CN115948014A - Nano polymer fiber reinforced polymethacrylimide foam and preparation method thereof - Google Patents
Nano polymer fiber reinforced polymethacrylimide foam and preparation method thereof Download PDFInfo
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- 229920007790 polymethacrylimide foam Polymers 0.000 title claims abstract description 56
- 229920005594 polymer fiber Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 39
- 239000002121 nanofiber Substances 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000005187 foaming Methods 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000002667 nucleating agent Substances 0.000 claims abstract description 7
- 239000004088 foaming agent Substances 0.000 claims abstract description 5
- 229920006934 PMI Polymers 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 5
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methyl-2-butanol Substances CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 38
- 230000000379 polymerizing effect Effects 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 5
- 238000007142 ring opening reaction Methods 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 239000001257 hydrogen Chemical group 0.000 abstract description 4
- 229910052739 hydrogen Chemical group 0.000 abstract description 4
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 14
- 239000006261 foam material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a nano polymer fiber reinforced polymethacrylimide foam and a preparation method thereof. The foam is prepared by polymerizing and foaming raw materials comprising acrylic monomers, acrylonitrile monomers, an initiator, a foaming agent, a nucleating agent and a nylon 6 nanofiber solution. The foam is based on the synergistic effect among all components, the nylon 6 nanofiber solution is introduced, and the fibers are grafted on carboxyl and hydrogen bond sites in the PMI foam polymerization process, so that the reinforcement fibers are uniformly distributed in the foam, the foam density is not increased, the toughness of the foam is greatly improved, and the mechanical property of the foam is optimized. The foam adopts a one-pot preparation process, the components of the raw materials are mixed and then subjected to polymerization reaction and foaming treatment, the nylon 6 nanofiber solution and the acrylic monomer are subjected to pretreatment and ring opening, and are directly grafted on the PMI foam in the PMI polymerization process, deacidification treatment is not needed, new impurities are not introduced, and the foam is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a fiber-reinforced foam material, in particular to a nano polymer fiber-reinforced polymethacrylimide foam and a preparation method thereof, and belongs to the field of foam material preparation.
Background
Polymethacrylimide (PMI) foam material is used as isotropic closed-cell rigid foam, called 'foam king', and is widely applied to the fields of aerospace, ships, rail transit, wind power and the like. With the development of scientific technology, higher requirements are also put on PMI foams, such as the desire that the foams have higher toughness while maintaining high strength.
The traditional PMI formula system usually uses a cross-linking agent to reinforce the foam, and the use of the cross-linking agent enhances the strength of the foam, and meanwhile, the toughness is not improved. The toughening mechanism of the material mainly comprises two mechanisms of crack deflection and whisker extraction, and the principle is to increase the energy dissipation of material fracture. U.S. Pat. No. 4,988,02742 proposes the toughening modification of PMI foams by polysiloxane rubbers; japanese patent (JP 5263989) proposes polybutadiene grafted rubber and polyolefin rubber toughening PMI foam, when this kind of traditional rubber toughening material toughens PMI foam material and toughens PMI foam material, can produce negative effects for PMI foam strength and heat resistance, the loss of thermal property has been reduced, in addition rubber toughening agent also can have the compatibility problem in the PMI system, the auxiliary agent that the system compatibility is not good can lead to the mould reaction not good, prepolymer can appear local muddy and even appear unreacted supernatant, influence prepolymer foaming, can lead to foam cell can appear inhomogeneous, the aperture is inconsistent, and then lead to foam mechanical properties homogeneity poor. Therefore, an additive with good compatibility in PMI foam systems is needed, which can increase the toughness and maintain the original mechanical strength of the material.
Disclosure of Invention
In view of the problems of the prior art, the first object of the present invention is to provide a nano polymer fiber reinforced polymethacrylimide foam. The foam is based on the synergistic effect among all components, the nylon 6 nanofiber solution is introduced, the fibers of the reinforcement body are uniformly distributed in the foam, the toughness of the foam is greatly improved on the premise of not increasing the density of the foam, and the mechanical property of the foam is optimized.
