CN103554355A - Preparation method of needle-like wollastonite modified acrylic nitrile (AN)/methyl acrylic acid (MAA) copolymer foam material - Google Patents
Preparation method of needle-like wollastonite modified acrylic nitrile (AN)/methyl acrylic acid (MAA) copolymer foam material Download PDFInfo
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- CN103554355A CN103554355A CN201310502070.2A CN201310502070A CN103554355A CN 103554355 A CN103554355 A CN 103554355A CN 201310502070 A CN201310502070 A CN 201310502070A CN 103554355 A CN103554355 A CN 103554355A
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Abstract
The invention discloses a preparation method of a needle-like wollastonite modified acrylic nitrile (AN)/methyl acrylic acid (MAA) copolymer rigid foam material. The main materials are acrylonitrile (AN) and methyl acrylic acid (MAA) and the AN/ MAA copolymer rigid foam material is modified by adding the processed w needle-like wollastonite, so that the tensile strength and elongation at break of the prepared needle-like wollastonite modified AN/ MAA copolymer rigid foam material are remarkably improved. The foam material, as filling material or sandwich material, can be widely applied to space flight and aviation, high-speed trains, wind power, ships, health care and other fields.
Description
Technical field
The present invention relates to a kind of preparation method of acicular wollastonite modification AN/MAA copolymer foam material.
Background technology
AN/MAA copolymer foam is the rigid structure porous plastics of Good Heat-resistance, the equal decrease to some degree of its every mechanical property of Polymethacrylimide (PMI) foam relatively, yet its main raw material vinyl cyanide (AN) relatively prepare Polymethacrylimide (PMI) foam main raw material methacrylonitrile (MAN) but excellent price advantage, the cost ratio of vinyl cyanide and methacrylonitrile is about 1:40.And the technology of preparing of methacrylonitrile is also by abroad being monopolized, the every mechanical property that therefore improves AN/MAA copolymer foam makes it to compare favourably and become an important problem with Polymethacrylimide (PMI) foam, is of great practical significance.
Wollastonite is a kind of bisilicate mineral of calcium, theoretical chemistry composition (massfraction) CaO48.3%, SiO
251.7%.The wollastonite of natural output is needle-like, radial, fibrous agrregate etc. conventionally.Because it is nontoxic, the physico-chemical properties such as low oil absorbency, low water absorbable, high thermostability and chemical stability, good dielectric properties, whiteness height, are widely used in the industrial sectors such as architectural pottery, coating, plastics, machinery, electronics, rubber, chemical industry, metallurgy and refractory materials.The wollastonite of fibrous crystal structure, the acicular powder forming through special powder complete processing, can be applicable to engineering plastics and friction materials.Wollastonite be a kind of emerging mineral material it there is unique physicochemical property therefore have very large advantage and development prospect, along with the also diversification more of research direction of the scientific and technological development wollastonite of social progress.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of acicular wollastonite modification AN/MAA copolymer foam material, the method improves the mechanical property of AN/MAA copolymer foam material, is especially embodied in the raising of tensile strength.Because acicular wollastonite is inorganic materials, therefore by MMA, wollastonite modifying surface is processed, making it can be better compatible with AN/MAA system.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for acicular wollastonite modification AN/MAA copolymer foam material, is characterized in that: the method is with vinyl cyanide, methacrylic acid and the 3rd monomer, by adding the w acicular wollastonite of processing, gas phase SiO
2thickening 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, the foaming of process high temperature and thermal treatment make the AN/MAA copolymer foam of flame retardant type again, specifically comprise the following steps:
(1) processing of w acicular wollastonite:
With MMA to wollastonite surface modification treatment: take a certain amount of wollastonite powder and be placed in there-necked flask, add in proportion water and MMA, wherein, 100 parts of wollastonites add 80 parts of water, 20 parts of MMA, vigorous stirring, slowly be warming up to 70 ~ 75 ℃, by amount of monomer, add 0.6% ~ 0.7% water soluble starter, after reaction, filter, standby be dried to permanent quality in 120 ℃ of baking ovens after;
(2) formula is pressed following parts by weight:
Methacrylic acid 40-60
Vinyl cyanide 40-60
The 3rd monomer 5-20
The w acicular wollastonite 1-30 processing
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, the w acicular wollastonite of processing, thickening material are mixed, add initiator, whipping agent, linking agent, density-controlling agent, nucleator, mix and obtain homogeneous solution;
(3) 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;
(4) 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, acicular wollastonite modification AN/MAA multipolymer initial foam obtained;
(5) the acicular wollastonite modification 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 acicular wollastonite modification 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; The w acicular wollastonite of described processing is through MMA surface treatment; 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 improves the mechanical property of AN/MAA copolymer foam material, is especially embodied in the raising of tensile strength.Because acicular wollastonite is inorganic materials, therefore by MMA, wollastonite modifying surface is processed, making it can be better compatible with AN/MAA system.
