CN109575597B - Bismaleimide molding compound capable of being injection molded and preparation method thereof - Google Patents
Bismaleimide molding compound capable of being injection molded and preparation method thereof Download PDFInfo
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- CN109575597B CN109575597B CN201811579573.9A CN201811579573A CN109575597B CN 109575597 B CN109575597 B CN 109575597B CN 201811579573 A CN201811579573 A CN 201811579573A CN 109575597 B CN109575597 B CN 109575597B
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2312/00—Crosslinking
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a bismaleimide molding compound capable of being injection molded and a preparation method thereof. The molding compound is prepared from the following components in parts by weight: 25-45 parts of pre-crosslinking matter, 0.4-2.0 parts of initiator, 3-5 parts of plasticizer, 3-5 parts of flexibilizer, 15-30 parts of glass fiber, 16-48 parts of inorganic filler and 1-3 parts of other auxiliary agents; wherein the pre-cross-linked polymer is prepared by the following method: melting N, N '-4,4' -diphenylmethane bismaleimide and crystalline unsaturated polyester resin with melting point less than or equal to 125 ℃, uniformly stirring, and pre-crosslinking with an initiator which is 0.01-0.1% of the weight of the obtained material; the initiator is one or more than two selected from DCP, BP and bis 25; the plasticizer is vinyl epoxy resin with a softening point of 60-80 ℃; the toughening agent is low molecular polybutadiene. The molding compound can be molded by using a common thermosetting injection molding machine, and the molded molding compound has excellent electromechanical properties.
Description
Technical Field
The invention relates to a bismaleimide molding compound, in particular to a bismaleimide molding compound capable of being injection molded and a preparation method thereof.
Background
Bismaleimide resin (BMI) is widely applied to the industrial fields of aviation, aerospace, machinery, electronics and the like, such as resin matrix, high-temperature-resistant insulating material, adhesive and the like of advanced composite materials due to excellent heat resistance, electrical insulation, wave permeability, radiation resistance, flame resistance and good mechanical property and dimensional stability. Wherein, the long-term heat-resistant temperature of the bismaleimide resin condensate can reach 260 ℃, the short-term heat-resistant temperature can reach more than 400 ℃, and the self-lubricating property is excellent. However, bismaleimide resins have relatively poor processability, slow crosslinking speed and poor toughness of cured products, and can only be made into compression molding materials or be dissolved to be made into impregnating materials at present, so that the bismaleimide resins are difficult to be processed into molding compounds for processing and molding by a common thermosetting injection molding machine.
Disclosure of Invention
The invention aims to provide a bismaleimide molding compound which can be injection molded by using a common thermosetting injection molding machine and a preparation method thereof.
The bismaleimide molding compound capable of being injection molded is prepared from the following components in parts by weight:
25-45 parts of pre-crosslinking matter, 0.4-2.0 parts of initiator, 3-5 parts of plasticizer, 3-5 parts of flexibilizer, 15-30 parts of glass fiber, 16-48 parts of inorganic filler and 1-3 parts of other auxiliary agents;
wherein:
the pre-crosslinking substance is prepared by the following method: taking N, N '-4,4' -diphenylmethane bismaleimide and crystalline unsaturated polyester resin with the melting point less than or equal to 125 ℃ according to the weight ratio of 3-5: 1, heating to melt, discharging, placing the obtained material in a mixing roll, and adding an initiator which is 0.01-0.1% of the weight of the obtained material for pre-crosslinking to obtain the material; wherein the crystalline unsaturated polyester resin is p-benzene unsaturated polyester resin and/or m-benzene unsaturated polyester resin;
the initiator is one or the combination of more than two of dicumyl peroxide (DCP), alpha' -di-tert-butyl peroxide diisopropylbenzene (BP) and 2, 5-dimethyl-2, 5-di-tert-butyl peroxide hexane (bis 25);
the plasticizer is vinyl epoxy resin with a softening point of 60-80 ℃;
the toughening agent is low molecular polybutadiene.
Preferably, the weight ratio of each component for composing the injection moldable bismaleimide molding compound is as follows:
28-42 parts of pre-crosslinking matter, 0.5-1.5 parts of initiator, 3-5 parts of plasticizer, 3-5 parts of toughening agent, 15-28 parts of glass fiber, 19.5-46 parts of inorganic filler and 1-3 parts of other auxiliary agents.