The second purpose of the invention is to provide a preparation method of the nano polymer fiber reinforced polymethacrylimide foam. Based on the synergistic effect among the steps, the method adopts two-stage heating polymerization reaction and thermal foaming treatment, so that the reaction rate of polymerized monomers is improved, and the uniformity of pore forming and the uniformity of pore diameter of the foam material are ensured, thereby improving the structural uniformity of the foam.
In order to achieve the technical purpose, the invention provides a nano polymer fiber reinforced polymethacrylimide foam which is obtained by polymerizing and foaming the following raw materials in parts by mass:
the nylon 6 nanofiber solution is prepared by pretreating the following components in parts by mass: 1-10 parts of nylon 6 nano fiber and 10-40 parts of acrylic monomer.
The nylon 6 nanofiber adopted by the invention has larger specific surface area and strong compatibility, can be well combined with a PMI foam system, and can be used as a reinforcing component to improve the mechanical strength of the foam in a small range and greatly improve the toughness of the foam on the premise of ensuring that the density of the foam is not increased; the nylon 6 nanofiber solution contains the ring structure and the chain structure of nylon 6 at the same time, a large amount of carboxyl and hydrogen bonds are always generated in the PMI foam polymerization process, a large amount of binding sites are provided for the nylon 6 nanofiber, and therefore the number of the ring structure and the chain structure in the PMI foam is increased, and the toughness of the foam material is greatly improved.
As a preferable scheme, the nylon 6 nanofiber solution is obtained by pretreating the following components in parts by mass: 1 to 3 parts of nylon 6 nano fiber and 10 to 20 parts of propylene monomer.
The proportion of the nylon 6 nanofibers and the propylene monomers in the nylon 6 nanofiber solution is strictly executed according to the proportion, the nylon 6 nanofibers can be hydrolyzed and opened in an open loop under an acidic condition to form a chain-shaped structure, the nylon 6 nanofiber solution with good compatibility can be obtained by controlling the proportion of the nylon 6 nanofibers and the methacrylic acid, the solution contains the chain-shaped structure formed after the nylon 6 is opened in the loop and an annular structure which is not opened in the loop, the two structures can be combined on the PMI structure through carboxyl and hydrogen bonds generated in PMI polymerization, the quantity of branched chains of PMI can be increased by the increase of the chain-shaped structure, the toughness of PMI foam is improved, the annular structure can play a supporting role, the rigidity of PMI foam is improved, therefore, the nylon 6 nanofiber solution with the optimal proportion of the annular structure and the chain-shaped structure can be obtained only under the proportion, the mechanical strength of the PMI foam is not reduced, and the toughness of the PMI foam can also be greatly improved.
As a preferred embodiment, the acrylic monomer is acrylic acid and/or methacrylic acid.
In a preferred embodiment, the acrylonitrile-based monomer is acrylonitrile and/or methacrylonitrile.
In a preferred embodiment, the initiator is one of lauroyl peroxide, azobisisobutyronitrile, dibenzoyl peroxide and tert-butyl peroxypivalate.
As a preferred embodiment, the foaming agent is one of ethanol, propanol, isopropanol, water, butanol, t-butanol, pentanol and isoamyl alcohol.
In a preferred embodiment, the nucleating agent is one of carbamide, formamide, methacrylamide, N-methylformamide, N-dimethylformamide, methyl acrylate, tert-butyl acrylate, methyl methacrylate and tert-butyl methacrylate.
The invention also provides a preparation method of the nano polymer fiber reinforced polymethacrylimide foam, which comprises the steps of uniformly mixing raw materials including acrylic monomers, acrylonitrile monomers, an initiator, a foaming agent, a nucleating agent and a nylon 6 nano fiber solution to obtain a mixture; carrying out polymerization reaction on the mixture in a closed mold to obtain a PMI prepolymer; carrying out thermal foaming treatment on the PMI prepolymer to obtain the PMI prepolymer; the conditions of the polymerization reaction are as follows: the temperature is 30-50 ℃ and the time is 120-210 h.
The preparation method provided by the invention adopts a one-pot process, and the raw materials are fully mixed and then subjected to polymerization reaction and foaming treatment, wherein the nylon 6 nanofiber solution is subjected to ring opening through pretreatment with an acrylic monomer, and is directly grafted on PMI foam in the PMI polymerization process, so that deacidification treatment is not required, new impurities are not introduced, and the preparation method is suitable for large-scale industrial production.
