CN116731443A - High-toughness SMMA composite material and preparation method thereof - Google Patents
High-toughness SMMA composite material and preparation method thereof Download PDFInfo
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- CN116731443A CN116731443A CN202310649073.2A CN202310649073A CN116731443A CN 116731443 A CN116731443 A CN 116731443A CN 202310649073 A CN202310649073 A CN 202310649073A CN 116731443 A CN116731443 A CN 116731443A
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 title claims abstract 22
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000007493 shaping process Methods 0.000 claims abstract description 14
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 abstract description 10
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 43
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 43
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 230000005501 phase interface Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001485 positron annihilation lifetime spectroscopy Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The application discloses a high-toughness SMMA composite material and a preparation method thereof. The preparation method comprises the following steps: mixing SMMA, TPU and SMA at 225-235 ℃ in an banburying way, crushing and drying the obtained blend, putting the mixture into a flat vulcanizing machine, setting the temperature of the flat vulcanizing machine to 225-235 ℃, setting the pressure to 9-11 MPa, hot-pressing for 9-11 minutes, cold-pressing for 4-6 minutes at room temperature under the pressure of 9-11 MPa, and shaping to obtain the high-toughness SMMA composite material; based on 100% of total mass of the SMMA and the TPU, the mass percentage of the SMMA is 60% -70%, the mass percentage of the TPU is 30% -40%, and the mass percentage of the SMA is 1% -5%. The notch impact toughness of the high-toughness SMMA composite material is more than 3kJ/m 2 The impact toughness without gaps is more than 10kJ/m 2 。
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a high-toughness SMMA composite material and a preparation method thereof.
Background
Polymeric materials have been widely used in various aspects of human production and life for more than one hundred years recently. The polymer material has the advantages of excellent performance, lower density, easy processing and the like. However, for most polymeric materials, poor toughness tends to be a critical factor limiting their use.
Styrene dimethyl methyl acrylate copolymer (SMMA) has a series of advantages of higher strength, easiness in processing, high surface glossiness and the like as a glassy plastic, but has extremely poor toughness due to the existence of a large number of rigid groups in a molecular chain, and thus, further wide application of the SMMA is limited. From the energy dissipation point of view, SMMA energy dissipation in the event of an impact is mainly performed in the form of silver marks. And SMMA has poor compatibility with common elastomers such as POE (polyolefin elastomer), TPU (thermoplastic polyurethane elastomer) and the like, so that the SMMA matrix is difficult to trigger to generate a shearing yield zone simply by adding the elastomer, thereby dissipating a large amount of energy and improving the impact performance of the SMMA.
Patent specification with publication number CN 116120679A discloses an SMMA microporous foam material with high toughness and a preparation method thereof. SMMA microporous foam material with high toughness has a notched impact strength of 2KJ/m 2 The elongation at break is more than 2.5%, the weight loss is more than 25%, the average size of the cells is less than 40 microns, and the density of the cells is more than 10 7 Individual/cm 3 . The preparation method comprises the following steps: passing 60wt% to 90wt% of SMMA, 10wt% to 40wt% of elastomer SBS and 0 to 5wt% of nucleating agent through doubleAnd (3) carrying out blending extrusion by a screw extruder, drying the obtained composite material, adding the dried composite material into a foaming injection molding machine, pre-molding under the pressure of 4-10MPa to obtain uniform composite material melt and gas melt, injecting the uniform composite material melt into a mold cavity, maintaining the pressure, opening the mold, foaming, and cooling to obtain the SMMA microporous foaming material with high toughness.
Jiang Zhongying et al obtained an SMMA/SMA mixture by co-dissolving a polystyrene-methyl methacrylate copolymer (SMMA, containing 40wt% of polystyrene) and a polystyrene-maleic anhydride copolymer (SMA, containing 7wt% of maleic anhydride MA) in a tetrahydrofuran solvent, and then cast drying, and further studied the free volume thermodynamic properties of the mixture and the PALS study of the phase separation behavior (Proprietary report, volume 55, 6, 2006).
Disclosure of Invention
The application provides a preparation method of a high-toughness SMMA composite material, aiming at the problem of poor compatibility of SMMA and TPU (especially TPU without benzene ring structure), the SMA is adopted for compatibilization, benzene ring and maleic anhydride groups on the SMA are utilized for bridging, the reaction distance between the SMA and polar groups of the SMMA and the TPU is shortened, and the compatibility of the SMMA and the TPU elastomer groups is improved, so that the effect of improving impact toughness is realized.
