A high flow polyetherimide composite and method of making the same
By adding a modified polyetherimide with a specific structure as a compatibilizer to polyetherimide, the dielectric loss problem caused by thermotropic liquid crystal polymer materials is solved, and a composite material with high fluidity and low dielectric loss is realized, which is suitable for electrical components.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WUZHEN LABORATORY
- Filing Date
- 2023-08-15
- Publication Date
- 2026-05-12
Smart Images
Figure QLYQS_1 
Figure BDA0004395323710000011 
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of polymer materials, in particular to a high-fluidity polyetherimide composite material and a preparation method thereof. BACKGROUND
[0002] Polyetherimide is a kind of thermoplastic special engineering plastic with a large number of aromatic groups and amide bonds in the molecular chain, which has good high-temperature resistance, dimensional stability, excellent chemical resistance, certain flame retardance, good electrical properties, high strength and high rigidity mechanical properties. Due to its excellent properties, it is widely used in high-temperature resistant terminals, IC bases, lighting equipment, FPCB (flexible printed circuit board), liquid delivery equipment, aircraft interior parts, medical equipment and household appliances. However, due to its high melt viscosity and processing temperature, the flow performance is difficult to meet the processing of complex products or thin products.
[0003] Thermotropic liquid crystal polymer (TLCP) has good melt processing performance, dimensional stability, self-reinforcement and other characteristics. Using it as a processing aid and blending with thermoplastic plastics can reduce the viscosity and processing temperature of the composite system and improve the flowability of the composite material, which has become a research hotspot. However, when using thermotropic liquid crystal polymer material as a processing aid to improve the flowability of polyetherimide, the dielectric loss of polyetherimide is usually increased due to the poor compatibility of the two, which affects its application in electrical components. SUMMARY
[0004] The present application is to overcome the problem that when using thermotropic liquid crystal polymer material as a processing aid to improve the flowability of polyetherimide, the dielectric loss of polyetherimide is usually increased, which affects its application in electrical components. A high-fluidity polyetherimide composite material and a preparation method thereof are provided. Using modified polyetherimide containing a specific structure as a compatibilizer can improve the flowability of polyetherimide without increasing the dielectric loss of the composite material.
[0005] In order to achieve the above-mentioned purpose, the present application adopts the following technical scheme:
[0006] A high-fluidity polyetherimide composite material, by weight, the raw materials include: 85-99 parts of polyetherimide, 0.1-5 parts of compatibilizer, 1-10 parts of thermotropic liquid crystal polymer, 0.1-0.3 parts of antioxidant, and 0.1-0.3 parts of acid absorbent;
[0007] The compatibilizer is a modified polyetherimide, and the modified polyetherimide contains the following chain segment:
[0008]
[0009] n=65-75.
[0010] This invention adds a thermotropic liquid crystal polymer (TLCP) to polyetherimide, which improves the flowability of polyetherimide. The resulting composite material has a flowability more than 1.5 times that of the original polyetherimide material, thus enhancing the processing performance of polyetherimide. Simultaneously, the addition of TLCP also enhances the toughness of the composite material and increases its elongation at break. To improve the compatibility between TLCP and polyetherimide and avoid increasing the dielectric loss of the composite material due to the addition of TLCP, this invention adds a modified polyetherimide with a specific structure as a compatibilizer. The main chain structure of the modified polyetherimide in this invention is basically consistent with the polyetherimide matrix, thus exhibiting good compatibility with the polyetherimide matrix. Its carboxyl side groups have good compatibility with the ester groups in TLCP and undergo a certain degree of transesterification reaction, effectively improving the compatibility between the polyetherimide matrix and TLCP. This results in improved mechanical properties of the composite material while maintaining low dielectric loss, which is beneficial for its application in electrified components.
[0011] The degree of polymerization of compatibilizers affects their distribution in the matrix resin and the activity of carboxyl groups. When the polymerization degree is too high, the activity of the carboxyl groups is low, leading to a decrease in compatibility with TLCP and poorer uniformity of distribution in the polyetherimide matrix, resulting in increased dielectric loss of the composite material. Conversely, when the polymerization degree is too low, its mobility in the polyetherimide matrix is too strong, leading to a decrease in the tensile strength of the product. This invention controls the degree of polymerization of the modified polyetherimide within an appropriate range, enabling the composite material to simultaneously possess high mechanical properties and low dielectric loss.