In the above technical solution, the inorganic filler is selected from the same as the prior art, and specifically may be one or a combination of two or more selected from calcium carbonate, quartz powder, kaolin, aluminum hydroxide and magnesium hydroxide.
In the above technical scheme, the glass fiber is alkali-free glass fiber treated by coupling agent, and the length of the glass fiber is preferably 3-6 mm.
In the technical scheme, the other auxiliary agents are release agents or release agents and coloring agents. The selection of the release agent and the coloring agent is the same as the prior art, wherein the release agent is preferably one or the combination of more than two of calcium stearate, zinc stearate, magnesium stearate, stearic acid and the like.
The invention also provides a preparation method of the bismaleimide molding compound capable of being injection molded, which comprises the following steps:
1) taking N, N '-4,4' -diphenylmethane bismaleimide and crystalline unsaturated polyester resin with the melting point less than or equal to 125 ℃ according to the weight ratio of 3-5: 1, heating to melt, uniformly stirring, discharging, placing the obtained material in a mixing roll, adding an initiator which is 0.01-0.1% of the weight of the obtained material, and pre-crosslinking to obtain a pre-crosslinked substance; wherein the crystalline unsaturated polyester resin is p-benzene unsaturated polyester resin and/or m-benzene unsaturated polyester resin; the initiator is one or the combination of more than two of dicumyl peroxide (DCP), alpha' -di-tert-butyl peroxide diisopropylbenzene (BP) and 2, 5-dimethyl-2, 5-di-tert-butyl peroxide hexane (bis 25);
2) weighing the components according to the formula, uniformly mixing, placing the obtained mixture in a double-screw extruder, fully plasticizing, extruding in a single-screw extruder, and granulating to obtain the bismaleimide molding compound capable of being injection molded.
In step 1) of the above preparation method, the pre-crosslinking is usually carried out at 100-130 ℃, preferably at 120-130 ℃; the pre-crosslinking time is more than or equal to 5min, preferably 10-20 min.
In step 2) of the preparation method, the process parameters of the obtained mixture when plasticizing in a double-screw extruder are as follows: the temperature of the material cylinder is 80-115 ℃, and the rotation speed of the screw is 100-120 rpm; the parameters during extrusion and granulation in the single screw extruder are as follows: the barrel temperature is 90-115 ℃ and the screw revolution is 40-90 rpm.
The bismaleimide molding compound prepared by the method has the following process parameters when a common thermosetting injection machine is adopted for injection molding: the temperature of the die is 175-185 ℃, the temperature of the charging barrel is 80-110 ℃, the injection pressure is 30-60MPa, and the curing time is 25-40 s/mm.
The bismaleimide molding compound can be continuously molded under the molding conditions, the obtained product is flat and full, the thermal rigidity is good, the batch molding requirement of a common thermosetting injection molding machine is met, and the actual measurement performance of a standard sample is shown in the following table 1:
table 1:
compared with the prior art, the N, N '-4,4' -diphenylmethane bismaleimide is used as a main resin, the crystalline unsaturated polyester resin with the melting point lower than 125 ℃ is used as a cross-linking agent, and the N, N '-4,4' -diphenylmethane bismaleimide and the crystalline unsaturated polyester resin are premixed and pre-cross-linked before use, so that the uniformity of the material is improved, and the curing speed of the bismaleimide resin in a mold is accelerated; the subsequent matching of an initiator with higher decomposition temperature avoids the rapid crosslinking reaction of the N, N '-4,4' -diphenylmethane bismaleimide and the crystalline unsaturated polyester resin in the charging barrel, and does not hinder the rapid crosslinking of the N, N '-4,4' -diphenylmethane bismaleimide and the crystalline unsaturated polyester resin at high temperature; vinyl epoxy resin with a specific softening point is used as a plasticizer, so that the plasticizing performance of N, N '-4,4' -diphenylmethane bismaleimide and crystalline unsaturated polyester resin can be remarkably improved, and the vinyl epoxy resin finally participates in crosslinking reaction, so that the vinyl epoxy resin cannot migrate to the surface of a cured product; the matched toughening agent low molecular polybutadiene has the effect of remarkably reducing the brittleness of a BMI cured product. The above components act together to overcome the defects of relatively poor processing manufacturability, slow crosslinking and curing, poor toughness of a cured product and the like existing in the process of manufacturing common injection molding plastic by using N, N '-4,4' -diphenylmethane bismaleimide, and the prepared bismaleimide molding plastic has excellent electromechanical properties, as shown in the table 1.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