As a preferable mode, the uniform mixing mode is stirring mixing, and the conditions are as follows: the stirring speed is 180-300 r/min, and the time is 4-6 h.
In a preferred embodiment, the polymerization reaction is a two-stage temperature-rising polymerization, and the conditions of the first-stage temperature-rising polymerization are as follows: the temperature is 30-40 ℃, the time is 90-150 h, and the conditions of the second-stage heating polymerization are as follows: the temperature is 40-50 ℃ and the time is 30-60 h. In the initial stage of polymerization reaction, acrylic monomers are polymerized under the action of an initiator, when the initiator is exhausted, a small amount of acrylic monomers are left, and the residual acrylic monomers can be effectively and completely reacted through two-stage heating polymerization, so that the utilization rate of raw materials is improved.
As a preferable mode, the thermal foaming treatment is two-stage temperature-rising foaming, and the conditions of the first stage temperature-rising foaming are as follows: the temperature is 140-180 ℃, and the time is 2-6 h; the conditions of the second-stage temperature rise foaming are as follows: the temperature is 180-220 ℃, and the time is 2-8 h.
As a preferable scheme, the preparation method further comprises a pretreatment process of the nylon 6 nanofiber solution, wherein the pretreatment process comprises the following steps: soaking nylon 6 nano fiber in acrylic acid monomer at 10-40 deg.c for 30-90 min and stirring to obtain the product; the stirring conditions are as follows: the stirring speed is 100-240 r/min, and the time is 1-4 h. The pretreatment process of the nylon 6 nanofiber solution is strictly performed according to the requirements, if the temperature is too high or the time is too long, the chain structures in the PMI foam are too many, so that the mechanical strength is seriously reduced, and if the temperature is too low or the time is too short, the ring structures in the PMI foam are too many, so that the brittleness is increased, and the toughness is seriously reduced.
Compared with the prior art, the invention has the following excellent technical effects:
1) The nanometer polymer fiber reinforced polymethacrylimide foam provided by the invention is based on the synergistic effect among all components, the nylon 6 nanometer fiber solution is introduced, and the reinforcement fibers are uniformly distributed in the foam through grafting on carboxyl and hydrogen bond sites in the PMI foam polymerization process, so that the obdurability of the foam is greatly improved on the premise of not increasing the foam density, and the mechanical property of the foam is optimized.
2) In the technical scheme provided by the invention, the adopted nylon 6 nanofiber solution contains a chain structure formed after nylon 6 is subjected to ring opening and an annular structure which is not subjected to ring opening, the increase of the chain structure can increase the number of branched chains of PMI, so that the toughness of PMI foam is improved, and the annular structure can play a supporting role, so that the rigidity of PMI foam is improved, therefore, the nylon 6 nanofiber solution is adopted as a reinforcement solution, so that the foam can be endowed with high toughness, the original strength of a foam material can be maintained, and the foam density is not obviously changed.
3) According to the technical scheme provided by the invention, a one-pot process is adopted, all the components of the raw materials are fully mixed and then subjected to polymerization reaction and foaming treatment, wherein a nylon 6 nanofiber solution is subjected to ring opening through pretreatment with an acrylic monomer and is directly grafted on PMI foam in the PMI polymerization process, deacidification treatment is not required, no new impurities are introduced, and the method is suitable for large-scale industrial production.
The specific implementation mode is as follows:
the present invention is further illustrated below with reference to specific examples so that a person skilled in the art may better understand the present invention, but without restricting the present invention.
Example 1
Soaking 2 parts of nylon 6 nano-fiber in 16 parts of methacrylic acid for 45min at 25 ℃, and stirring for 2h at 200r/min to obtain a pretreated nylon 6 nano-fiber solution.