Foam materials tensile strength and elongation at break that the present invention makes significantly improve.Can be used as in various fields such as space flight and aviation, bullet train, wind-powered electricity generation, boats and ships, medical treatment packing material or sandwich material.
Embodiment
Embodiment 1
A preparation for acicular wollastonite modification AN/MAA copolymer foam material, fill a prescription as follows:
| Methacrylic acid | 50 |
| Vinyl cyanide | 50 |
| Methacrylamide | 8 |
| Gas phase SiO 2 | 10 |
| The acicular wollastonite of processing | 30 |
| Peroxidized t-butyl perbenzoate | 0.5 |
| 2,2'-Azobis(2,4-dimethylvaleronitrile) | 0.05 |
| N methylformamide | 10 |
| Allyl methacrylate(AMA) | 4 |
| Maleimide | 3 |
| Tert-butyl Methacrylate | 8 |
Above-mentioned a kind of acicular wollastonite modification AN/MAA copolymer foam material material preparation method step is as follows:
(1) processing of w acicular wollastonite:
With MMA to wollastonite surface modification treatment: take a certain amount of wollastonite powder and be placed in there-necked flask, add in proportion water and MMA(100 part wollastonite to add 80 parts of water, 20 parts of MMA), vigorous stirring, slowly be warming up to 70 ~ 75 ℃, by amount of monomer, add 0.7% azo diisobutyl amidine hydrochloride, after reaction for some time, filter.Standby be dried to permanent quality in 120 ℃ of baking ovens after.
(2) by methacrylic acid, vinyl cyanide, Methacrylamide, gas phase SiO
2, the acicular wollastonite of processing, add peroxidized t-butyl perbenzoate, 2,2'-Azobis(2,4-dimethylvaleronitrile), N methylformamide, allyl methacrylate(AMA), maleimide, Tert-butyl Methacrylate to mix according to as above formula.
(3) step (2) 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.
(4) by preheating under 100-150 ℃ of condition of copolymerization plate placement 6 hours, then the 60min that foams under 210 ℃ of conditions, acicular wollastonite modification AN/MAA multipolymer initial foam obtained.
(5) the acicular wollastonite modification AN/MAA multipolymer initial foam making is kept to 2 hours under 180 ℃ of conditions, and naturally cool to room temperature, obtain acicular wollastonite modification AN/MAA copolymer foam material.
The AN/MAA copolymer foam material of the acicular wollastonite modification that the present embodiment makes, its density is 52Kg/m after tested
3, tensile strength is 2.5MPa.
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 |
| Peroxidized t-butyl perbenzoate | 0.5 |
| 2,2'-Azobis(2,4-dimethylvaleronitrile) | 0.05 |
| N methylformamide | 10 |
| Allyl methacrylate(AMA) | 4 |
| Maleimide | 3 |
| Tert-butyl Methacrylate | 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 peroxidized t-butyl perbenzoate, 2,2'-Azobis(2,4-dimethylvaleronitrile), N methylformamide, allyl methacrylate(AMA), maleimide, Tert-butyl Methacrylate 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 the present embodiment makes is AN/MAA copolymer foam material routinely, and its density is 54Kg/m after tested
3, tensile strength is 1.6MPa.
By embodiment 1 and comparative example 1, can be found out, acicular wollastonite modification AN/MAA copolymer foam material tensile strength obviously improve.
A kind of acicular wollastonite modification AN/MAA copolymer foam material that the present invention obtains can be used as packing material or sandwich material in various fields such as space flight and aviation, bullet train, wind-powered electricity generation, boats and ships, medical treatment, aspect tensile strength, its performance can compare favourably with PMAm imine foam material.
