CN103304731B - A kind of homogeneous phase foaming multipolymer and preparation method thereof - Google Patents
A kind of homogeneous phase foaming multipolymer and preparation method thereof Download PDFInfo
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- CN103304731B CN103304731B CN201310252198.8A CN201310252198A CN103304731B CN 103304731 B CN103304731 B CN 103304731B CN 201310252198 A CN201310252198 A CN 201310252198A CN 103304731 B CN103304731 B CN 103304731B
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Abstract
The invention discloses a kind of homogeneous phase foaming multipolymer and preparation method thereof.By acrylic ester monomer, acrylamide monomers, initiator, solubilizing agent, ratio mixing by weight, obtains homogeneous phase foaming multipolymer through prepolymerization and post polymerization.The invention solves acrylamide monomers in preparation process from reaction system, easily separate out the problem causing severe delamination, there is reaction process comparatively stable, the advantage that easy control of reaction conditions, scrap rate are low simultaneously, there is excellent mechanical property.Homogeneous phase foaming multipolymer prepared by the present invention can directly be widely used in the fields such as aerospace, launch vehicle, railway locomotive, boats and ships, wind power generation blade, sports goods, has obvious economic benefit and social benefit.
Description
Technical field
The present invention relates to a kind of multipolymer and preparation method thereof, be specifically related to a kind of homogeneous phase foaming multipolymer and preparation method thereof.
Background technology
Polymethacrylimide (PMI) porous plastics is the rigid foam of a kind of lightweight, closed pore, is the porous plastics that in all polymeric foam plastics, specific tenacity is the highest.Temperature tolerance reaches 240 DEG C, high specific strength and excellent incompressible creep property, the high specific pressure contracting intensity of Polymethacrylimide (PMI) porous plastics can bear the composite resin curing process of 180 ~ 200 DEG C to the dimensional stability requirements of foam, be manufacture the desirable core of Lightweight high-strength composite material sandwich structure, in airliner and conveyor, bullet train, blade of wind-driven generator, launch vehicle and motion and medical device etc., obtain a large amount of application.
Patent CN103073672A and CN103012670A for principal monomer, has prepared polymethacrylimide foam material with esters of acrylic acid and acrylamide monomers, and the monomer polymerization wherein after batching is divided into two steps:
(1) high-temperature stirring prepolymerization: by described uniform mixing liquid at 80 ~ 130 DEG C of electric stirrings, magnetic agitation, ultrasonic agitation or shaking table stirring reaction 5 ~ 60min, obtain pre-polymerization liquid.
(2) low temperature repolymerization: injected by described pre-polymerization liquid in mould, normal temperature places 1 ~ 30min, is then placed in 30 ~ 60 DEG C of water-baths, retains 70 ~ 100h, takes out and obtains transparent block.
Because the fusing point of acrylamide monomers is more than 80 DEG C, lower than being solid-state during fusing point, from reaction system, very easily separating out the bottom depositing to reaction system, occur serious monomer demixing phenomenon.In order to address this problem, above-mentioned patent adopts two-stage polymerization method, efficiently solves the problem of two monomer severe delamination in preparation process.But the pre-polymerization liquid that high-temperature stirring prepolymerisation stage obtains needs to have higher monomer conversion, just can obtain more prepolymer.Thus, with the solublization by prepolymer during low temperature repolymerization, make acrylamide monomers be dissolved in reaction system, present the state of clear homogeneous, polymerization obtains transparent block.Therefore, high-temperature stirring prepolymerisation stage is consuming time longer, and implode easily occurs and obtains waste product, reaction process is unstable, the more difficult control of reaction conditions.
Along with the civil areas such as aircarrier aircraft, railway locomotive, boats and ships, wind power generation blade, sports goods are to the increase of polymethacrylimide plastic foam demand, in order to meet the needs of the national economic development, update existing preparation method, the polymethacrylimide plastic foam that processability is more excellent and kind will cause people to pay close attention to greatly.
Summary of the invention
The object of this invention is to provide a kind of homogeneous phase foaming multipolymer and preparation method thereof.Adopt acrylic ester monomer and acrylamide monomers to be main monomer, after batching, prepare homogeneous phase foaming multipolymer by prepolymerization and post polymerization.