[0012] Preferably, the preparation method of the modified polyetherimide includes the following steps:
[0013] A) Dissolve bisphenol A type diether dianhydride in an organic solvent to obtain a bisphenol A type diether dianhydride solution;
[0014] B) Add 3,5-diaminobenzoic acid dropwise to a bisphenol A type diether dianhydride solution, and stir the reaction under nitrogen protection and in an ice-water bath to obtain polyetherimide acid;
[0015] C) Remove the nitrogen gas and ice-water bath, add acetic anhydride and pyridine to the polyetherimide acid, heat and reflux the reaction, then pour the product into excess anhydrous ethanol, the product precipitates out, and the modified polyetherimide is obtained.
[0016] This invention uses bisphenol A type diether dianhydride as the dianhydride monomer and 3,5-diaminobenzoic acid as the diamine monomer to prepare a modified polyetherimide containing a carboxyl side group. The reaction route is as follows:
[0017]
[0018]
[0019] This invention uses bisphenol A type diether dianhydride as the dianhydride monomer and 3,5-diaminobenzoic acid as the diamine monomer. The resulting modified polyetherimide has a molecular structure that is essentially identical to the matrix resin and exhibits good affinity with it. Furthermore, the carboxyl group is an electron-withdrawing group, which enhances the reactivity of the amino group on the benzene ring, thereby increasing the reaction rate. The use of 3,5-diaminobenzoic acid with a meta-structure as the diamine monomer further facilitates the exposure of the carboxyl group, improving the compatibilization effect.
[0020] Preferably, in step A), bisphenol A type diether dianhydride is dissolved in an organic solvent under nitrogen protection and an ice-water bath; the organic solvent is N-methylpyrrolidone, and the mass fraction of the bisphenol A type diether dianhydride solution is 10-20%.
[0021] Preferably, the molar ratio of 3,5-diaminobenzoic acid to bisphenol A diether dianhydride added in step B) is 1 to 1.2:1; and the stirring reaction time is 7 to 9 hours.
[0022] Preferably, the mass ratio of acetic anhydride and pyridine added in step C) to the bisphenol A type diether dianhydride solution in step B) is 10-15:5-10:100; the reflux reaction temperature is 150-170°C, and the reaction time is 3-4 hours.
[0023] Preferably, the thermotropic liquid crystal polymer is one or more of the LAPEROS@LCP C series.
[0024] Preferably, the antioxidant is selected from one or more of antioxidants 1010, 1076, 1098, and 330.
[0025] Preferably, the acid absorbent is selected from one or more of aluminum oxide, magnesium oxide, and calcium oxide.
[0026] The present invention also provides a method for preparing the above-mentioned high-flow polyetherimide composite material, comprising the following steps: mixing each raw material in proportion and uniformly, adding it to a granulator for granulation, and obtaining the high-flow polyetherimide composite material.
[0027] Preferably, the granulation temperature is 300–390℃.
[0028] Therefore, the present invention has the following beneficial effects: a modified polyetherimide with a specific structure is added as a compatibilizer. The modified polyetherimide in the present invention contains carboxyl side groups, which can effectively improve the compatibility between polyetherimide and TLCP. It can improve the flowability of polyetherimide while maintaining low dielectric loss of the composite material. Detailed Implementation
[0029] The present invention will be further described below with reference to specific embodiments.
[0030] In this invention, unless otherwise specified, all equipment and raw materials are available from the market or commonly used in the industry. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.
[0031] General Implementation Examples:
[0032] A high-flowability polyetherimide composite material, comprising, by weight, 85-99 parts of polyetherimide, 0.1-5 parts of compatibilizer, 1-10 parts of thermotropic liquid crystal polymer, 0.1-0.3 parts of antioxidant, and 0.1-0.3 parts of acid scavenger;
[0033] The thermotropic liquid crystal polymer is the LAPEROS@LCP C series;
[0034] The antioxidant is selected from one or more of antioxidants 1010, 1076, 1098, and 330;
[0035] The acid absorbent is selected from one or more of aluminum oxide, magnesium oxide, and calcium oxide;
[0036] The compatibilizer is a modified polyetherimide, which contains the following segments:
[0037]
[0038] Where n = 65 to 75;
[0039] The preparation method of the modified polyetherimide includes the following steps:
[0040] A) Bisphenol A type diether dianhydride was dissolved in the organic solvent N-methylpyrrolidone (NMP) under nitrogen protection and ice-water bath conditions to obtain a 10-20% (w / w) bisphenol A type diether dianhydride solution.
