CN103524663A - Method for preparing high-temperature-resistance AN/MAA (acrylonitrile /methacrylic acid) copolymer foam material - Google Patents
Method for preparing high-temperature-resistance AN/MAA (acrylonitrile /methacrylic acid) copolymer foam material Download PDFInfo
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Abstract
The invention discloses a method for preparing a high-temperature-endurance AN/MAA (acrylonitrile /methacrylic acid) copolymer foam material. The method comprises the following steps: directly copolymerizing methacrylic acid, acrylonitrile and a third monomer by adding bismaleimide reinforced resin, gaseous-phase SiO2 or various thickening agents and further simultaneously adding an initiating agent, a foaming agent, a crosslinking agent, a density control agent and a nucleating agent by virtue of a one-step method so as to obtain an AN/MAA copolymer board; performing high-temperature foaming and heat treatment to prepare a high-temperature-endurance AN/MAA copolymer foam. According to the method, the bismaleimide reinforced resin is added to prepare the AN/MAA copolymer hard foam material, so that the problem that the hard AN/MAA copolymer foam is limited in the high-temperature-endurance field can be solved; the thermal deformation temperature of the prepared hard foam material can be over 210 DEG C, and the hard foam material can be widely applied to various fields of high temperature endurance.
Description
Technical field
The present invention relates to the preparation of high temperature resistant AN/MAA copolymer foam material.
Background technology
With respect to soft and semi-rigid foamed plastics, rigid foam has higher mechanical property and resistance toheat, thereby can be widely used in as the core of sandwich structure bearing part Aeronautics and Astronautics and wind-powered electricity generation field.Along with the mold temperature of sandwich structure composite material and the raising of use temperature, to the resistance toheat of rigid foam, require also more and more higher.
What in the rigid foam so far, resistance toheat was best is Polymethacrylimide (PMI) foam, and its heat-drawn wire can be up to 220 ℃.But Polymethacrylimide (PMI) foam obtains that one of body material methacrylonitrile price is very expensive is generally 1000 yuan/Kg, and its gordian technique is also monopolized by external.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of high temperature resistant AN/MAA multipolymer foam material, the method improves its resistance toheat by adding bismaleimides to strengthen resin, cost is low, and high temperature resistant its heat-drawn wire of AN/MAA copolymer foam material of preparation can reach more than 210 ℃.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for high temperature resistant AN/MAA multipolymer foam material, is characterized in that: the method strengthens with bismaleimides the resistance toheat that resin improves AN/MAA copolymer foam material, improves the heat-drawn wire of material; Specifically comprise the following steps:
(1) formula is pressed following parts by weight:
Methacrylic acid 40-60
Vinyl cyanide 40-60
The 3rd monomer 5-20
Bismaleimides 1-30
Thickening material 1-30
Initiator 0.05-0.6
Whipping agent 1-16
Linking agent 1-12
Density-controlling agent 0.1-3
Nucleator 0.3-18
According to above-mentioned formula, methacrylic acid, vinyl cyanide, the 3rd monomer, bismaleimides are strengthened to resin, thickening material mixing, add initiator, whipping agent, linking agent, density-controlling agent, nucleator, mix and obtain homogeneous solution;
(2) solution obtaining is injected in two parallel glass by India-rubber strip good seal, polyreaction 10-70 hour under 30 ℃ of-70 ℃ of bath temperature conditions, forms AN/MAA copolymerization plate;
(3) copolymerization plate is placed on to preheating 2-10 hour under 80 ℃ of-180 ℃ of conditions, then the 10min-200min that foams under 180 ℃ of-230 ℃ of conditions, high temperature resistant AN/MAA multipolymer initial foam obtained;
(4) the high temperature resistant AN/MAA multipolymer initial foam making is kept to 1-5 hour under 100 ℃ of-200 ℃ of conditions, and naturally cool to room temperature, obtain high temperature resistant AN/MAA copolymer foam material.
