CN103936896A - Preparation method of polymeric material - Google Patents
Preparation method of polymeric material Download PDFInfo
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- CN103936896A CN103936896A CN201310021172.2A CN201310021172A CN103936896A CN 103936896 A CN103936896 A CN 103936896A CN 201310021172 A CN201310021172 A CN 201310021172A CN 103936896 A CN103936896 A CN 103936896A
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Abstract
The invention provides a preparation method of polyurethane or polyacrylate and composite materials thereof by use of a frontal polymerization reaction. The method comprises the following steps: A, the following components are evenly mixed, the components are as follows: 70-98% by weight of polymer monomer, 2-4% by weight of an initiator, 0-2% by weight of a catalyst and 0-28% by weight of a solvent; B, the components are mixed into a reactor for a short time of heating in one end of the reactor, then the heating is stopped, and the frontal polymerization reaction can be completed with the help of heat from exothermic reaction. According to the method the energy consumption in the process of synthesis can be greatly reduced, materials with more excellent performances can be synthesized.
Description
Technical field
The present invention relates to a kind of preparation method of polymer materials, relate in particular to a kind of method of preparing urethane or polyacrylic ester and matrix material thereof with Frontal Polymerization reaction.
Background technology
Frontal Polymerization (frontal polymerization, FP) is polymer and the matrix material preparation and the new technology of processing developing rapidly in recent years.It is that the heat of utilizing monomer id reaction to produce maintains polyreaction and carries out, a kind of new polymerization process that is polymkeric substance by conversion of monomer.Typical reaction process is: first the mixture that contains monomer and initiator packed in tube-type reactor, and in any one end heating of reactor, initiator decomposes, trigger monomer polymerization reaction take place, emits heat; Polymerization reaction heat, to the unreacted regional diffusion of low temperature, forms narrow conversion zone in tube-type reactor, is polymkeric substance by conversion of monomer, is called polymerization front end (front); Polymerization front end, withdrawing after thermal source from being sent to unreacted monomer regional diffusion, continues trigger monomer polymerization, produces the working cycle that reaction-thermodiffusion intercouples, and reaction front end is constantly pushed ahead until whole reactor.
Compared with traditional polymerization, it is energy-conservation that Frontal Polymerization tool has the following advantages (1): polyreaction is to be provided by the heat release of monomer id reaction, does not need the external world to continue to provide energy; (2) pollution-free: reaction system is not used solvent, without removing solvent; (3) unique product pattern: because Frontal Polymerization reaction zone temperature is high, reaction is fast, can effectively suppress to be separated, and obtains the more uniform polymer blending material of microtexture; (4) reaction fast: reaction is carried out a narrow front end area, and temperature is high, and fast, transformation efficiency is high in reaction.Based on this, Frontal Polymerization can be fast and convenient prepare polymkeric substance and matrix material thereof, obtain the material that performance is more excellent, and can obtain the thicker material that photopolymerization or conventional polymeric mode are difficult to obtain, also can be used for the Rapid-Repair of space flight, naval vessel composite material structural member.
Polyacrylic ester and urethane are two base polymers of industrial large usage quantity.Polyacrylic ester is formed by the chain reaction polymerization of acrylate free radical, the multipolymer that the soft or hard section that urethane is progressively polymerized by polyethers or polyester polyol and isocyanic ester alternately forms, and the conventional traditional bulk polymerization of this two classes material is synthetic.Because bulk polymerization speed is slow, need the external world to continue to provide energy, efficiency is low, if adopt the method for Frontal Polymerization, can greatly reduce the energy consumption in building-up process, synthesizes the material that performance is more excellent.
Summary of the invention
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or at least provides a kind of useful business to select.
The present invention be intended to solve prior art problem one of at least.One aspect of the present invention provides a kind of preparation method of polymer materials, and its step comprises successively:
Following component is mixed, and wherein the weight percent of the shared total amount of each component is:
Polymer monomer 70-98%
Initiator 2-4%
Catalyzer 0-2%
Solvent 0-28%
Said components is mixed and poured in reactor, carry out after short period of time heating in one end of reactor, stop heating, complete Frontal Polymerization by the caloric autocataiysis of thermopositive reaction.