[0041] B) Take 100 parts by weight of bisphenol A type diether dianhydride solution, add 3,5-diaminobenzoic acid dropwise to it, and the molar ratio of the added 3,5-diaminobenzoic acid to bisphenol A type diether dianhydride is 1 to 1.2:1; stir and react in a nitrogen atmosphere and ice-water bath for 7 to 9 hours to obtain polyetherimide acid;
[0042] C) Remove the nitrogen gas and ice-water bath, add 10-15 parts of acetic anhydride and 5-10 parts of pyridine to the polyetherimide acid, heat and reflux at 150-170°C for 3-4 hours, then pour the product into excess anhydrous ethanol, the product precipitates, and the modified polyetherimide is obtained; the preparation method of the above high-flowability polyetherimide composite material is as follows: mix the raw materials evenly in proportion, add them to a twin-screw granulator for extrusion granulation, and obtain the high-flowability polyetherimide composite material; the granulation temperature is set to 300-390°C, and the screw speed is 200-250 rpm.
[0043] Example 1:
[0044] A method for preparing a high-flowability polyetherimide composite material:
[0045] (1) Preparation of compatibilizer:
[0046] A) Bisphenol A type diether dianhydride was dissolved in NMP under nitrogen protection and ice-water bath conditions to obtain a 15% (w / w) bisphenol A type diether dianhydride solution.
[0047] B) Take 100 parts by weight of bisphenol A type diether dianhydride solution, add 3,5-diaminobenzoic acid dropwise to it, the molar ratio of the added 3,5-diaminobenzoic acid to bisphenol A type diether dianhydride is 1:1; stir the reaction under nitrogen protection and ice-water bath for 8 hours to obtain polyetherimide acid;
[0048] C) Remove the nitrogen gas and ice-water bath, add 12 parts acetic anhydride and 8 parts pyridine to the polyetherimide acid, heat and reflux at 160°C for 3.5 h, then pour the product into excess anhydrous ethanol. The product precipitates, yielding a modified polyetherimide with the following chain segments, which can be used as a compatibilizer:
[0049]
[0050] Where n = 70;
[0051] (2) Mixing and granulation: By weight, 95 parts of polyetherimide (ULTEM) TM The following ingredients were mixed evenly: Resin 1010, 1 part compatibilizer, 4 parts thermotropic liquid crystal polymer (LAPEROS@LCP C0711A), 0.2 parts antioxidant 1010, and 0.1 parts alumina (particle size 10-50 nm). The mixture was then added to a twin-screw granulator for extrusion granulation to obtain the high-flowability polyetherimide composite material. The granulation temperature was set at 350°C and the screw speed was 250 rpm.
[0052] Example 2:
[0053] A method for preparing a high-flowability polyetherimide composite material:
[0054] (1) Preparation of compatibilizer:
[0055] A) Bisphenol A type diether dianhydride was dissolved in NMP under nitrogen protection and ice-water bath conditions to obtain a 15% (w / w) bisphenol A type diether dianhydride solution.
[0056] B) Take 100 parts by weight of bisphenol A type diether dianhydride solution, add 3,5-diaminobenzoic acid dropwise to it, the molar ratio of the added 3,5-diaminobenzoic acid to bisphenol A type diether dianhydride is 1:1; stir the reaction in a nitrogen atmosphere and ice-water bath for 7 hours to obtain polyetherimide acid;
[0057] C) Remove the nitrogen gas and ice-water bath, add 12 parts acetic anhydride and 8 parts pyridine to the polyetherimide acid, heat and reflux at 160°C for 3 hours, then pour the product into excess anhydrous ethanol. The product precipitates out, yielding a modified polyetherimide with the following chain segments as a compatibilizer:
[0058]
[0059] Where n = 65;
[0060] (2) Mixing and granulation: By weight, 91 parts of polyetherimide (same as in Example 1), 5 parts of compatibilizer, 4 parts of thermotropic liquid crystal polymer (same as in Example 1), 0.2 parts of antioxidant 1010, and 0.1 parts of alumina (same as in Example 1) are mixed evenly and added to a twin-screw granulator for extrusion granulation to obtain the high-flowability polyetherimide composite material; the granulation temperature is set to 350°C and the screw speed is 250 rpm.
[0061] Example 3:
[0062] A method for preparing a high-flowability polyetherimide composite material:
[0063] (1) Preparation of compatibilizer:
[0064] A) Bisphenol A type diether dianhydride was dissolved in NMP under nitrogen protection and ice-water bath conditions to obtain a 15% (w / w) bisphenol A type diether dianhydride solution.
