively.
Preferably, in the plasticizing mixing, the temperature of the die head of the screw extruder is 275-295 ℃.
Preferably, in the plasticizing mixing, the screw rotating speed of the screw extruder is 130-140 r/min.
Preferably, in the plasticizing mixing, the feeding rotating speed is 4-10 r/min.
Preferably, in the preparation method, the LCP resin and the chain extender are mixed and then subjected to extrusion granulation twice.
The LCP resin and the chain extender can be fully mixed by extruding and granulating twice, the tackifying and modifying effects are better, and the film forming performance of the modified LCP material is better.
Preferably, in the preparation process, extrusion granulation is performed in the apparatus according to the second aspect of the present invention.
In a fourth aspect the present invention provides the use of a modified LCP material according to the first aspect of the present invention in the field of electronics, communications or aerospace.
Preferably, the communication field is a 5G communication field; further preferably, the 5G communication field is a field of antenna film materials for 5G communication.
The beneficial effects of the invention are as follows: the invention adopts the specific chain extender to modify the LCP resin, improves the viscosity of the LCP material even under the condition of no compatibilizer, and solves the problems of poor compatibility and uneven dispersion of the chain extender and matrix resin, and the modified LCP material has better film forming property.
Specifically, compared with the prior art, the invention has the following advantages:
1. in the chain extender adopted by the invention, the epoxy chain extender contains two or more alicyclic epoxy groups, so that the epoxy chain extender is easier to react with hydroxyl or carboxyl of a main chain of an LCP molecule to form a branched chain, the problem of compatibility is solved, the viscosity of the LCP material is improved, and the problems of poor compatibility and uneven dispersion of the chain extender and matrix resin are solved.
2. The equipment provided by the invention adopts the meshing block with specific composition, the meshing block is combined with the screw conveying element, the low-shear strong mixing characteristic is realized, the dispersion mixing effect of the chain extender and the resin matrix can be improved, meanwhile, in order to prevent gel caking caused by overlong material flow residence time, the conveying element is embedded between the meshing block components, the sufficient reaction time of the chain extender and the LCP is ensured, and meanwhile, the molten material flows to be conveyed forwards.
3. The modified LCP material obtained by the invention has higher viscosity, good compatibility among raw materials, better film forming performance and wide application in the fields of electronics, communication and aerospace.
Drawings
Fig. 1 is a schematic view of a screw structure of a screw extruder in an example.
Fig. 2 is a schematic view of a meshing block of a screw extruder in an embodiment.
Fig. 3 is a schematic view of a screw conveying element of the screw extruder in the example.
Fig. 4 is a graph showing viscosity change of LCP materials of example 1, comparative example 1 and comparative example 2.
Fig. 5 is a physical diagram of the LCP material of example 1 when subjected to a film blowing test.
Fig. 6 is a physical diagram of the LCP material of example 2 when subjected to a film blowing test.
Fig. 7 is a diagram of the embodiment of the LCP material of comparative example 2 in a blown film experiment.
Fig. 8 is a diagram of a real object of the LCP material of comparative example 2 in a film blowing experiment.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since various modifications and adaptations may be made by those skilled in the art in light of the teachings herein. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the suitable ranges by the description herein and are not intended to be limited to the specific data described below. The starting materials, reagents or apparatus used in the following examples and comparative examples were obtained from conventional commercial sources or by known methods unless otherwise specified.
In some embodiments of the invention, the engagement blocks, the conveying elements are commercially available products, in combination form of self-assembly; the manufacturer is Nanjing Ruixin, and the model is 45 degrees/5/16.
In some embodiments of the present invention, the method of preparing a modified LCP includes the steps of: a) Compounding raw materials; b) Plasticizing and mixing; c) Extruding a brace; d) And (5) cooling and granulating.