Stirring the prepared 10 parts of nylon 6 nanofiber solution, 30 parts of methacrylonitrile, 30 parts of methacrylic acid, 0.5 part of lauroyl peroxide, 5 parts of isopropanol and 5 parts of formamide in a 5L glass kettle for 4 hours at the rotating speed of 260r/min, then filling into a mold, polymerizing for 120hours at the temperature of 35 ℃, polymerizing for 36 hours at the temperature of 45 ℃, and demolding to obtain the polymethacrylimide prepolymer. Then foaming is carried out for 2.5h at 160 ℃ and 2.5h at 210 ℃ to obtain the PMI foam with high strength and toughness. The density of the PMI foam produced was found to be 52kg/m 3 。
The PMI foam prepared in this example had a tensile strength of 1.70MPa and an elongation at break of 5.6% as measured according to GB/T9641-1988; the compressive strength is 0.90Mpa according to the GB/T8813-2008 standard test, and the shear strength is 1.15Mpa according to the GB/T10007-2008 standard test.
Example 2
Exactly the same PMI foam as in example 1 was prepared, except that 3 parts of nylon 6 nanofibers were soaked in 18 parts of methacrylic acid, and the PMI foam prepared by the test had a density of 51kg/m 3 。
The PMI foam prepared in this example had a tensile strength of 1.70MPa and an elongation at break of 5.5% as measured in accordance with GB/T9641-1988; the compressive strength is 0.90Mpa according to the GB/T8813-2008 standard test, and the shear strength is 1.10Mpa according to the GB/T10007-2008 standard test.
Example 3
Exactly the same PMI foam as in example 1 was prepared, except that 3.5 parts of isopropanol and 3.5 parts of formamide were used, and that PMI foam having a density of 75kg/m was prepared by testing 3 。
The PMI foam prepared in the example has a tensile strength of 2.30MPa and an elongation at break of 6.0% according to a test of GB/T9641-1988; the compressive strength is 1.75Mpa according to the GB/T8813-2008 standard test, and the shear strength is 1.70Mpa according to the GB/T10007-2008 standard test.
Comparative example 1
30 parts of methacrylonitrile and 30 parts of methacrylic acid0.5 part of lauroyl peroxide, 5 parts of isopropanol and 5 parts of formamide are stirred in a 5L glass kettle for 4 hours at the rotating speed of 260r/min, then poured into a mold, polymerized at 35 ℃ for 120hours, polymerized at 45 ℃ for 36 hours, and demolded to obtain the polymethacrylimide prepolymer. Then foaming at 160 ℃ for 2.5h and at 210 ℃ for 2.5h to obtain a foam with density of 52kg/m 3 。
The PMI foam prepared in the example has a tensile strength of 1.60MPa and an elongation at break of 4.0% according to a test of GB/T9641-1988; the compressive strength is 0.850MPa according to the GB/T8813-2008 standard test, and the shear strength is 0.80MPa according to the GB/T10007-2008 standard test.
Comparative example 2
Stirring 30 parts of methacrylonitrile, 30 parts of methacrylic acid, 0.5 part of lauroyl peroxide, 3.5 parts of isopropanol and 3.5 parts of formamide in a 5L glass kettle for 4 hours at the rotating speed of 260r/min, filling into a mold, polymerizing at 35 ℃ for 120hours, polymerizing at 45 ℃ for 36 hours, and demolding to obtain the polymethacrylimide prepolymer. Then foaming at 160 ℃ for 2.5h and at 210 ℃ for 2.5h to obtain a foam with a density of 75kg/m 3 。
The PMI foam prepared in this example had a tensile strength of 1.30MPa and an elongation at break of 4.5% as measured according to GB/T9641-1988; the compressive strength is 1.7Mpa according to the GB/T8813-2008 standard test, and the shear strength is 1.30Mpa according to the GB/T10007-2008 standard test.
The tensile strength, elongation at break, compressive strength and shear strength of the foams prepared in examples 1 to 3 and comparative examples 1 and 2 are measured according to national standards, and the specific data are shown in Table 1:
TABLE 1
From the density and compressive strength data of the PMI foams obtained in examples 1 to 3, it is understood that the density of the foams and the compressive strength are in a positive correlation, because the foam density is mainly determined by the amounts of the blowing agent and the nucleating agent added, and the mechanical strength of the foams increases as the density of the foams obtained increases with decreasing amounts of the blowing agent and the nucleating agent added.