[0065] B) Take 100 parts by weight of bisphenol A type diether dianhydride solution, add 3,5-diaminobenzoic acid dropwise to it, and the molar ratio of the added 3,5-diaminobenzoic acid to bisphenol A type diether dianhydride is 1:1; stir the reaction in a nitrogen atmosphere and ice-water bath for 9 hours to obtain polyetherimide acid;
[0066] C) Remove the nitrogen gas and ice-water bath, add 12 parts acetic anhydride and 8 parts pyridine to the polyetherimide acid, heat and reflux at 160°C for 4 hours, then pour the product into excess anhydrous ethanol. The product precipitates out, yielding a modified polyetherimide with the following chain segments as a compatibilizer:
[0067]
[0068] Where n = 75;
[0069] (2) Mixing and granulation: By weight, 90 parts of polyetherimide (same as in Example 1), 2 parts of compatibilizer, 8 parts of thermotropic liquid crystal polymer (same as in Example 1), 0.2 parts of antioxidant 1010, and 0.1 parts of alumina (same as in Example 1) are mixed evenly and added to a twin-screw granulator for extrusion granulation to obtain the high-flowability polyetherimide composite material; the granulation temperature is set to 350°C and the screw speed is 250 rpm.
[0070] The raw material formulations of the polyetherimide composite materials in Examples 4-6 and Comparative Examples 1-3 are shown in Table 1, and the rest are the same as in Example 1.
[0071] Table 1: Raw material formulation of polyetherimide composite materials
[0072]
[0073]
[0074] Comparative Example 4 (n is too small in modified polyetherimide):
[0075] The difference between Comparative Example 4 and Example 1 is that the compatibilizer is prepared by the following method:
[0076] A) Bisphenol A type diether dianhydride was dissolved in NMP under nitrogen protection and ice-water bath conditions to obtain a 15% (w / w) bisphenol A type diether dianhydride solution.
[0077] B) Take 100 parts by weight of bisphenol A type diether dianhydride solution, add 3,5-diaminobenzoic acid dropwise to it, and the molar ratio of the added 3,5-diaminobenzoic acid to bisphenol A type diether dianhydride is 1:1; stir the reaction in a nitrogen atmosphere and ice-water bath for 4 hours to obtain polyetherimide acid.
[0078] C) Remove the nitrogen gas and ice-water bath, add 12 parts acetic anhydride and 8 parts pyridine to the polyetherimide acid, heat and reflux at 160°C for 3 hours, then pour the product into excess anhydrous ethanol. The product precipitates out, yielding a modified polyetherimide with the following chain segments as a compatibilizer:
[0079]
[0080] Where n = 30;
[0081] Everything else is the same as in Example 1.
[0082] Comparative Example 5 (n is too large in modified polyetherimide):
[0083] The difference between Comparative Example 5 and Example 1 is that the compatibilizer is prepared by the following method:
[0084] A) Bisphenol A type diether dianhydride was dissolved in NMP under nitrogen protection and ice-water bath conditions to obtain a 15% (w / w) bisphenol A type diether dianhydride solution.
[0085] B) Take 100 parts by weight of bisphenol A type diether dianhydride solution, add 3,5-diaminobenzoic acid dropwise to it, and the molar ratio of the added 3,5-diaminobenzoic acid to bisphenol A type diether dianhydride is 1:1; stir the reaction in a nitrogen atmosphere and ice-water bath for 12 hours to obtain polyetherimide acid;
[0086] C) Remove the nitrogen gas and ice-water bath, add 12 parts acetic anhydride and 8 parts pyridine to the polyetherimide acid, heat and reflux at 160°C for 4 hours, then pour the product into excess anhydrous ethanol. The product precipitates out, yielding a modified polyetherimide with the following chain segments as a compatibilizer:
[0087]
[0088] Where n = 90;
[0089] Everything else is the same as in Example 1.
[0090] Comparative Example 6 (with altered structure of the diamine monomer):
[0091] The difference between Comparative Example 6 and Example 1 is that the compatibilizer is prepared by the following method:
[0092] A) Bisphenol A type diether dianhydride was dissolved in NMP under nitrogen protection and ice-water bath conditions to obtain a 15% (w / w) bisphenol A type diether dianhydride solution.
[0093] B) Take 100 parts by weight of bisphenol A type diether dianhydride solution, add 2,3-diaminobenzoic acid dropwise to it, the molar ratio of the added 2,3-diaminobenzoic acid to bisphenol A type diether dianhydride is 1:1; stir the reaction under nitrogen protection and ice-water bath for 8 hours to obtain polyetherimide acid;
[0094] C) Remove the nitrogen gas and ice-water bath, add 12 parts of acetic anhydride and 8 parts of pyridine to the polyetherimide acid, heat and reflux at 160°C for 3.5 h, then pour the product into excess anhydrous ethanol. The product precipitates out, and the modified polyetherimide is obtained as a compatibilizer.