According to concrete example of the present invention, above-mentioned preparation method further comprises:
Following component is mixed, and wherein the weight percent of the shared total amount of each component is:
Polymer monomer 76%
Initiator 3%
Catalyzer 1%
Solvent 20%
B, by said components mix pour in reactor, carry out after short period of time heating in one end of reactor, stop heating, complete Frontal Polymerization by the caloric autocataiysis of thermopositive reaction.
According to concrete example of the present invention, wherein polymer monomer is any one or more in acrylate monomer, polyester polyol and multicomponent isocyanate system.
Aforesaid propylene acid ester monomer is any one or more in vinylformic acid, Hydroxyethyl acrylate, sodium methacrylate, zinc dimethacrylate, methacrylic acid 2-hydroxyl ethyl ester and dimethacrylate glycol ester.
Above-mentioned polyester polyol is any one or more in polyether glycol, polyester polyol, Viscotrol C, epoxy resin.
Above-mentioned polyester polyol is any one or more in polyether glycol or polyester polyol.Especially polypropylene glycol.
Above-mentioned multicomponent isocyanate is 2,4 toluene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 1, any one or more in 6-di-isocyanate, isophorone diisocyanate, poly methylene poly phenyl poly isocyanate.
In above-mentioned polyester polyol and multicomponent isocyanate system, the ratio of polyester polyol and multicomponent isocyanate is 10 ~ 16:60 ~ 76, is preferably 14:62.
According to concrete example of the present invention, in step B, Heating temperature is selected from 60-90 DEG C, is selected from 30 ~ 60 seconds heat-up time, and heated pressure is selected from 1 × 105 ~ 3 × 105pa.
According to concrete example of the present invention, initiator is any one or more in BDO, 2,3-butanediol, glycol ether, glycerine, Glycerin, sorbyl alcohol, Sodium Persulfate (potassium), ammonium persulphate, benzoyl peroxide.
According to concrete example of the present invention, catalyzer is the metallic compound of aliphatics and alicyclic tertiary amine or solubility, especially organo-tin compound.Comprise triethylenediamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, N methyldiethanol amine, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, trolamine, tetramethyl guanidine, N, N, N ', N '-tetramethyl-Edamine, N, N-dimethyl C10-C16 amine, N, N-dimethyl cyclohexyl amine, N, N-diformazan piperazine, two (2-hydroxypropyl)-2-first piperazine, two (β-diformazan aminoethyl) ether, stannous octoate, dibutyl tin laurate, stannous oleate, dibutyltin diacetate.
According to concrete example of the present invention, catalyzer is any one or more in stannous octoate or dibutyl tin laurate.
According to concrete example of the present invention, solvent is any one or more in toluene, dimethylbenzene, N-BUTYL ACETATE, dimethyl sulfoxide (DMSO), dimethyl formamide.
According to concrete example of the present invention, said components also comprises thickening material or filler, auxiliary agent, and filler is any one or more in titanium dioxide, zinc oxide, lithopone, hollow glass micropearl.
In monomer polymerization process of the present invention, emit a large amount of heats, heat conducts by forms such as convection current, cause between front reaction district and monomer having larger temperature head, and density polymer is greater than monomer, is difficult to form stable front reaction district.By solidifying agent encapsulated, add the method such as auxiliary agent, suppress solidifying agent activity at low temperatures, but do not affect activity at high temperature.Object is to increase shelf lives of reaction system, the front reaction district that formation can steady growth.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Brief description of the drawings
Fig. 1 urethane Frontal Polymerization reaction Fourier infrared spectra.Wherein a place is expressed as reactor synthetic spectrum figure, and b place is expressed as Frontal Polymerization synthetic spectrum figure.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example is only for the present invention is described, and should not be considered as limiting scope of the present invention.