1) Weighing the following components in parts by weight for later use:
wherein the pre-cross-linked polymer is prepared by the following method: taking N, N '-4,4' -diphenylmethane bismaleimide and m-benzene unsaturated polyester resin with the melting point of 125 ℃ according to the weight ratio of 3: 1, heating to 170 ℃, melting, fully stirring for 30min, discharging, cooling the obtained material to 125 ℃, then putting into an internal mixer, adding DCP accounting for 0.02% of the weight of the obtained material, keeping the temperature and mixing at 125 ℃, pre-crosslinking for 10min, discharging, and crushing to 120 meshes to obtain the pre-crosslinked material;
2) uniformly mixing the weighed components, and putting the obtained mixed material into a double-screw extruder for extrusion to obtain a softened material; wherein the temperature of a cylinder of the double-screw extruder is 105-115 ℃, and the rotation number of the screw is 100-105 rpm;
3) the softened material is sent into a single screw extruder to be extruded and cut into particles, and the bismaleimide molding compound capable of being injection molded is obtained; wherein the cylinder temperature of the single-screw extruder is 100-115 ℃, and the screw revolution is 80-90 rpm.
Example 2
1) Weighing the following components in parts by weight for later use:
wherein the pre-cross-linked polymer is prepared by the following method: taking N, N '-4,4' -diphenylmethane bismaleimide and m-benzene unsaturated polyester resin with the melting point of 120 ℃ according to the weight ratio of 3.2: 1, heating to 170 ℃, melting, fully stirring for 10min, discharging, cooling the obtained material to 130 ℃, then putting into an internal mixer, adding DCP accounting for 0.04 percent of the weight of the obtained material, keeping the temperature and mixing at 125 ℃, pre-crosslinking for 10min, discharging, and crushing to 120 meshes to obtain the pre-crosslinked material;
2) uniformly mixing the weighed components, and putting the obtained mixed material into a double-screw extruder for extrusion to obtain a softened material; wherein the temperature of a cylinder of the double-screw extruder is 95-105 ℃, the rotation number of the screw is 105-115 rpm;
3) the softened material is sent into a single screw extruder to be extruded and cut into particles, and the bismaleimide molding compound capable of being injection molded is obtained; wherein the cylinder temperature of the single-screw extruder is 100-105 ℃, and the screw revolution is 60-70 rpm.
Example 3
1) Weighing the following components in parts by weight for later use:
wherein the pre-cross-linked polymer is prepared by the following method: taking N, N '-4,4' -diphenylmethane bismaleimide and m-benzene unsaturated polyester resin with the melting point of 115 ℃ according to the weight ratio of 3.5: 1, heating to 180 ℃ for melting, fully stirring for 20min, discharging, cooling the obtained material to 120 ℃, then putting into an internal mixer, adding BP (back propagation) which is 0.03 percent of the weight of the obtained material and bis-25 which is 0.03 percent of the weight of the obtained material, keeping the temperature and mixing at 130 ℃, pre-crosslinking for 15min, discharging, and crushing to 100 meshes to obtain the pre-crosslinked material;
2) uniformly mixing the weighed components, and putting the obtained mixed material into a double-screw extruder for extrusion to obtain a softened material; wherein the temperature of a cylinder of the double-screw extruder is 95-105 ℃, the rotation number of the screw is 105-115 rpm;
3) the softened material is sent into a single screw extruder to be extruded and cut into particles, and the bismaleimide molding compound capable of being injection molded is obtained; wherein the cylinder temperature of the single-screw extruder is 100-105 ℃, and the screw revolution is 60-70 rpm.