Claims (9)
1. a preparation method for acicular wollastonite modification AN/MAA copolymer foam material, is characterized in that: the method is with vinyl cyanide, methacrylic acid and the 3rd monomer, by adding the w acicular wollastonite of processing, gas phase SiO
2thickening 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, the foaming of process high temperature and thermal treatment make the AN/MAA copolymer foam of flame retardant type again, specifically comprise the following steps:
(1) processing of w acicular wollastonite:
With MMA to wollastonite surface modification treatment: take a certain amount of wollastonite powder and be placed in there-necked flask, add in proportion water and MMA, wherein, 100 parts of wollastonites add 80 parts of water, 20 parts of MMA, vigorous stirring, slowly be warming up to 70 ~ 75 ℃, by amount of monomer, add 0.6% ~ 0.7% water soluble starter, after reaction, filter, standby be dried to permanent quality in 120 ℃ of baking ovens after;
(2) formula is pressed following parts by weight:
Methacrylic acid 40-60
Vinyl cyanide 40-60
The 3rd monomer 5-20
The w acicular wollastonite 1-30 processing
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, the w acicular wollastonite of processing, thickening material are mixed, add initiator, whipping agent, linking agent, density-controlling agent, nucleator, mix and obtain homogeneous solution;
(3) 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;
(4) 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, acicular wollastonite modification AN/MAA multipolymer initial foam obtained;
(5) the acicular wollastonite modification 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 acicular wollastonite modification AN/MAA copolymer foam material.
2. the preparation method of acicular wollastonite modification AN/MAA copolymer foam material according to claim 1, is characterized in that: the w acicular wollastonite of processing is for to process wollastonite modifying surface with MMA.
3. the preparation method of acicular wollastonite modification AN/MAA copolymer 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 acicular wollastonite modification AN/MAA copolymer 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 acicular wollastonite modification AN/MAA copolymer foam material according to claim 1, is characterized in that: the 3rd monomer is acrylic amide or the alkyl-acrylates that contains two keys.
6. the preparation method of acicular wollastonite modification AN/MAA copolymer 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 acicular wollastonite modification AN/MAA copolymer 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 acicular wollastonite modification AN/MAA copolymer 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 acicular wollastonite modification AN/MAA copolymer 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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| CN201310502070.2A CN103554355A (en) | 2013-10-23 | 2013-10-23 | Preparation method of needle-like wollastonite modified acrylic nitrile (AN)/methyl acrylic acid (MAA) copolymer foam material |
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| CN201310502070.2A CN103554355A (en) | 2013-10-23 | 2013-10-23 | Preparation method of needle-like wollastonite modified acrylic nitrile (AN)/methyl acrylic acid (MAA) copolymer foam material |
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Cited By (3)
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| CN109082879A (en) * | 2018-07-05 | 2018-12-25 | 惠州市恒吉纺织品有限公司 | Flame retardant fabric and its processing technology with comfort |
| CN111040230A (en) * | 2019-12-12 | 2020-04-21 | 浙江中科恒泰新材料科技有限公司 | PMI foam with high elongation at break and preparation method thereof |
| EP3705505B1 (en) * | 2017-10-31 | 2024-05-22 | Cashem Advanced Materials Hi-tech Co., Ltd. Zhejiang | Method for preparing polymethacrylimide foam using one-step-feeding gelation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3705505B1 (en) * | 2017-10-31 | 2024-05-22 | Cashem Advanced Materials Hi-tech Co., Ltd. Zhejiang | Method for preparing polymethacrylimide foam using one-step-feeding gelation |
| CN109082879A (en) * | 2018-07-05 | 2018-12-25 | 惠州市恒吉纺织品有限公司 | Flame retardant fabric and its processing technology with comfort |
| CN109082879B (en) * | 2018-07-05 | 2020-12-04 | 惠州市恒吉纺织品有限公司 | Comfortable flame-retardant fabric and processing technology thereof |
| CN111040230A (en) * | 2019-12-12 | 2020-04-21 | 浙江中科恒泰新材料科技有限公司 | PMI foam with high elongation at break and preparation method thereof |
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Application publication date: 20140205 |