The method comprises the following specific steps:
step a), compounding the raw materials, namely weighing 0.05-1 part of chain extender and 99-99.95 parts of LCP resin in parts by weight, wherein the specifically used chain extender is selected from ADR-4468; the LCP resin is selected from the group consisting of polyplasics a950 or CelanesA950LCP particles; placing the chain extender ADR4468 and LCP resin particles into a high-speed mixer, and performing dispersion mixing for 5-30min at 50-110 ℃ to obtain a mixed material;
and b) plasticizing and mixing, namely placing the mixed material prepared in the step into a hopper of a double-screw extruder with the screw diameter of 35mm and the screw length-diameter ratio of 44, respectively setting the temperature of each region of the extruder and the die head temperature at 220 ℃, 235 ℃, 240 ℃, 260 ℃, 265 ℃, 270 ℃, 280 ℃, 285 ℃ and the feeding speed of 6r/min and the screw speed of 135r/min, and plasticizing and mixing the mixed material to obtain a molten material with a uniformly dispersed chain extender. Wherein the screw combination adopts two threaded elements of a conveying element and a meshing block, has the characteristic of low shear and strong mixing, and in order to realize the effect of improving the dispersion mixing of the chain extender and the resin matrix, 9 meshing block assemblies (shown in figure 1, 4, 2 and 3 meshing block assemblies are respectively adopted in areas (1), (2) and (3), a is a meshing block, b is a threaded conveying element), and each meshing block is formed by 5 meshing pieces as shown in figure 2The staggered angle is 45 DEG, the material flow is divided into two material flows when passing through one meshing piece, the material flow is fully mixed while the screw rotates, and the material flow is divided into 2 after passing through 45 meshing pieces of 9 meshing pieces 45 The strand material flows are divided and mixed for a plurality of times, so as to achieve good dispersing and mixing effects. Meanwhile, in order to prevent gel caking caused by overlong material residence time, screw conveying elements (shown in figure 3) are embedded between the meshing block assemblies, so that the chain extender and the LCP are ensured to have sufficient reaction time, and meanwhile, molten materials are conveyed forwards;
step c) extruding a brace, wherein the molten material is extruded outwards through a cylindrical hole on a die under the extrusion force of an extruder, and simultaneously forms a continuous cylindrical strip under the action of traction force;
and d) cooling and granulating, namely cooling the cylindrical long strips to a proper temperature through a cooling water tank, and then entering a granulator for granulating to obtain modified LCP particles 1, namely the modified LCP material.
In other embodiments of the present invention, the method of preparing a modified LCP includes the steps of: a) Compounding raw materials; b) Plasticizing and mixing; c) Extruding a brace; d) Cooling and granulating; e) And (5) secondary extrusion granulation.
The method comprises the following specific steps:
the specific steps of steps a) to d) are the same as those in the previous examples;
step e) secondary extrusion granulation, repeating the operations of step b), step c) and step d) on the modified LCP particles 1 to obtain modified LCP particles 2, namely the modified LCP material.
In some embodiments of the invention, the LCP is commercially available A950, specifically Polyplastics A950, celaneseA 950, ticonaA950, with commercially available A950 without added chain extender, with a melt index of 1.9g/10min (285 ℃,1.2 kg) and a viscosity in the range of 1X 10 5 ～7×10 8 mPa·s(0.01Hz-100Hz)。
In some embodiments of the invention, the use of specific screw combinations may enhance the dispersion of the chain extender in the LCP matrix. The modified LCP material prepared by the common double screws has weaker dispersion effect than the specific screw combination in the embodiment of the invention, so that the chain extender is poor in dispersion in the LCP resin, gel-like phenomenon is easy to appear, and the modified LCP is broken in a discontinuous way in the film blowing process and cannot be formed continuously.
In some embodiments of the present invention, the addition of chain extender affects the melt and viscosity of the LCP, and ADR-4468 chain extender may increase the viscosity of the LCP resin and decrease the melt of the LCP resin, while TDE-85 may decrease the viscosity of the LCP resin and increase the melt of the LCP resin. Therefore, the embodiment of the invention uses the epoxy chain extender containing two or more alicyclic epoxy groups, can improve the viscosity of the LCP resin, reduce the melt index of the LCP resin and obtain the modified LCP material with good film forming performance.
Example 1
The example provides a preparation method of a modified LCP material, which comprises the following steps:
according to parts by weight, 0.7 part of chain extender ADR-4468 and 99.3 parts of A950LCP are placed into a high-speed mixer to be mixed, mixed for 5-30min at 50-110 ℃, then mixed materials are poured out, meanwhile, the mixed materials are placed into a hopper of a double-screw extruder combined by low-shear strong-dispersion screws, the temperature of each area of the extruder and the temperature of a die head are respectively set to 220 ℃, 235 ℃, 260 ℃, 265 ℃, 270 ℃, 280 ℃, 285 ℃ and the feeding speed of 6r/min, the screw speed of 135r/min, the mixed materials are subjected to melting plasticizing granulation to obtain modified LCP particles 1, then the modified LCP1 is placed into the hopper of the double-screw extruder, and extrusion granulation is carried out again by the same technological parameters to obtain modified LCP particles 2, namely the modified LCP material.