The specific technical scheme is as follows:
the preparation method of the high-toughness SMMA composite material comprises the steps of banburying and blending SMMA, TPU and SMA at 225-235 ℃, crushing and drying the obtained blend, and then placing the obtained blend in a flat vulcanizing machine, wherein the temperature of the flat vulcanizing machine is 225-235 ℃, the pressure of the flat vulcanizing machine is 9-11 MPa, after hot pressing for 9-11 minutes, cold pressing for 4-6 minutes at room temperature under the pressure of 9-11 MPa for shaping, thus obtaining the high-toughness SMMA composite material;
based on 100% of total mass of the SMMA and the TPU, the mass percentage of the SMMA is 60% -70%, the mass percentage of the TPU is 30% -40%, and the mass percentage of the SMA is 1% -5%.
The preparation method adopts the banburying blending-hot pressing reaction-cold pressing shaping process, wherein: the temperature of banburying and blending and the temperature of a vulcanizing press are set to 225-235 ℃, the temperature is too high, SMMA, TPU and SMA are easy to decompose, and the temperature process is difficult or even impossible to process; the pressure of the vulcanizing press is set to 9-11 MPa, the pressure is too low, the product is concave, and the surface is uneven; the hot pressing time of the press vulcanizer is 9-11 minutes, the time is too short, the banburying blend of the SMMA, the TPU and the SMA is not thoroughly melted, the time is too long, and the SMMA, the TPU and the SMA are easy to degrade; the cold pressing process at room temperature is used for shaping products, and needs enough pressure and time, and the pressure is too small or the time is too short, so that the shaping is difficult or impossible.
The application also defines the composition ratio of the SMMA, the TPU and the SMA in the high-toughness SMMA composite material, wherein the mass percentage of the SMMA is 60-70 percent, the mass percentage of the TPU is 30-40 percent, the mass percentage of the SMA is 1-5 percent, too much SMMA can cause poor toughness of the composite material, too much TPU can cause poor rigidity of the composite material, and under the preparation process of banburying blending-hot pressing reaction-cold pressing shaping, the excellent compatibility effect can be shown only by using the SMA with the consumption of 1-5 percent (calculated by 100 percent of the total mass of the SMMA and the TPU), the consumption is further improved, and the toughness improvement effect of the composite material is not obvious. Too low an SMA amount may result in insufficient compatibility and poor toughness of the composite.
In a preferred embodiment, the high-toughness SMMA composite material is prepared by the method, wherein the styrene content in the SMMA is 45-55wt%, and the SMMA has better rigidity in the range.
In order to obtain a better toughening effect, in a preferred embodiment, the preparation method of the high-toughness SMMA composite material, the Shore hardness of the TPU is 65A-95A, and the too soft or too hard TPU has poor toughening effect on the SMMA.
In a preferred embodiment, the method for preparing the high-toughness SMMA composite material comprises the step of enabling the maleic anhydride content in the SMA to be 15-40 wt%, so that the SMA is not easy to decompose in the preparation process, and sufficient compatibility is provided.
In a preferred embodiment, the method for preparing the high-toughness SMMA composite material is characterized in that the banburying time is 10-20 min, so that good dispersibility of the SMMA, the TPU and the SMA is guaranteed, and a blend which is uniformly mixed is formed.
In a preferred embodiment, the preparation method of the high-toughness SMMA composite material is characterized in that the banburying is carried out in an internal mixer, and the rotating speed of the internal mixer is 40-80 rpm, so that good dispersibility of the SMMA, TPU and SMA is guaranteed, and a blend which is uniformly mixed is formed.
In a preferred embodiment, the drying temperature is 60-80 ℃ and the time is 6-8 hours.
As a general inventive concept, the application also provides the high-toughness SMMA composite material prepared by the preparation method.
The notch impact toughness of the high-toughness SMMA composite material is more than 3kJ/m 2 The impact toughness without gaps is more than 10kJ/m 2 . Test standard: GB/T1834-1996.
Compared with the prior art, the application has the beneficial effects that:
aiming at the problem of poor compatibility of SMMA and TPU (especially TPU without benzene ring structure), the application adopts SMA to carry out compatibilization, and on the basis of limiting the dosage proportion of the SMMA and the TPU to ensure that the composite material can be compatible with toughness and rigidity, the SMA can play a remarkable role of compatibility under lower dosage through a specific banburying blending-hot pressing reaction-cold pressing shaping process.
According to the application, the benzene ring and the maleic anhydride group on the SMA are utilized to carry out bridging action, the reaction distance between the SMA and the polar groups of the SMMA and the TPU is shortened, and the compatibility between the SMMA and the TPU elastomer group is improved, so that the effect of improving the impact toughness is realized.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the high toughness SMMA composite prepared in example 2.
Fig. 2 is a scanning electron micrograph of the high toughness SMMA composite prepared in example 3.