The body material that the present invention prepares high temperature resistant foam is vinyl cyanide (AN) and methacrylic acid (MAA), by adding bismaleimides to strengthen resin for AN/MAA multipolymer hard foam.The high temperature resistant AN/MAA copolymer foam material that the present invention obtains, can meet rigid foam in the application in high temperature resistant field.Mainly to improve its resistance toheat by adding bismaleimides to strengthen resin.It is ditane type bismaleimides, N-2 that the bismaleimides using strengthens resin, 6-3,5-dimethylphenyl maleimide, allyloxy phenyl maleimide, N, the mixing of the arbitrary proportion of one or more in N '-different types of bismaleimide resins such as a penylene bismaleimides.By adding bismaleimides to strengthen standby high temperature resistant its heat-drawn wire of AN/MAA copolymer foam material of resin, can reach more than 210 ℃.
The present invention is with methacrylic acid, vinyl cyanide and the 3rd monomer, by adding bismaleimides to strengthen resin, gas phase SiO
2or various thickening materials, add initiator, whipping agent, linking agent, density-controlling agent and the direct copolymerization of nucleator single stage method to obtain AN/MAA copolymerization plate simultaneously, then make high temperature resistant AN/MAA copolymer foam through high temperature foaming and thermal treatment.
Thickening material of the present invention is gas phase SiO
2, in organobentonite, diatomite, methylcellulose gum, gelatin one or more; It is ditane type bismaleimides, N-2 that described bismaleimides strengthens resin, 6-3,5-dimethylphenyl maleimide, allyloxy phenyl maleimide, N, the mixing of the arbitrary proportion of one or more in N '-different types of bismaleimide resins such as a penylene bismaleimides; Described gas phase SiO
2order 50-250m
2/ g; Described the 3rd monomer is acrylic amide or the alkyl-acrylates that contains two keys, as one or more in acrylamide, Methacrylamide, methyl acrylate, ethyl propenoate, butyl acrylate; Described whipping agent is carboxamide, methane amide, N, one or more in N-dimethyl urea, Virahol or isopropylcarbinol; Described linking agent be allyl acrylate, allyl methacrylate(AMA), magnesium oxide or or Ethylene glycol dimethacrylate; Described nucleator is Tert-butyl Methacrylate, N-METHYLFORMAMIDE or Propenoic acid, 2-methyl, isobutyl ester.
The present invention prepares AN/MAA copolymer foam with cheap vinyl cyanide substituent methyl vinyl cyanide, and cost is low.Its resistance toheat is relatively low with respect to Polymethacrylimide (PMI) foam, and heat-drawn wire is generally 190 ℃.Vinyl cyanide has lacked a methyl with respect to methacrylonitrile, has caused the difference of reactivity ratio and speed of reaction.The major cause that the resistance toheat of AN/MAA copolymer foam will be worse than polymethacrylimide foam is that the quantity of methacrylic acid adjacent in copolyreaction process and vinyl cyanide is on the low side, thereby causes forming relatively less imide structure when high temperature foams.But strengthen adding of resin by bismaleimides, the imide structure of increase system, its resistance toheat can significantly improve, and adds the bismaleimides of 10wt% based on matrix resin, and the high temperature resistant AN/MAA copolymer foam heat-drawn wire preparing can reach 210 ℃.
The high temperature resistant AN/MAA copolymer foam material that the present invention obtains meets rigid foam in the application in high temperature resistant field.Can space flight and aviation, bullet train, wind-powered electricity generation, boats and ships, medical treatment etc. various to the high temperature resistant field that has certain requirements as packing material or sandwich material.
Embodiment
Embodiment 1
The preparation of high temperature resistant AN/MAA copolymer foam material, fill a prescription as follows:
| Methacrylic acid | 50 |
| Vinyl cyanide | 50 |
| Methacrylamide | 8 |
| Gas phase SiO 2 | 10 |
| Ditane type bismaleimides | 6 |
| N, a N '-penylene bismaleimides | 5 |
| Benzoyl peroxide | 0.3 |
| Diisopropyl azodicarboxylate | 0.2 |
| N methylformamide | 10 |
| Allyl methacrylate(AMA) | 4 |
| Maleimide | 3 |
| Virahol | 8 |
Above-mentioned high temperature resistant AN/MAA copolymer foam material material preparation method step is as follows:
(1) by methacrylic acid, vinyl cyanide, Methacrylamide, gas phase SiO
2, ditane type bismaleimides, N, a N '-penylene bismaleimides, add benzoyl peroxide, Diisopropyl azodicarboxylate, N methylformamide, allyl methacrylate(AMA), maleimide, Virahol to mix according to as above formula.