Embodiment mono-
The reaction of polyacrylic ester Frontal Polymerization
100g acrylate monomer, pours 10mm diameter test tube into, slowly drips 0.1% benzoyl peroxide, with 0.5cm place under heating rod immersed in liquid level be heated to 60 DEG C of reaction 40s recession from.Pressure is 1 normal atmosphere.Show that by Fourier's infrared spectra Frontal Polymerization has identical characteristic peak with the polyacrylic ester of still reaction synthesized, the polyacrylic ester of being schemed known Frontal Polymerization synthesized by SEM has good dispersiveness, prove that Frontal Polymerization has stable conversion zone, make the polyacrylic ester Stability Analysis of Structures of synthesized.
Example two
The reaction of urethane Frontal Polymerization
Solvent adopts dimethylbenzene, its massfraction is 20%, 2,4-tolylene diisocyanate (TDI) massfraction 14%, 1,4-butyleneglycol (BG) massfraction is 3%, molecular weight is that 2000 polypropylene glycol (PPG) massfraction is 62%, dibutyl tin laurate (DBTDL) massfraction is 1%, first by BG, and PPG, dimethylbenzene and DBTDL pour 10mm diameter test tube into according to aforementioned proportion, slight concussion test tube makes it to mix, the last TDI that slowly drips, with the heating 40s of 0.5cm place under heating rod immersed in liquid level drop back from.Pressure is 1 normal atmosphere.Show that by Fourier's infrared spectra Frontal Polymerization has identical characteristic peak with the urethane of still reaction synthesized, the urethane of being schemed known Frontal Polymerization synthesized by SEM has good dispersiveness, prove that Frontal Polymerization has stable conversion zone, make the polyurethane structural of synthesized stable.
Example three
Urethane acrylate Frontal Polymerization reaction scheme
First add the TDI of metering, the polyether Glycols of dehydration ([NCO]/[OH]=2/1, mol/ mol), 45 % (quality) DMSO (solvent), appropriate DBTDL (catalyzer), be warmed up to 75 DEG C, insulation reaction 4 h, are cooled to 45 DEG C, must hold NCO base performed polymer.At 45 DEG C, in above-mentioned reaction solution, drip the HPA ([TDI]/[HPA]=1/2, mol/ mol) measuring.Be added dropwise to complete (approximately 1 h) after, be warming up to 55 DEG C, insulation reaction 10 h, FTIR follows the tracks of reaction, when the NCO at 2270～2273cm-1 place absorption peak disappear, stopped reaction, is down to room temperature, must hold thiazolinyl macromonomer.At room temperature, to above-mentioned HPA ([end thiazolinyl macromonomer]/[the HPA]=1:4 that adds metering in the reaction flask of holding thiazolinyl macromonomer that is equipped with, mol/ mol), the methyl-sulphoxide (DMSO) of thermal free radical initiator and 45% (quality), stir.Appropriate this mixture is injected to the test tube of 10mm diameter, with 0.5cm place under heating rod immersed in liquid level be heated to react drop back from, obtain urethane acrylate multipolymer.The infrared absorption peak of multipolymer of measuring Frontal Polymerization with Fourier infrared spectrograph is similar to the absorption peak of batchwise polymerization product.Measure the thermostability of Frontal Polymerization product higher than the product of batchwise polymerization by TGA
Above about specific descriptions of the present invention, only for being described, the present invention is not limited to the technical scheme that embodiment of the present invention rope is described, those of ordinary skill in the art should be appreciated that still and can modify or be equal to replacement the present invention, reached constructed effect; Use needs as long as meet, all within protection scope of the present invention.
Claims (10)
1. a preparation method for polymer materials, its step comprises successively:
A, following component is mixed, wherein the weight percent of the shared total amount of each component is:
Polymer monomer 70-98%
Initiator 2-4%
Catalyzer 0-2%
Solvent 0-28%
B, by said components mix pour in reactor, carry out after short period of time heating in one end of reactor, stop heating, complete Frontal Polymerization by the caloric autocataiysis of thermopositive reaction.
2. preparation method according to claim 1, is characterized in that, polymer monomer is any one or more in acrylate monomer or polyester polyol and multicomponent isocyanate system.
3. preparation method according to claim 2, it is characterized in that, acrylate monomer is any one or more in vinylformic acid, Hydroxyethyl acrylate, sodium methacrylate, zinc dimethacrylate, methacrylic acid 2-hydroxyl ethyl ester and dimethacrylate glycol ester.