Fig. 3 is a scanning electron micrograph of the high toughness SMMA composite prepared in example 4.
Fig. 4 is a scanning electron micrograph of the SMMA composite prepared in comparative example 2.
Detailed Description
The application will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Unless otherwise specified, "parts" in the following examples and comparative examples refer to parts by mass.
The notched impact toughness and the unnotched impact toughness in the examples and comparative examples below were measured according to GB/T1834-1996 standard.
Example 1
70 parts of SMMA (styrene content 50 wt%) were blended with 30 parts of TPU (Shore hardness 95A) and 3 parts of SMA (maleic anhydride content 15 wt%) were prepared, namely a 70SMMA/30TPU/3SMA blend.
70 parts of SMMA, 30 parts of TPU and 3 parts of SMA are blended by an internal mixer at a speed of 60rpm and at a temperature of 230℃for a period of 10 minutes.
The blend obtained by internal mixing is crushed by a crusher and then is dried in an oven at 80 ℃ for 8 hours.
And (3) placing the dried material in a flat vulcanizing machine, hot-pressing for 10min at 230 ℃ and 10MPa, and cold-pressing for 5 min at room temperature and the pressure of 10MPa in another flat vulcanizing machine for shaping to obtain the high-toughness SMMA composite material.
The performance of the high-toughness SMMA composite material prepared in the embodiment is analyzed and characterized, and the notch impact strength is 3.62kJ/m 2 The unnotched impact strength was 13.5kJ/m 2 Through SEM characterization, the SMA is introduced to achieve a better compatibilization effect, and an obvious phase interface is not formed between the SMMA matrix and the TPU.
Example 2
Preparation of 60 parts SMMA (styrene content 50 wt%) blended 40 parts TPU (Shore 95A) and 1 part SMA (maleic anhydride content 15 wt%), namely 60SMMA/40TPU/1SMA blend.
60 parts of SMMA, 40 parts of TPU and 1 part of SMA are blended by an internal mixer at a speed of 60rpm and at a temperature of 230℃for a period of 10 minutes.
The blend obtained by internal mixing is crushed by a crusher and then is dried in an oven at 80 ℃ for 8 hours.
And (3) placing the dried material in a flat vulcanizing machine, hot-pressing for 10min at 230 ℃ and 10MPa, and cold-pressing for 5 min at room temperature and the pressure of 10MPa in another flat vulcanizing machine for shaping to obtain the high-toughness SMMA composite material.
The performance of the high-toughness SMMA composite material prepared in the embodiment is analyzed and characterized, and the notch impact strength is 3.24kJ/m 2 The unnotched impact strength was 26.9kJ/m 2 As can be seen from SEM characterization, the SMA prepared by the preparation process provided by the application has a better compatibilization effect, and an SMMA matrix and TPU have no obvious phase interface, as shown in figure 1.
Example 3
Preparation of 60 parts SMMA (styrene content 50 wt%) blended 40 parts TPU (Shore 95A) and 3 parts SMA (maleic anhydride content 15 wt%), namely 60SMMA/40TPU/3SMA blend.
60 parts of SMMA, 40 parts of TPU and 3 parts of SMA are blended by an internal mixer at a speed of 60rpm and at a temperature of 230℃for a period of 10 minutes.
The blend obtained by internal mixing is crushed by a crusher and then is dried in an oven at 80 ℃ for 8 hours.
And (3) placing the dried material in a flat vulcanizing machine, hot-pressing for 10min at 230 ℃ and 10MPa, and cold-pressing for 5 min at room temperature and the pressure of 10MPa in another flat vulcanizing machine for shaping to obtain the high-toughness SMMA composite material.
The performance of the high-toughness SMMA composite material prepared in the embodiment is analyzed and characterized, and the notch impact strength is 3.48kJ/m 2 The unnotched impact strength was 35.9kJ/m 2 As can be seen from SEM characterization, the SMA prepared by the preparation process provided by the application has a better compatibilization effect, and the SMMA matrix and the TPU have no obvious phase interface, so that the compatibility between the phase interfaces is further improved compared with that of the example 2, as shown in figure 2.
Example 4
Preparation of 60 parts SMMA (styrene content 50 wt%) blend 40 parts TPU (Shore 95A) and 5 parts SMA (maleic anhydride content 15 wt%), namely 60SMMA/40TPU/5SMA blend.
60 parts of SMMA, 40 parts of TPU and 5 parts of SMA are blended by an internal mixer at a speed of 60rpm and at a temperature of 230℃for a period of 10 minutes.
The blend obtained by internal mixing is crushed by a crusher and then is dried in an oven at 80 ℃ for 8 hours.