Example 4
1) Weighing the following components in parts by weight for later use:
wherein the pre-cross-linked polymer is prepared by the following method: taking N, N '-4,4' -diphenylmethane bismaleimide and m-benzene unsaturated polyester resin with the melting point of 115 ℃ according to the weight ratio of 3.8: 1, heating to 180 ℃ for melting, fully stirring for 20min, discharging, cooling the obtained material to 120 ℃, then putting into an internal mixer, adding BP (back propagation) accounting for 0.08 percent of the weight of the obtained material, keeping the temperature and mixing at 120 ℃, pre-crosslinking for 15min, discharging, and crushing to 100 meshes to obtain the pre-crosslinked material;
2) uniformly mixing the weighed components, and putting the obtained mixed material into a double-screw extruder for extrusion to obtain a softened material; wherein the temperature of a charging barrel of the double-screw extruder is 90-100 ℃, the rotation number of the screw is 100-115 rpm;
3) the softened material is sent into a single screw extruder to be extruded and cut into particles, and the bismaleimide molding compound capable of being injection molded is obtained; wherein the barrel temperature of the single screw extruder is 95-105 ℃, and the screw revolution is 55-65 rpm.
Example 5
1) Weighing the following components in parts by weight for later use:
wherein the pre-cross-linked polymer is prepared by the following method: taking N, N '-4,4' -diphenylmethane bismaleimide and p-benzene unsaturated polyester resin with the melting point of 112 ℃ according to the weight ratio of 4: 1, heating to 170 ℃, melting, fully stirring for 30min, discharging, cooling the obtained material to 120 ℃, then putting into an internal mixer, adding bis-25 accounting for 0.1 percent of the weight of the obtained material, keeping the temperature and mixing at 125 ℃, pre-crosslinking for 20min, discharging, and crushing to 160 meshes to obtain the pre-crosslinked material;
2) uniformly mixing the weighed components, and putting the obtained mixed material into a double-screw extruder for extrusion to obtain a softened material; wherein the temperature of a charging barrel of the double-screw extruder is 85-100 ℃, and the rotation number of the screw is 115 and 120 rpm;
3) the softened material is sent into a single screw extruder to be extruded and cut into particles, and the bismaleimide molding compound capable of being injection molded is obtained; wherein the cylinder temperature of the single screw extruder is 90-100 ℃, and the screw revolution is 55-75 rpm.
Comparative example: examples of Molding materials
1) According to the following steps of 8: 1: 1: 0.5: 5: 7: weighing N, N ' -4,4' -diphenylmethane bismaleimide, diallyl bisphenol A, o-cresol epoxy resin (chain extender), 4' -diphenylsulfone diamine (modifier), aluminum hydroxide, 6mm short-cut alkali-free glass fiber and ethylene bisstearamide (release agent) according to the weight ratio of 0.5 for later use;
2) adding N, N '-4,4' -diphenylmethane bismaleimide, diallyl bisphenol A and o-cresol epoxy resin into a reaction kettle, heating to 160 ℃, mixing for 5min, directly discharging into an internal mixer, and keeping the temperature of the internal mixer at 155-160 ℃; and adding the rest raw materials into an internal mixer, fully kneading for 5min, discharging, cooling, crushing, and sieving with a 80-mesh sieve to obtain the bismaleimide resin matrix molding material.
And (3) carrying out compression molding on the obtained molded material, wherein the molding process comprises the following steps: the temperature of the die is 200 ℃, the pressure is 30Mpa, and the heat preservation time is 30 min. The post-treatment conditions of the molded sample were as follows: 220 ℃ and 230 ℃ for 5 h.
According to the corresponding molding process, the injection moldable bismaleimide molding compound prepared in the above examples 1-5 is respectively used for injection molding of a standard part with a maximum thickness of 4mm by a thermosetting injection machine. The molding compound obtained in each embodiment is fully automatically and continuously molded for 8h, and respectively molded into a 480 mold, a 451 mold, a 424 mold, a 400 mold and a 378 mold, the molding process is continuous and smooth, and the sample is full, bright and flat and has good thermal rigidity. The post-treatment conditions of the molded sample were as follows: 200 ℃ and 220 ℃ for 2 h. The molding process and the performance test results are shown in table 2 below.