[0095] Everything else is the same as in Example 1.
[0096] The polyetherimide composite materials prepared in the above examples and comparative examples were cast into films with a thickness of 20 μm using a single screw extruder, and their properties were tested. The results are shown in Table 2.
[0097] Table 2: Performance Test Results of Polyetherimide Composite Materials
[0098]
[0099]
[0100] As can be seen from Table 1, the polyetherimide composite materials prepared using the formulations of this invention in Examples 1 to 6 have significantly improved melt flow rate, good fluidity, and significantly improved processing performance compared with the pure polyetherimide material in Comparative Example 1; at the same time, the tensile strength and elongation at break are also significantly improved, resulting in good mechanical properties; and the dielectric loss is low.
[0101] In Comparative Examples 2 and 3, without the addition of TLCP, the flow properties and mechanical properties of the composite materials could not be effectively improved. In Comparative Example 4, the molecular chain of the compatibilizer-modified polyetherimide was too short, resulting in excessive mobility in the polyetherimide matrix and a decrease in tensile strength compared to Example 1. In Comparative Example 5, the molecular chain of the modified polyetherimide was too long, resulting in lower activity of its carboxyl groups, reduced compatibility with TLCP, and poorer uniformity of distribution in the polyetherimide matrix, leading to a decrease in tensile strength and elongation at break of the composite material and an increase in dielectric loss. In Comparative Example 6, using ortho-position 2,3-diaminobenzoic acid as a diamine monomer, the modified polyetherimide prepared as a compatibilizer did not easily expose the carboxyl groups in its molecular chain to interact with TLCP, resulting in a decrease in compatibilization effect and a decrease in tensile strength and elongation at break of the composite material compared to Example 1.
Claims
1. A high-flowability polyetherimide composite material, characterized in that, By weight, the raw materials include: 85-99 parts of polyetherimide, 0.1-5 parts of compatibilizer, 1-10 parts of thermotropic liquid crystal polymer, 0.1-0.3 parts of antioxidant, and 0.1-0.3 parts of acid scavenger; The compatibilizer is a modified polyetherimide, which contains the following segments: ； Where n = 65~75; The thermotropic liquid crystal polymer contains ester groups.
2. The high-flowability polyetherimide composite material according to claim 1, characterized in that, The preparation method of the modified polyetherimide includes the following steps: A) Dissolve bisphenol A type diether dianhydride in an organic solvent to obtain a bisphenol A type diether dianhydride solution; B) Add 3,5-diaminobenzoic acid dropwise to a bisphenol A type diether dianhydride solution, and stir the reaction under nitrogen protection and an ice-water bath to obtain polyetherimide acid; C) Remove the nitrogen gas and ice-water bath, add acetic anhydride and pyridine to the polyetherimide acid, heat and reflux the reaction, and then pour the product into excess anhydrous ethanol. The product precipitates out to obtain the modified polyetherimide.
3. The high-flowability polyetherimide composite material according to claim 2, characterized in that, In step A), bisphenol A type diether dianhydride is dissolved in an organic solvent under nitrogen protection and ice-water bath conditions; the organic solvent is N-methylpyrrolidone, and the mass fraction of the bisphenol A type diether dianhydride solution is 10~20%.
4. The high-flowability polyetherimide composite material according to claim 2, characterized in that, In step B), the molar ratio of 3,5-diaminobenzoic acid to bisphenol A type diether dianhydride is 1~1.2:1; the stirring reaction time is 7~9h.
5. The high-flowability polyetherimide composite material according to claim 2, characterized in that, The mass ratio of acetic anhydride and pyridine added in step C) to the bisphenol A type diether dianhydride solution in step B) is 10~15:5~10:100; the reflux reaction temperature is 150~170℃, and the reaction time is 3~4h.
6. The high-flowability polyetherimide composite material according to claim 1, characterized in that, The antioxidant is selected from one or more of antioxidants 1010, 1076, 1098, and 330.
7. The high-flowability polyetherimide composite material according to claim 1, characterized in that, The acid absorbent is selected from one or more of aluminum oxide, magnesium oxide, and calcium oxide.
8. A method for preparing a high-flowability polyetherimide composite material as described in any one of claims 1 to 7, characterized in that, step... The process involves mixing the raw materials in a specific ratio, adding them to a granulator for granulation, and obtaining the high-flowability polyetherimide composite material.
9. The preparation method according to claim 8, characterized in that, The granulation temperature is 300~390℃.