The technical solution used in the present invention is:
One, a homogeneous phase foaming multipolymer, be made up of the raw material of following weight part:
Acrylic ester monomer 30 ~ 80 parts;
Acrylamide monomers 20 ~ 70 parts;
Initiator 0.1 ~ 3 part;
Solubilizing agent 5 ~ 20 parts;
Two, a preparation method for homogeneous phase foaming multipolymer, comprises the steps:
(1) prepare burden: by acrylic ester monomer 30 ~ 80 parts; Acrylamide monomers 20 ~ 70 parts; Initiator 0.1 ~ 3 part; Solubilizing agent 5 ~ 20 parts, mixes by weight, is stirred and stirs 10 ~ 30min at normal temperatures, obtain uniform mixing liquid by electric stirring, magnetic agitation, ultrasonic agitation or shaking table;
(2) prepolymerization: by described uniform mixing liquid at 80 ~ 130 DEG C of electric stirrings, magnetic agitation, ultrasonic agitation or shaking table stirring reaction 2 ~ 20min, obtain pre-polymerization liquid;
(3) post polymerization: injected in mould by described pre-polymerization liquid, be then placed in 30 ~ 60 DEG C of water-baths, retains 70 ~ 100h, takes out and obtains homogeneous phase foaming multipolymer;
Described acrylic ester monomer be in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate any one or with both mixtures of arbitrary proportion.
Described acrylamide monomers be in acrylamide, Methacrylamide any one or with both mixtures of arbitrary proportion.
Described initiator is the mixture of any one or any two kinds and above arbitrary proportion in dicumyl peroxide, dibenzoyl peroxide, di-cyclohexylperoxy dicarbonate, peroxy dicarbonate isopropyl ester, peroxide tert pivalate ester, dilauroyl peroxide, Potassium Persulphate, ammonium persulphate, Sulfothiorine, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Described solubilizing agent is a kind of in ethanol, propyl alcohol, the trimethyl carbinol, Pentyl alcohol, hexalin, n-Heptyl alcohol, n-Octanol or with the mixture of any two kinds and above arbitrary proportion.
Compared with background technology, the beneficial effect that the present invention has is:
The invention solves the problem of two monomer severe delamination in preparation process, there is reaction process comparatively stable simultaneously, the advantage that easy control of reaction conditions, scrap rate are low.Because the fusing point of acrylamide monomers is more than 80 DEG C, lower than being solid-state during fusing point, the bottom depositing to reaction system can being separated out from reaction system, occurring serious monomer demixing phenomenon.
The present invention adopts the method for adding solubilizing agent in reaction system, effectively increases the solubility property of acrylamide monomers in reaction system, can obtain the system of homogeneous phase transparent, thus the effective difficult problem solving acrylamide monomers and separate out from reaction system.Thus, high-temperature stirring prepolymerisation stage does not need to extend the pre-polymerization time, obtains higher monomer conversion with this.Therefore, whole polymerization stage is effectively to avoid the generation of implode, and reaction process is comparatively stable, easy control of reaction conditions, and scrap rate is lower.
Homogeneous phase foaming multipolymer prepared by the present invention can directly be widely used in the fields such as aerospace, launch vehicle, railway locomotive, boats and ships, wind power generation blade, sports goods, has obvious economic benefit and social benefit.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but the present invention is not restricted to following examples.
Embodiment 1:
(1) prepare burden: by 50g methyl methacrylate, 50g acrylamide, 0.05g dibenzoyl peroxide, 0.05g dicumyl peroxide, 2g ethanol, the mixing of 3g propyl alcohol, stir 10min at normal temperatures by electric stirring, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 80 DEG C of electric stirring reaction 20min, obtain pre-polymerization liquid;
(3) repolymerization: injected in mould by described pre-polymerization liquid, be then placed in 60 DEG C of water-baths, retains 70h, takes out and obtains homogeneous phase foaming multipolymer.
The compressive strength of homogeneous phase foaming multipolymer prepared by the present embodiment and modulus of compression are respectively 93.5Mpa and 1.06Gpa.
Embodiment 2:
(1) prepare burden: by 30g β-dimethyl-aminoethylmethacrylate, 70g Methacrylamide, 0.5g dibenzoyl peroxide, the 4g trimethyl carbinol, the mixing of 4g Pentyl alcohol, stir 20min at normal temperatures by magnetic agitation, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 100 DEG C of magnetic agitation reaction 12min, obtain pre-polymerization liquid;
(3) repolymerization: injected in mould by described pre-polymerization liquid, be then placed in 30 DEG C of water-baths, retains 100h, takes out and obtains homogeneous phase foaming multipolymer.
