CN103524662A - Preparation method of microporous AN/MAA (acrylic nitrile/methacrylic acid) copolymer foam - Google Patents
Preparation method of microporous AN/MAA (acrylic nitrile/methacrylic acid) copolymer foam Download PDFInfo
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- CN103524662A CN103524662A CN201310502170.5A CN201310502170A CN103524662A CN 103524662 A CN103524662 A CN 103524662A CN 201310502170 A CN201310502170 A CN 201310502170A CN 103524662 A CN103524662 A CN 103524662A
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Abstract
The invention discloses a preparation method of microporous AN/MAA (acrylonitrile/methyl acrylic acid) copolymer foam. The preparation method is characterized by comprising the steps of preparing AN, MAA and third monomers, adding gas phase SiO2 or other thickeners and simultaneously adding an initiator, a foamer, a crosslinking agent, a density control agent and a nucleating agent, firstly copolymerizing to obtain an AN/MAA copolymerization board and preparing the AN/MAA copolymer foam through high temperature foaming and heat treatment; and as a sandwich material, the prepared foam can be applied to the high and new technology fields such as aerospace, high speed trains, wind power, ships, medical treatment and the like.
Description
Technical field
The present invention relates to a kind of preparation method of fine pass AN/MAA copolymer foam.
Background technology
AN/MAA copolymer foam is that a kind of abscess is 100% unicellular structure, the rigid foam of light weight, the material of its even crosslinked hole wall knot and hole wall coideal distributes and makes it have outstanding structural stability and excellent mechanical property, heat-drawn wire is up to 150-200 ℃, slightly being worse than Polymethacrylimide (PMI) foam (220 ℃), is the rigid structure porous plastics of Good Heat-resistance.
Because AN/MAA copolymer foam belongs to unicellular structure foam, sandwich material as polymer matrix composites, there is again resistant to elevated temperatures excellent properties simultaneously, therefore being very suitable for the resin injection techniques such as resin transfer moulding (RTM) or VA RTM moulding (VARTM) prepares sandwich structure composite material (DE-C2726260, DE-C2822885, DE-A3304882, US Pat.4316934).For in RTM moulding and VARTM moulding, there is to relatively strict requirement in the aperture of foam, thereby thereby require the less weight that has relatively less suction glue amount to alleviate whole core filled composite material in aperture of foam.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of fine pass AN/MAA copolymer foam, the method is mainly prepared the less AN/MAA copolymer foam in aperture, the different application place of preparing sandwich structure composite material in resin injection techniques such as resin transfer moulding (RTM) or VA RTM moulding (VARTM) to meet copolymer foam by changing initiator amount and whipping agent kind.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for fine pass AN/MAA copolymer foam, with methacrylic acid (MAA), vinyl cyanide (AN) and the 3rd monomer, by adding 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 AN/MAA copolymer foam through high temperature foaming and thermal treatment, 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
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, thickening material are mixed, 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, AN/MAA multipolymer initial foam obtained;
4) the 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 AN/MAA copolymer foam material.
Thickening material of the present invention is gas phase SiO
2, in organobentonite, diatomite, methylcellulose gum, gelatin one or more; 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 N, N-dimethyl urea, one or more in 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 AN/MAA copolymer foam material that the present invention obtains, can meet the different application place that copolymer foam is prepared sandwich structure composite material in resin injection techniques such as resin transfer moulding (RTM) or VA RTM moulding (VARTM).In the Foam Core Sandwich Structure part of space flight and aviation, bullet train, wind-powered electricity generation, boats and ships, medical device equipment, be used widely.
Embodiment
Embodiment 1
A preparation for fine pass AN/MAA copolymer foam, fill a prescription as follows:
| Methacrylic acid | 50 |
| Vinyl cyanide | 50 |
| Methacrylamide | 8 |
| Gas phase SiO 2 | 10 |
| The peroxidation acid tert-butyl ester | 0.4 |
| Diisopropyl azodicarboxylate | 0.15 |
| N, N-dimethyl urea | 10 |
| Allyl methacrylate(AMA) | 4 |
| Maleimide | 3 |
| Propenoic acid, 2-methyl, isobutyl ester | 8 |
Above-mentioned fine pass AN/MAA copolymer foam material preparation method step is as follows:
(1) by methacrylic acid, vinyl cyanide, Methacrylamide, gas phase SiO
2, adding the peroxidation acid tert-butyl ester, Diisopropyl azodicarboxylate, N, N-dimethyl urea, allyl methacrylate(AMA), maleimide, Propenoic acid, 2-methyl, isobutyl ester are according to as above filling a prescription and mix.
(2) step (1) gained solution 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, AN/MAA multipolymer initial foam obtained.
(4) the AN/MAA copolymer foam making is kept to 2 hours under 180 ℃ of conditions, and naturally cool to room temperature, obtain AN/MAA copolymer foam material.
The mean pore size of the AN/MAA copolymer foam material that the present embodiment makes is 50um, is the AN/MAA copolymer foam of fine pass, can be applicable to prepare core filled composite material requirement in RTM or VARTM moulding and inhales the few application scenario of glue amount.
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 |
| The peroxidation acid tert-butyl ester | 0.3 |
| Diisopropyl azodicarboxylate | 0.05 |
| Virahol | 10 |
| Allyl methacrylate(AMA) | 5 |
| Maleimide | 2.2 |
| Tert-butyl Methacrylate | 4 |
Above-mentioned conventional type AN/MAA copolymer foam material preparation method step is as follows:
(1), by methacrylic acid, vinyl cyanide, Methacrylamide, gas-phase silica, add the peroxidation acid tert-butyl ester, Diisopropyl azodicarboxylate, Virahol, allyl methacrylate(AMA), maleimide, Tert-butyl Methacrylate according to as above filling a prescription and mix.