Table 2:
Claims (6)
1. a bismaleimide molding compound capable of being molded by injection molding is characterized in that: the composition is prepared from the following components in parts by weight:
25-45 parts of pre-crosslinking matter, 0.4-2.0 parts of initiator, 3-5 parts of plasticizer, 3-5 parts of flexibilizer, 15-30 parts of glass fiber, 16-48 parts of inorganic filler and 1-3 parts of other auxiliary agents;
wherein:
the pre-crosslinking substance is prepared by the following method: taking N, N '-4,4' -diphenylmethane bismaleimide and crystalline unsaturated polyester resin with the melting point less than or equal to 125 ℃ according to the weight ratio of 3-5: 1, heating to melt, discharging, placing the obtained material in a mixing roll, and adding an initiator which is 0.01-0.1% of the weight of the obtained material for pre-crosslinking to obtain the material; wherein the crystalline unsaturated polyester resin is p-benzene unsaturated polyester resin and/or m-benzene unsaturated polyester resin;
the initiator is one or the combination of more than two of dicumyl peroxide, alpha' -di-tert-butyl peroxide diisopropylbenzene and 2, 5-dimethyl-2, 5-di-tert-butyl peroxide hexane;
the plasticizer is vinyl epoxy resin with a softening point of 60-80 ℃;
the toughening agent is low molecular polybutadiene.
2. The injection moldable bismaleimide molding compound of claim 1, wherein: the weight ratio of each component is as follows:
28-42 parts of pre-crosslinking matter, 0.5-1.5 parts of initiator, 3-5 parts of plasticizer, 3-5 parts of toughening agent, 15-28 parts of glass fiber, 19.5-46 parts of inorganic filler and 1-3 parts of other auxiliary agents.
3. The injection moldable bismaleimide molding compound of claim 1 or 2, wherein: the inorganic filler is one or the combination of more than two of calcium carbonate, quartz powder, kaolin, aluminum hydroxide and magnesium hydroxide.
4. The injection moldable bismaleimide molding compound of claim 1 or 2, wherein: the other auxiliary agents are release agents or release agents and coloring agents.
5. A process for preparing an injection moldable bismaleimide molding compound as claimed in claim 1, comprising the steps of:
1) taking N, N '-4,4' -diphenylmethane bismaleimide and crystalline unsaturated polyester resin with the melting point less than or equal to 125 ℃ according to the weight ratio of 3-5: 1, heating to melt, uniformly stirring, discharging, placing the obtained material in a mixing roll, adding an initiator which is 0.01-0.1% of the weight of the obtained material, and pre-crosslinking to obtain a pre-crosslinked substance; wherein the crystalline unsaturated polyester resin is p-benzene unsaturated polyester resin and/or m-benzene unsaturated polyester resin; the initiator is one or the combination of more than two of dicumyl peroxide, alpha' -di-tert-butyl peroxide diisopropylbenzene and 2, 5-dimethyl-2, 5-di-tert-butyl peroxide hexane;
2) weighing the components according to the formula, uniformly mixing, placing the obtained mixture in a double-screw extruder, fully plasticizing, extruding in a single-screw extruder, and granulating to obtain the bismaleimide molding compound capable of being injection molded.
6. The method of claim 5, wherein: in the step 1), the pre-crosslinking is carried out at the temperature of 100-130 ℃, and the pre-crosslinking time is not less than 5 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3712933A (en) * | 1970-08-27 | 1973-01-23 | Rhone Poulenc Sa | Polyimide compositions |
| JPS57179215A (en) * | 1981-04-30 | 1982-11-04 | Hitachi Ltd | Thermosetting resin composition |
| DE3726286A1 (en) * | 1987-08-07 | 1989-02-16 | Basf Ag | MOLDS FROM UNSATURATED POLYESTER RESIN |
| CN101544839A (en) * | 2009-04-23 | 2009-09-30 | 上海交通大学 | Method for preparing pultrusion composite materials for highway guardrails |
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2018
- 2018-12-24 CN CN201811579573.9A patent/CN109575597B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3712933A (en) * | 1970-08-27 | 1973-01-23 | Rhone Poulenc Sa | Polyimide compositions |
| JPS57179215A (en) * | 1981-04-30 | 1982-11-04 | Hitachi Ltd | Thermosetting resin composition |
| DE3726286A1 (en) * | 1987-08-07 | 1989-02-16 | Basf Ag | MOLDS FROM UNSATURATED POLYESTER RESIN |
| CN101544839A (en) * | 2009-04-23 | 2009-09-30 | 上海交通大学 | Method for preparing pultrusion composite materials for highway guardrails |
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