(2) step (1) gained viscous liquid is injected in two parallel glass by India-rubber strip good seal, under 45 ℃ of bath temperature conditions, polyreaction forms AN/MAA copolymerization plate for 50 hours.
(3) by preheating under 100-150 ℃ of condition of copolymerization plate placement 6 hours, then the 60min that foams under 210 ℃ of conditions, high temperature resistant AN/MAA multipolymer initial foam obtained.
(4) the high temperature resistant AN/MAA multipolymer initial foam making is kept to 2 hours under 180 ℃ of conditions, and naturally cool to room temperature, obtain high temperature resistant AN/MAA copolymer foam material.
The resistant to elevated temperatures AN/MAA copolymer foam material that the present embodiment makes can be up to 215 ℃ through its heat-drawn wire of test.
Comparative example 1
The preparation of conventional type AN/MAA copolymer foam, fill a prescription as follows:
| Methacrylic acid | 50 |
| Vinyl cyanide | 50 |
| Methacrylamide | 8 |
| Gas phase SiO 2 | 10 |
| Benzoyl peroxide | 0.3 |
| Diisopropyl azodicarboxylate | 0.2 |
| N methylformamide | 10 |
| Allyl methacrylate(AMA) | 4 |
| Maleimide | 3 |
| Virahol | 8 |
Above-mentioned conventional type AN/MAA copolymer foam material preparation method step is as follows:
(1) by methacrylic acid, vinyl cyanide, Methacrylamide, gas phase SiO
2, add benzoyl peroxide, Diisopropyl azodicarboxylate, N methylformamide, allyl methacrylate(AMA), maleimide, Virahol according to as above filling a prescription and mix.
(2) step (1) gained viscous liquid is injected in two parallel glass by India-rubber strip good seal, under 45 ℃ of bath temperature conditions, polyreaction forms AN/MAA copolymerization plate for 50 hours.
(3) by preheating under 100-150 ℃ of condition of copolymerization plate placement 5 hours, then the 50min that foams under 200 ℃ of conditions, AN/MAA multipolymer initial foam obtained.
(4) by the AN/MAA multipolymer initial foam making thermal treatment 2 hours under 170 ℃ of conditions, obtain AN/MAA copolymer foam material.
The AN/MAA copolymer foam material that this comparative example makes is AN/MAA copolymer foam material routinely, and its heat-drawn wire is 195 ℃ after tested.
By embodiment 1 and comparative example 1, can be found out, the interpolation of bismaleimides enhancing resin has obviously improved the resistance toheat of AN/MAA copolymer foam material.The high temperature resistant AN/MAA copolymer foam material that the present invention obtains can meet sandwich material preparation and use procedure in to resistant to elevated temperatures requirement.
Claims (9)
1. a preparation method for high temperature resistant AN/MAA multipolymer foam material, is characterized in that: the method strengthens with bismaleimides the resistance toheat that resin improves AN/MAA copolymer foam material, improves the heat-drawn wire of material; Specifically comprise the following steps:
(1) formula is pressed following parts by weight:
Methacrylic acid 40-60
Vinyl cyanide 40-60
The 3rd monomer 5-20
Bismaleimides 1-30
Thickening material 1-30
Initiator 0.05-0.6
Whipping agent 1-16
Linking agent 1-12
Density-controlling agent 0.1-3
Nucleator 0.3-18
According to above-mentioned formula, methacrylic acid, vinyl cyanide, the 3rd monomer, bismaleimides are strengthened to resin, thickening material mixing, add initiator, whipping agent, linking agent, density-controlling agent, nucleator, mix and obtain homogeneous solution;
(2) solution obtaining is injected in two parallel glass by India-rubber strip good seal, polyreaction 10-70 hour under 30 ℃ of-70 ℃ of bath temperature conditions, forms AN/MAA copolymerization plate;
(3) copolymerization plate is placed on to preheating 2-10 hour under 80 ℃ of-180 ℃ of conditions, then the 10min-200min that foams under 180 ℃ of-230 ℃ of conditions, high temperature resistant AN/MAA multipolymer initial foam obtained;
(4) the high temperature resistant AN/MAA multipolymer initial foam making is kept to 1-5 hour under 100 ℃ of-200 ℃ of conditions, and naturally cool to room temperature, obtain high temperature resistant AN/MAA copolymer foam material.