Example 2
The example provides a preparation method of a modified LCP material, which comprises the following steps:
and (2) placing 0.5 part of chain extender ADR-4468 and 99.5 parts of A950LCP into a high-speed mixer for mixing according to parts by weight, pouring out the mixed material after mixing for 5-30min at 50-110 ℃, simultaneously placing the mixed material into a hopper of a double-screw extruder combined by a low-shear strong-dispersion screw, respectively setting the temperature of each region of the extruder and the temperature of a die head at 220 ℃, 235 ℃, 240 ℃, 260 ℃, 265 ℃, 280 ℃, 285 ℃ and the feeding speed at 6r/min and the screw speed at 135r/min, and carrying out melt plasticizing granulation on the mixed material to obtain the modified LCP particles 1, namely the modified LCP material.
Comparative example 1
The example provides a preparation method of LCP material, which comprises the following steps:
placing pure material A950LCP particles into a hopper of a double-screw extruder combined by low-shear strong-dispersion screws, respectively setting the temperature of each zone of the extruder and the temperature of a die head to 220 ℃, 235 ℃, 240 ℃, 260 ℃, 265 ℃, 270 ℃, 280 ℃, 285 ℃, and the feeding speed to 6r/min and the screw speed to 135r/min, and carrying out melt plasticizing granulation on the pure material A950LCP to obtain the LCP material.
Comparative example 2
The example provides a preparation method of a modified LCP material, which comprises the following steps:
the preparation method comprises the steps of placing 0.7 part of chain extender TDE-85 (4, 5-epoxyhexane-1, 2-diglycidyl ester) and 99.3 parts of A950LCP into a high-speed mixer, mixing for 5-30min at 50-110 ℃, pouring out the mixed material, simultaneously placing the mixed material into a hopper of a double-screw extruder combined by a low-shear strong-dispersion screw, setting the temperature of each region of the extruder and the temperature of a die head at 220 ℃, 235 ℃, 240 ℃, 260 ℃, 270 ℃, 280 ℃, 285 ℃ and 285 ℃, and the feeding speed of 6r/min and the screw speed of 135r/min, and performing melt plasticization granulation on the mixed material to obtain the modified LCP material.
Performance testing
1) The current level of the extruder during pelletization was recorded. The magnitude of the extruder current can reflect the energy consumption of the materials in the plasticizing process of the double-screw extruder, and indirectly reflects the viscosity increase of the modified materials. Under the same technological parameters (same barrel temperature, screw speed and feeding speed), the molecular chains of the LCP are blocked or grafted due to the introduction of the chain extender, so that the molecular chains can be disentangled and flowed only by more energy consumption in the melting plasticizing process, namely, the higher the extruder current is, the higher the viscosity of the material is.
2) The material was tested for melt index at 285℃at 1.2 kg.
3) The viscosity change of the material at 285℃was measured with a rotarheometer.
4) And (5) performing a film blowing experiment to test the film forming performance of the material.
The results are recorded in table 1.
Table 1 results of performance testing of materials
Note that: "0" indicates a viscosity change reference, "+" indicates an increase in viscosity, and "-" indicates a decrease in viscosity.
Comparative example 1 was modified without the addition of a chain extender to an LCP resin neat, with comparative example 1 as a viscosity change reference group. Viscosity change diagrams of the LCP materials of example 1, comparative example 1 and comparative example 2 As shown in FIG. 4, the modified LCP material of example 1 has a viscosity of 2X 10 at 25℃and a frequency of 0.01 to 100/sec 5 ～8×10 8 mPas, while the modified LCP material of comparative example 2 has a viscosity of 7X 10 at 25℃and a frequency of 0.01 to 100/s 4 ～1.2×10 8 In the mPas range, the viscosity of comparative example 2 was lower at the same frequency. It can be seen that the viscosity of the LCP material can be increased by using the ADR chain extender of example 1, while the viscosity of the LCP material cannot be increased by using the TDE chain extender also containing an epoxy group, since it has only one alicyclic epoxy group, the effect of modifying the LCP material is poor.