The compressive strength of homogeneous phase foaming multipolymer prepared by the present embodiment and modulus of compression are respectively 89.5Mpa and 1.13Gpa.
Embodiment 3:
(1) prepare burden: by 40g butyl methacrylate, 30g acrylamide, 30g Methacrylamide, 0.5g di-cyclohexylperoxy dicarbonate, 0.5g peroxy dicarbonate isopropyl ester, 2g hexalin, 3g n-Heptyl alcohol, the mixing of 5g n-Octanol, stir 30min at normal temperatures by ultrasonic agitation, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 110 DEG C of ultrasonic agitation reaction 8min, obtain pre-polymerization liquid;
(3) repolymerization: injected in mould by described pre-polymerization liquid, be then placed in 35 DEG C of water-baths, retains 95h, takes out and obtains homogeneous phase foaming multipolymer.
The compressive strength of homogeneous phase foaming multipolymer prepared by the present embodiment and modulus of compression are respectively 95.3Mpa and 1.07Gpa.
Embodiment 4:
(1) prepare burden: by 60g propyl acrylate, 40g acrylamide, 0.5g peroxide tert pivalate ester, 0.5g dilauroyl peroxide, 0.5g Potassium Persulphate, the mixing of 15g ethanol, stirred by shaking table and stir 15min at normal temperatures, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 120 DEG C of shaking table stirring reaction 5min, obtain pre-polymerization liquid;
(3) repolymerization: injected in mould by described pre-polymerization liquid, be then placed in 40 DEG C of water-baths, retains 85h, takes out and obtains homogeneous phase foaming multipolymer.
The compressive strength of homogeneous phase foaming multipolymer prepared by the present embodiment and modulus of compression are respectively 100.4Mpa and 1.03Gpa.
Embodiment 5:
(1) prepare burden: by 50g methyl acrylate, 20g butyl acrylate, 30g Methacrylamide, 0.5g Potassium Persulphate, 0.5g ammonium persulphate, 0.5g Sulfothiorine, 0.5g Diisopropyl azodicarboxylate, the mixing of the 20g trimethyl carbinol, stir 25min at normal temperatures by electric stirring, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 130 DEG C of shaking table stirring reaction 2min, obtain pre-polymerization liquid;
(3) repolymerization: injected in mould by described pre-polymerization liquid, be then placed in 45 DEG C of water-baths, retains 85h, takes out and obtains homogeneous phase foaming multipolymer.
The compressive strength of homogeneous phase foaming multipolymer prepared by the present embodiment and modulus of compression are respectively 110.3Mpa and 1.21Gpa.
Embodiment 6:
(1) prepare burden: by 40g butyl acrylate, 40g ethyl propenoate, 10g acrylamide, 10g Methacrylamide, 2.5g 2,2'-Azobis(2,4-dimethylvaleronitrile), the mixing of 12g hexalin, stir 12min at normal temperatures by magnetic agitation, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 95 DEG C of ultrasonic agitation reaction 15min, obtain pre-polymerization liquid;
(3) repolymerization: injected in mould by described pre-polymerization liquid, be then placed in 48 DEG C of water-baths, retains 90h, takes out and obtains homogeneous phase foaming multipolymer.
The compressive strength of homogeneous phase foaming multipolymer prepared by the present embodiment and modulus of compression are respectively 108.5Mpa and 1.15Gpa.
Embodiment 7:
(1) prepare burden: by 50g β-dimethyl-aminoethylmethacrylate, 15g propyl methacrylate, 35g acrylamide, 1.5g di-cyclohexylperoxy dicarbonate, 1.5g Sulfothiorine, 6g ethanol, the mixing of 3g Pentyl alcohol, stir 18min at normal temperatures by ultrasonic agitation, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 85 DEG C of electric stirring reaction 17min, obtain pre-polymerization liquid;
(3) repolymerization: injected in mould by described pre-polymerization liquid, be then placed in 52 DEG C of water-baths, retains 80h, takes out and obtains homogeneous phase foaming multipolymer.
The compressive strength of homogeneous phase foaming multipolymer prepared by the present embodiment and modulus of compression are respectively 113.4Mpa and 1.19Gpa.