4. preparation method according to claim 2, is characterized in that, polyester polyol is any one or more in polyether glycol, polyester polyol, Viscotrol C, epoxy resin.
5. preparation method according to claim 2, it is characterized in that, multicomponent isocyanate is 2,4-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 1, any one or more in 6-di-isocyanate, isophorone diisocyanate, poly methylene poly phenyl poly isocyanate.
6. preparation method according to claim 2, is characterized in that, the ratio of polyester polyol and multicomponent isocyanate is 10 ~ 16:60 ~ 76.
7. preparation method according to claim 1, is characterized in that, in step B, Heating temperature is selected from 60-90 DEG C, is selected from 30 ~ 60 seconds heat-up time, and heated pressure is selected from 1 × 105 ~ 3 × 105pa.
8. preparation method according to claim 1, it is characterized in that, initiator is any one or more in BDO, 2,3-butanediol, glycol ether, glycerine, Glycerin, sorbyl alcohol, Sodium Persulfate (potassium), ammonium persulphate, benzoyl peroxide.
9. preparation method according to claim 1, is characterized in that, catalyzer is the metallic compound of aliphatics and alicyclic tertiary amine or solubility.
10. preparation method according to claim 1, is characterized in that, solvent is any one or more in toluene, dimethylbenzene, N-BUTYL ACETATE, dimethyl sulfoxide (DMSO), dimethyl formamide.
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| CN201310021172.2A CN103936896A (en) | 2013-01-21 | 2013-01-21 | Preparation method of polymeric material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225901A (en) * | 2020-09-30 | 2021-01-15 | 华南理工大学 | Modified castor oil based UV (ultraviolet) curing polyurethane acrylate and preparation method thereof |
| CN113214451A (en) * | 2021-04-08 | 2021-08-06 | 东莞市米儿塑胶原料有限公司 | TPU preparation method based on front-end polymerization process |
Citations (3)
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| CN1305970A (en) * | 2000-01-20 | 2001-08-01 | 希尔蒂股份公司 | Mortar able to harden by polymerized in-situ and method of reinforcing roofbolt |
| US6313237B1 (en) * | 1998-08-03 | 2001-11-06 | The University Of Southern Mississippi | Functionally gradient polymeric materials |
| CN1664006A (en) * | 2005-02-05 | 2005-09-07 | 南京工业大学 | Polyurethane and process for preparing nano composite materials thereof |
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2013
- 2013-01-21 CN CN201310021172.2A patent/CN103936896A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6313237B1 (en) * | 1998-08-03 | 2001-11-06 | The University Of Southern Mississippi | Functionally gradient polymeric materials |
| CN1305970A (en) * | 2000-01-20 | 2001-08-01 | 希尔蒂股份公司 | Mortar able to harden by polymerized in-situ and method of reinforcing roofbolt |
| CN1664006A (en) * | 2005-02-05 | 2005-09-07 | 南京工业大学 | Polyurethane and process for preparing nano composite materials thereof |
Non-Patent Citations (2)
| Title |
|---|
| ROBERTA SANNA等: "Polymer Hydrogels of 2-Hydroxyethyl Acrylate and Acrylic Acid Obtained by Frontal Polymerization", 《POLYMER CHEMISTRY》, vol. 50, no. 8, 31 January 2012 (2012-01-31), pages 1515 - 1520 * |
| 吴校彬等: "聚氨酯-丙烯酸酯的前端自由基聚合", 《化工学报》, vol. 58, no. 6, 30 June 2007 (2007-06-30), pages 1581 - 1586 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225901A (en) * | 2020-09-30 | 2021-01-15 | 华南理工大学 | Modified castor oil based UV (ultraviolet) curing polyurethane acrylate and preparation method thereof |
| CN112225901B (en) * | 2020-09-30 | 2022-03-29 | 华南理工大学 | Modified castor oil based UV (ultraviolet) curing polyurethane acrylate and preparation method thereof |
| CN113214451A (en) * | 2021-04-08 | 2021-08-06 | 东莞市米儿塑胶原料有限公司 | TPU preparation method based on front-end polymerization process |
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Application publication date: 20140723 |