2. the preparation method of high temperature resistant AN/MAA multipolymer foam material according to claim 1, it is characterized in that: it is ditane type bismaleimides, N-2 that the bismaleimides using strengthens resin, 6-3,5-dimethylphenyl maleimide, allyloxy phenyl maleimide, N, the mixing of the arbitrary proportion of one or more in a N '-penylene bismaleimides in different types of bismaleimide resin.
3. the preparation method of high temperature resistant AN/MAA multipolymer foam material according to claim 1, is characterized in that: thickening material is gas phase SiO
2, in organobentonite, diatomite, methylcellulose gum, gelatin one or more.
4. the preparation method of high temperature resistant AN/MAA multipolymer foam material according to claim 3, is characterized in that: gas phase SiO
2specific surface area be 50-250m
2/ g.
5. the preparation method of high temperature resistant AN/MAA multipolymer foam material according to claim 1, is characterized in that: copolymerization process has been used the 3rd monomer as comonomer, and the 3rd monomer is acrylic amide or the alkyl-acrylates that contains two keys.
6. the preparation method of high temperature resistant AN/MAA multipolymer foam material according to claim 5, is characterized in that: the 3rd monomer is one or more in acrylamide, Methacrylamide, methyl acrylate, ethyl propenoate, butyl acrylate.
7. the preparation method of high temperature resistant AN/MAA multipolymer foam material according to claim 1, is characterized in that: whipping agent is carboxamide, methane amide, N N-dimethyl urea, one or more in Virahol or isopropylcarbinol.
8. the preparation method of high temperature resistant AN/MAA multipolymer foam material according to claim 1, is characterized in that: linking agent is allyl acrylate, allyl methacrylate(AMA), magnesium oxide or Ethylene glycol dimethacrylate.
9. the preparation method of high temperature resistant AN/MAA multipolymer foam material according to claim 1, is characterized in that: nucleator is Tert-butyl Methacrylate, N-METHYLFORMAMIDE or Propenoic acid, 2-methyl, isobutyl ester.
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| CN106632831A (en) * | 2016-10-18 | 2017-05-10 | 湖南兆恒材料科技有限公司 | Polymethacrylimide foam plastic and preparation method thereof |
| WO2019085940A1 (en) * | 2017-10-31 | 2019-05-09 | 浙江中科恒泰新材料科技有限公司 | Method for preparing polymethacrylimide foam using one-step-feeding gelation |
| CN110317288A (en) * | 2019-05-21 | 2019-10-11 | 湖南兆恒材料科技有限公司 | A kind of polymethacrylimide foam and preparation method thereof |
| CN111363085A (en) * | 2020-04-24 | 2020-07-03 | 维赛(江苏)复合材料科技有限公司 | High-temperature-resistant monomethylpolymethacrylimide structural foam and preparation method thereof |
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Cited By (7)
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| CN111363085A (en) * | 2020-04-24 | 2020-07-03 | 维赛(江苏)复合材料科技有限公司 | High-temperature-resistant monomethylpolymethacrylimide structural foam and preparation method thereof |
| CN111363085B (en) * | 2020-04-24 | 2022-04-05 | 维赛(江苏)复合材料科技有限公司 | High-temperature-resistant monomethylpolymethacrylimide structural foam and preparation method thereof |
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Application publication date: 20140122 |