Embodiment 8:
(1) prepare burden: by 25g methyl methacrylate, 30g propyl acrylate, 20g Methacrylamide, 25g acrylamide, 0.4g dicumyl peroxide, 0.4g Diisopropyl azodicarboxylate, 9g n-Octanol, the mixing of 9g propyl alcohol, stirred by shaking table and stir 28min at normal temperatures, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 105 DEG C of magnetic agitation reaction 10min, obtain pre-polymerization liquid;
(3) repolymerization: injected in mould by described pre-polymerization liquid, be then placed in 38 DEG C of water-baths, retains 100h, takes out and obtains homogeneous phase foaming multipolymer.
The compressive strength of homogeneous phase foaming multipolymer prepared by the present embodiment and modulus of compression are respectively 86.7Mpa and 1.01Gpa.
Claims (5)
1. a preparation method for homogeneous phase foaming multipolymer, is characterized in that: be made up of the raw material of following weight part:
Acrylic ester monomer 30 ~ 80 parts;
Acrylamide monomers 20 ~ 70 parts;
Initiator 0.1 ~ 3 part;
Solubilizing agent 5 ~ 20 parts;
The step of the method is as follows:
(1) prepare burden: by acrylic ester monomer 30 ~ 80 parts; Acrylamide monomers 20 ~ 70 parts; Initiator 0.1 ~ 3 part; Solubilizing agent 5 ~ 20 parts; Mix by weight, stirred by electric stirring, magnetic agitation, ultrasonic agitation or shaking table and stir 10 ~ 30min at normal temperatures, obtain uniform mixing liquid;
(2) prepolymerization: by described uniform mixing liquid at 80 ~ 130 DEG C of electric stirrings, magnetic agitation, ultrasonic agitation or shaking table stirring reaction 2 ~ 20min, obtain pre-polymerization liquid;
(3) post polymerization: injected in mould by described pre-polymerization liquid, be then placed in 30 ~ 60 DEG C of water-baths, retains 70 ~ 100h, takes out and obtains homogeneous phase foaming multipolymer.
2. the preparation method of a kind of homogeneous phase foaming multipolymer according to claim 1, is characterized in that: described acrylic ester monomer be in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate any one or with both mixtures of arbitrary proportion.
3. the preparation method of a kind of homogeneous phase foaming multipolymer according to claim 1, is characterized in that: described acrylamide monomers be in acrylamide, Methacrylamide any one or with both mixtures of arbitrary proportion.
4. the preparation method of a kind of homogeneous phase foaming multipolymer according to claim 1, is characterized in that: described initiator is the mixture of any one or any two kinds and above arbitrary proportion in dicumyl peroxide, dibenzoyl peroxide, di-cyclohexylperoxy dicarbonate, peroxy dicarbonate isopropyl ester, peroxide tert pivalate ester, dilauroyl peroxide, Potassium Persulphate, ammonium persulphate, Sulfothiorine, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
5. the preparation method of a kind of homogeneous phase foaming multipolymer according to claim 1, is characterized in that: described solubilizing agent is the mixture of any one or any two kinds and above arbitrary proportion in ethanol, propyl alcohol, the trimethyl carbinol, Pentyl alcohol, hexalin, n-Heptyl alcohol, n-Octanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102225983A (en) * | 2011-05-03 | 2011-10-26 | 浙江理工大学 | Imide group-containing polymer foam material and preparation method thereof |
| CN103012670A (en) * | 2012-12-21 | 2013-04-03 | 浙江理工大学 | Isotrope polymethacrylimide foam material and preparation method thereof |
| CN103073672A (en) * | 2013-01-15 | 2013-05-01 | 浙江理工大学 | In-situ reinforced polymethacrylimide foam material and preparation method thereof |
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| DE102010038716A1 (en) * | 2010-07-30 | 2012-02-02 | Evonik Degussa Gmbh | Process for in-mold foaming with a foamable medium and cover layers and plastic molding obtainable thereby |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102225983A (en) * | 2011-05-03 | 2011-10-26 | 浙江理工大学 | Imide group-containing polymer foam material and preparation method thereof |
| CN103012670A (en) * | 2012-12-21 | 2013-04-03 | 浙江理工大学 | Isotrope polymethacrylimide foam material and preparation method thereof |
| CN103073672A (en) * | 2013-01-15 | 2013-05-01 | 浙江理工大学 | In-situ reinforced polymethacrylimide foam material and preparation method thereof |
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