And (3) placing the dried material in a flat vulcanizing machine, hot-pressing for 10min at 230 ℃ and 10MPa, and cold-pressing for 5 min at room temperature and the pressure of 10MPa in another flat vulcanizing machine for shaping to obtain the high-toughness SMMA composite material.
The performance of the high-toughness SMMA composite material prepared in the embodiment is analyzed and characterized, and the notch impact strength is 3.61kJ/m 2 The unnotched impact strength was 40.8kJ/m 2 As can be seen from SEM characterization, the SMA prepared by the preparation process provided by the application has a better compatibilization effect, and the SMMA matrix and the TPU have no obvious phase interface, so that compared with example 3, the compatibility between the phase interfaces is further improved, as shown in figure 3.
Comparative example 1
70 parts of SMMA (styrene content 50 wt%) were blended with 30 parts of TPU (Shore 95A), i.e., 70SMMA/30TPU blend.
70 parts of SMMA and 30 parts of TPU were blended by means of an internal mixer at a speed of 60rpm and at a temperature of 230℃for a period of 10 minutes.
The blend obtained by internal mixing is crushed by a crusher and then is dried in an oven at 80 ℃ for 8 hours.
And (3) placing the dried material in a flat vulcanizing machine, hot-pressing for 10min at 230 ℃ and 10MPa, and cold-pressing for 5 min at room temperature and the pressure of 10MPa in another flat vulcanizing machine for shaping to obtain the high-toughness SMMA composite material.
The SMMA composite material prepared in the comparative example has the performance characterized by analysis, and the notch impact strength of the SMMA composite material is 1.55kJ/m 2 The impact strength without gaps is 3.7kJ/m 2 By means ofSEM characterization revealed that the SMMA matrix had a distinct interfacial interface with the TPU, with significantly poorer compatibility.
Comparative example 2
Preparation of 60 parts SMMA (styrene content 50 wt%) blend 40 parts TPU (Shore 95A), i.e. 60SMMA/40TPU blend.
60 parts of SMMA and 40 parts of TPU were blended by means of an internal mixer at a speed of 60rpm and a temperature of 230℃for a period of 10 minutes.
The blend obtained by internal mixing is crushed by a crusher and then is dried in an oven at 80 ℃ for 8 hours.
And (3) placing the dried material in a flat vulcanizing machine, hot-pressing for 10min at 230 ℃ and 10MPa, and cold-pressing for 5 min at room temperature and the pressure of 10MPa in another flat vulcanizing machine for shaping to obtain the high-toughness SMMA composite material.
The SMMA composite material prepared in the comparative example has the performance analysis and characterization, and the notched impact strength of the SMMA composite material is 2.38kJ/m 2 The impact strength without gaps is 4.7kJ/m 2 As can be seen from SEM characterization, the SMMA matrix has a distinct interfacial interface with the TPU, and the compatibility is significantly worse, as shown in fig. 4.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (9)
1. A preparation method of a high-toughness SMMA composite material is characterized in that SMMA, TPU and SMA are mixed at 225-235 ℃ in an banburying way, the obtained mixture is crushed and dried and then is placed in a flat vulcanizing machine, the temperature of the flat vulcanizing machine is set to 225-235 ℃, the pressure is set to 9-11 MPa, after hot pressing is carried out for 9-11 minutes, cold pressing is carried out at room temperature for 4-6 minutes under the pressure of 9-11 MPa for shaping, and the high-toughness SMMA composite material is obtained;
based on 100% of total mass of the SMMA and the TPU, the mass percentage of the SMMA is 60% -70%, the mass percentage of the TPU is 30% -40%, and the mass percentage of the SMA is 1% -5%.
2. The method of preparing a high toughness SMMA composite material according to claim 1, wherein the styrene content of said SMMA is 45wt% to 55wt%.
3. The method of preparing a high toughness SMMA composite of claim 1, wherein the TPU has a shore hardness of 65A to 95A.
4. The method of preparing a high toughness SMMA composite material according to claim 1, wherein the content of maleic anhydride in said SMA is 15wt% to 40wt%.
5. The method for preparing a high toughness SMMA composite material according to claim 1, wherein said banburying time is 10-20 min.
6. The method for preparing a high toughness SMMA composite material according to claim 1, wherein said banburying is performed in an internal mixer with a rotation speed of 40-80 rpm.
7. The method for preparing a high toughness SMMA composite material according to claim 1, wherein said drying is performed at a temperature of 60-80 ℃ for a time of 6-8 hours.
8. The high-toughness SMMA composite material prepared by the preparation method according to any one of claims 1 to 7.
9. The high toughness SMMA composite of claim 8, wherein said high toughness SMMA composite has a notched impact toughness greater than 3kJ/m 2 The impact toughness without gaps is more than 10kJ/m 2 。
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