(2) step (1) gained solution 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 mean pore size of the AN/MAA copolymer foam material that this comparative example makes is 500um, is conventional type AN/MAA copolymer foam foam, can be applicable to generally to less demanding application scenario, aperture.
Claims (9)
1. a preparation method for fine pass AN/MAA copolymer foam, is characterized in that: the method is with vinyl cyanide, methacrylic acid and the 3rd monomer, by adding gas phase SiO
2and thickening material, add the first copolymerization of initiator, whipping agent, linking agent, density-controlling agent and nucleator to obtain the copolymerization plate of vinyl cyanide/methacrylic acid simultaneously, then make AN/MAA copolymer foam through high temperature foaming and thermal treatment, 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
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, thickening material are mixed, add initiator, whipping agent, linking agent, density-controlling agent, nucleator, mix and obtain homogeneous solution;
2) solution obtaining is injected by two folded India-rubber strips of parallel plate and seal in die cavity, polyreaction 10-70 hour under 30 ℃ of-70 ℃ of bath temperature conditions, forms methacrylic acid/acrylonitrile compolymer 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, AN/MAA multipolymer initial foam obtained;
4) the AN/MAA copolymer foam making is kept to 1-5 hour under 100 ℃ of-200 ℃ of conditions, and naturally cool to room temperature, obtain AN/MAA copolymer foam material.
2. the preparation method of fine pass AN/MAA copolymer foam according to claim 1, is characterized in that: thickening material is gas phase SiO
2, in organobentonite, diatomite, methylcellulose gum, gelatin one or more.
3. the preparation method of fine pass AN/MAA copolymer foam according to claim 2, is characterized in that: gas phase SiO
2specific surface area be 50-250m
2/ g.
4. the preparation method of fine pass AN/MAA copolymer foam according to claim 1, is characterized in that: the 3rd monomer is acrylic amide or the alkyl-acrylates that contains two keys.
5. the preparation method of fine pass AN/MAA copolymer foam according to claim 4, is characterized in that: the 3rd monomer is one or more in acrylamide, Methacrylamide, methyl acrylate, ethyl propenoate, butyl acrylate.
6. the preparation method of fine pass AN/MAA copolymer foam according to claim 1, is characterized in that: whipping agent is N N-dimethyl urea, one or more in Virahol or isopropylcarbinol.
7. the preparation method of fine pass AN/MAA copolymer foam according to claim 1, is characterized in that: linking agent is allyl acrylate, allyl methacrylate(AMA), magnesium oxide or or Ethylene glycol dimethacrylate.
8. the preparation method of fine pass AN/MAA copolymer foam according to claim 1, is characterized in that: nucleator is Tert-butyl Methacrylate, N-METHYLFORMAMIDE or Propenoic acid, 2-methyl, isobutyl ester.
9. the preparation method of fine pass AN/MAA copolymer foam according to claim 1, is characterized in that: the fine pass AN/MAA copolymer foam making is for the Foam Core Sandwich Structure part of space flight and aviation, bullet train, wind-powered electricity generation, boats and ships, medical device equipment.
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| CN104945553A (en) * | 2015-07-21 | 2015-09-30 | 江苏兆鋆新材料股份有限公司 | Preparation method and application of high-tenacity foam material |
| EP3705505A4 (en) * | 2017-10-31 | 2021-08-11 | Cashem Advanced Materials Hi-tech Co., Ltd. Zhejiang | Method for preparing polymethacrylimide foam using one-step-feeding gelation |
| CN114146489A (en) * | 2021-12-20 | 2022-03-08 | 淄博华源科技创新发展有限公司 | Active nano titanium dioxide microcapsule for denitration ceramic fiber filter tube, preparation method of active nano titanium dioxide microcapsule and denitration ceramic fiber filter tube |
| CN114146487A (en) * | 2021-12-20 | 2022-03-08 | 淄博华源科技创新发展有限公司 | Nano titanium dioxide microcapsule miniemulsion for denitration ceramic fiber filter tube, preparation method of nano titanium dioxide microcapsule miniemulsion and denitration ceramic fiber filter tube |
| CN114146488A (en) * | 2021-12-20 | 2022-03-08 | 淄博华源科技创新发展有限公司 | Denitration ceramic fiber filter tube and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104945553A (en) * | 2015-07-21 | 2015-09-30 | 江苏兆鋆新材料股份有限公司 | Preparation method and application of high-tenacity foam material |
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| CN114146489A (en) * | 2021-12-20 | 2022-03-08 | 淄博华源科技创新发展有限公司 | Active nano titanium dioxide microcapsule for denitration ceramic fiber filter tube, preparation method of active nano titanium dioxide microcapsule and denitration ceramic fiber filter tube |
| CN114146487A (en) * | 2021-12-20 | 2022-03-08 | 淄博华源科技创新发展有限公司 | Nano titanium dioxide microcapsule miniemulsion for denitration ceramic fiber filter tube, preparation method of nano titanium dioxide microcapsule miniemulsion and denitration ceramic fiber filter tube |
| CN114146488A (en) * | 2021-12-20 | 2022-03-08 | 淄博华源科技创新发展有限公司 | Denitration ceramic fiber filter tube and preparation method thereof |
| CN114146488B (en) * | 2021-12-20 | 2023-09-08 | 淄博华源科技创新发展有限公司 | Denitration ceramic fiber filter tube and preparation method thereof |
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Application publication date: 20140122 |