Fig. 5 is a physical diagram of the LCP material of example 1 when a film blowing experiment is performed, fig. 6 is a physical diagram of the LCP material of example 2 when a film blowing experiment is performed, and fig. 7 and 8 are physical diagrams 1 and 2 of the LCP material of comparative example 2 when a film blowing experiment is performed, it can be seen that the LCP film of example 1 has a smooth surface and no broken holes during the film blowing process, and the LCP modified by example 1 has a better film forming property; the LCP film of example 2 has pores broken on the surface, but the degree of the pores broken is smaller, and the modified LCP of example 1 has certain film forming property; the LCP film of comparative example 2 exhibited large holes and the modified LCP material of comparative example 2 had poor film forming properties.
As can be seen from the comparison of fig. 5 and fig. 7 and 8, the LCP film of example 1 in fig. 5 has no broken holes on the surface, and the cylindrical film bubble is stable in inflation and flat in shape; whereas the LCP film of comparative example 2 in FIGS. 7 and 8 exhibited holes in the surface, the cylindrical film bubble was very unstable when inflated and the shape was also unstable.
While the LCP film of example 2 in FIG. 6 exhibited pores on its surface, the pores were less broken, and the film forming properties of the material were not affected, and the cylindrical film bubble was more stable in inflation and flat in shape.
In the embodiment of the invention, when the film blowing experiment is carried out on the modified LCP material which is only subjected to one-time granulation, holes are broken intermittently, and the gel phenomenon is mainly caused by uneven dispersion of the chain extender in the LCP matrix, and under the condition that the technological conditions of the film blowing process are the same, infusions exist in the places with gel to cause air leakage of film bubbles.
Therefore, the specific chain extender is adopted to modify the LCP resin, so that the viscosity of the LCP material is improved even if the compatibilizer is not needed, and meanwhile, the problems of poor compatibility and uneven dispersion of the chain extender and the matrix resin are solved, and the film forming performance of the modified LCP material is better; the combination of the screw extruder with the meshing block and the screw conveying element with specific structures of the invention can obtain LCP materials which are fully mixed, thereby being beneficial to improving the dispersion degree of the materials.
The embodiment of the invention adopts a specific chain extender, combines a specific screw combination and extrusion granulation process, improves the viscosity of the LCP and solves the problems of poor compatibility and uneven dispersion of the chain extender and matrix resin at the same time under the condition of not using a compatibilizer, thereby realizing continuous film formation of the modified LCP material. The modified LCP material obtained by the invention has higher viscosity, good compatibility among raw materials, better film forming performance and wide application in the fields of electronics, communication and aerospace.
Claims (10)
1. The modified LCP material is characterized by comprising the following preparation raw materials: chain extenders, LCP resins; the chain extender is selected from epoxy chain extenders, and the epoxy chain extender contains two or more alicyclic epoxy groups.
2. A modified LCP material according to claim 2, wherein the chain extender is present in the preparation material in an amount of 0.1 to 2% by mass.
3. A modified LCP material according to claim 1, wherein the epoxy-based chain extender is selected from ADR chain extenders.
4. A modified LCP material according to claim 1, wherein the LCP resin is selected from thermotropic liquid crystalline polymers.
5. An apparatus for preparing a modified LCP material as claimed in any one of claims 1 to 4, wherein the apparatus comprises a screw extrusion device comprising an engagement block formed by the cross lamination of 4 or more strip-shaped engagement pieces, each adjacent two engagement pieces having an included angle of 30 to 60 °.
6. The apparatus of claim 5, wherein the apparatus comprises 8-12 engagement blocks.
7. The apparatus of claim 5, wherein threaded conveying elements are connected between the engagement blocks.
8. A method of preparing a modified LCP material as claimed in any one of claims 1 to 4, comprising the steps of: the LCP resin and the chain extender are mixed and then extruded and granulated.
9. The method of claim 8, wherein the extrusion granulation is performed in the apparatus of any one of claims 5 to 7.
10. Use of a modified LCP material according to any one of claims 1 to 4 in the fields of electronics, communications or aerospace.
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