The toughness indexes mainly comprise shear strength and elongation at break, and as can be seen from the table above, the PMI foam is toughened by adopting the pretreated nylon 6 nano fibers, the foam of each embodiment basically has the same compression strength as the foam of the comparative embodiment with the same density, the tensile strength is slightly improved, the shear strength is improved by more than 43.7 percent at most, the elongation at break is improved by 40 percent at most, the PMI prepared in embodiments 1 to 3 has obviously improved shear strength and elongation at break, and the toughness indexes are obviously enhanced. The comparison shows that the PMI foam material provided by the invention can greatly improve the toughness index and ensure that the rigidity strength of the material can maintain the original level or higher level.
Claims (10)
1. The nano polymer fiber reinforced polymethacrylimide foam is characterized by being prepared from the following raw materials in parts by mass through polymerization and foaming:
the nylon 6 nanofiber solution is prepared by pretreating the following components in parts by mass: 1-10 parts of nylon 6 nano fiber and 10-40 parts of acrylic monomer.
2. The nano-polymer fiber reinforced polymethacrylimide foam according to claim 1, wherein: the acrylic monomer is acrylic acid and/or methacrylic acid; the acrylonitrile monomer is acrylonitrile and/or methacrylonitrile.
3. The nano-polymer fiber reinforced polymethacrylimide foam according to claim 1, wherein: the initiator is one of lauroyl peroxide, azobisisobutyronitrile, dibenzoyl peroxide and tert-butyl peroxypivalate.
4. The nano-polymer fiber reinforced polymethacrylimide foam as set forth in claim 1, wherein: the foaming agent is one of ethanol, propanol, isopropanol, water, butanol, tert-butanol, amyl alcohol and isoamyl alcohol.
5. The nano-polymer fiber reinforced polymethacrylimide foam according to claim 1, wherein: the nucleating agent is one of carbamide, formamide, methacrylamide, N-methyl formamide, N-dimethyl formamide, methyl acrylate, tert-butyl acrylate, methyl methacrylate and tert-butyl methacrylate.
6. The method for preparing a nano polymer fiber reinforced polymethacrylimide foam according to any one of claims 1 to 5, wherein the method comprises the following steps: uniformly mixing raw materials including acrylic monomers, acrylonitrile monomers, an initiator, a foaming agent, a nucleating agent and a nylon 6 nanofiber solution to obtain a mixture; carrying out polymerization reaction on the mixture in a closed mold to obtain a PMI prepolymer; carrying out thermal foaming treatment on the PMI prepolymer to obtain the PMI prepolymer; the conditions of the polymerization reaction are as follows: the temperature is 30-50 ℃ and the time is 120-210 h.
7. The method for preparing the nano polymer fiber reinforced polymethacrylimide foam according to claim 6, wherein the method comprises the following steps: the uniform mixing mode is stirring mixing, and the conditions are as follows: the stirring speed is 180-300 r/min, and the time is 4-6 h.
8. The method for preparing the nano polymer fiber reinforced polymethacrylimide foam as claimed in claim 6, wherein the method comprises the following steps: the polymerization reaction is two-stage heating polymerization, and the conditions of the first stage heating polymerization are as follows: the temperature is 30-40 ℃, and the time is 90-150 h; the conditions of the second-stage heating polymerization are as follows: the temperature is 40-50 ℃ and the time is 30-60 h.
9. The method for preparing the nano polymer reinforced polymethacrylimide foam as claimed in claim 6, wherein the method comprises the following steps: the thermal foaming treatment is two-stage heating foaming, and the conditions of the first stage heating foaming are as follows: the temperature is 140-180 ℃, and the time is 2-6 h; the conditions of the second stage heating foaming are as follows: the temperature is 180-220 ℃, and the time is 2-8 h.
10. The method for preparing the nano polymer fiber reinforced polymethacrylimide foam as claimed in claim 6, wherein the method comprises the following steps: the method also comprises a pretreatment process of the nylon 6 nanofiber solution, wherein the pretreatment process comprises the following steps: soaking nylon 6 nano fiber in acrylic acid monomer at 10-40 deg.c for 30-90 min and stirring to obtain the product; the stirring conditions are as follows: the stirring speed is 100-240 r/min, and the time is 1-4 h.
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