CN101870749B - Method for inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation - Google Patents
Method for inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation Download PDFInfo
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- CN101870749B CN101870749B CN2009103113848A CN200910311384A CN101870749B CN 101870749 B CN101870749 B CN 101870749B CN 2009103113848 A CN2009103113848 A CN 2009103113848A CN 200910311384 A CN200910311384 A CN 200910311384A CN 101870749 B CN101870749 B CN 101870749B
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Abstract
The invention relates to a method for inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation, comprising the following steps of (1) purifying MMA (Methyl methacrylate) monomer; (2) dissolving PMMA (Polymethyl methacrylate) in the purified MMAmonomer with the PMMA (Polymethyl methacrylate) consumption amount being 3-20% of the MMA monomer in mass part; (3) ultrasonic radiating the MMA monomer with the PMMA dissolved therein for 1-5h in an ultrasonic field with the ultrasonic intensity of sound power intensity of 0.1-2w/cm2 and ultrasonic frequency of 20kHz-1MHz; and (4) performing reaction on the monomer radiated for 10-36h under the heat-preserved condition of 65-110 DEG C. The PMMA product obtained by using the invention has higher glass transition temperature and narrower molecular weight polydispersity indexes.
Description
Technical field
The present invention relates to a kind of method of utilizing inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation.
Background technology
Radical polymerization is development polymerization methods the earliest in the polymer science, still occupies larger specific gravity so far.Mass polymerization is to realize one of important way of radical polymerization, is commonly used to produce transparent light goods, the molecular weight distribution broad.Polymerization system is made up of monomer and a small amount of initiator (or nothing), and product is pure, and aftertreatment is simple.(MethylMethacrylate, mass polymerization MMA) generally constitute polymerization system by monomer and initiator such as Diisopropyl azodicarboxylate or dibenzoyl peroxide etc., obtain product after reacting certain hour at a certain temperature for methyl methacrylate.Because the use of initiator has inevitably retained its residue in the polymerization products obtained therefrom.
Ultrasonic wave is meant the sound wave of vibration frequency range between 20kHz～1000MHz.Since nineteen thirty had been reported hyperacoustic chemical action for Richards and Loomis, hyperacoustic various chemical effects had caused people's extensive concern.Sonochemistry Theoretical Calculation and corresponding experiment show, the ultrasonic cavitation effect produces the high temperature of thousands of K and the highly compressed extreme environment of tens of MPas around can making the cavitation bubble phase interface, solvent, monomer or macromolecular chain are decomposed or the generation free radical that breaks, and this free radical is expected to be applied to cause the mass polymerization of MMA.
Summary of the invention
The present invention utilizes the mass polymerization of ultrasonic irradiation initiation MMA, and the manufacturing polymethylmethacrylate (PolymethylMethacrylate, PMMA).This product does not contain initiator residue, the purity superelevation, and the field of material purity being had relatively high expectations at polymer optical fiber etc. is widely used.
Technical solution of the present invention is: the present invention is a kind of method of utilizing inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation, and its special character is: this method may further comprise the steps:
1) the MMA monomer is purified;
2) dissolve PMMA in the MMA monomer after purification, the PMMA consumption is 3%～20% of a monomer M MA mass fraction;
3) the MMA monomer that will dissolve behind the PMMA is that ultrasonic intensity is that sound power density is at 0.1～2w/cm in condition
2,, ultrasonic frequency is ultrasonic irradiation 1～5h in the ultrasonic wave field of 20kHz～1MHz;
4) with the monomer behind the irradiation be insulation reaction 10～36h under 65 ~ 110 ℃ the condition in temperature,
Above-mentioned steps 1) concrete steps in are as follows:
1.1) at first clean the MMA monomer repeatedly with isopyknic 10%NaOH solution, till washings is colourless;
1.2) secondly be washed till neutrality with deionized water;
1.3) use anhydrous sodium sulfate dehydration then;
1.4) last underpressure distillation.
Above-mentioned steps 1.4) underpressure distillation is divided into the collection of three parts in, collect distillation cut in the early stage (small amount of liquid that steams during the distillation beginning respectively, account for whole original monomer volumes to be distilled 5%～15%), distillation cut in mid-term and distillation later stage cut (remaining small amount of liquid when distillation is nearly finished, account for whole original monomer volumes to be distilled 5%～15%).
Above-mentioned steps 1.4) condition of underpressure distillation is that vacuum tightness is 0.03～0.1Mpa in, and distillation temperature is 45～65 ℃.
Above-mentioned steps 1.4) vacuum distillation process is twice in.
Above-mentioned steps 4) monomer in behind the irradiation is to be incubated 6～24h down at 65～80 ℃, is warmed up to 80～90 ℃ of insulation 2～6h, is warmed up to 100～110 ℃ of insulation 2～6h again.
Compare with the traditional method products obtained therefrom, gained PMMA product of the present invention has high glass transition and narrower molecular weight polydispersity coefficient.Thereby this invention products obtained therefrom thermotolerance height, molecule regularity height.And the present invention do not add any initiator in preparation process, and therefore this polymerization process products obtained therefrom does not contain initiator, based on very high purity.
Description of drawings
Fig. 1 is that the present invention invents the DSC curve contrast of adopting conventional initiated polymerization gained PMMA product in ultrasonic irradiation initiation and the prior art;
Fig. 2 is the GPC spectrogram contrast of three kinds of PMMA samples.
Embodiment
Specific implementation method of the present invention is as follows:
1) impurity such as stopper that commercially available MMA monomer is purified and wherein contained to remove;
2) dissolve a certain amount of PMMA in the MMA monomer after purification in advance;
PMMA: carry out polyreaction first and can purchase commercially available optical grade PMMA pellet, afterwards the PMMA product of available last time of ultrasonic reaction preparation; PMMA pellet consumption: 3%～20% of monomer M MA mass fraction.
3) place ultrasonic intensity then: sound power density is at 0.1～2w/cm
2, ultrasonic frequency: 20kHz～1MH ultrasonic wave field in irradiation, sound wave irradiation time 1～5h;
4) with the monomer behind the irradiation in holding temperature: be incubated 10～36h under 65～110 ℃ the condition, after the question response thing solidifies substantially, progressively improve temperature to 110 ℃ and be incubated 2h, promptly obtain polymeric articles.
Wherein monomer is purified and can be adopted purification mode of the prior art also can adopt method of purification of the present invention, and its concrete steps are as follows:
1.1) at first clean the MMA monomer for several times with isopyknic 10%NaOH solution, till washings is colourless;
1.2) ionized water is washed till neutrality;
1.3) handle with anhydrous sodium sulfate dehydration;
1.4) underpressure distillation.In vacuum tightness is 0.086MPa, and bath temperature begins to steam liquid when being 55 ℃.In order to guarantee the high purity of MMA, it is carried out twice underpressure distillation, take the method for " leaving out the beginning and the end ", promptly each distillation is divided into three parts and collects, collect distillation cut in the early stage (small amount of liquid that steams during the distillation beginning respectively, account for whole original monomer volumes to be distilled about 15%), distillation cut in mid-term and distillation later stage cut (remaining small amount of liquid when distillation is nearly finished, account for whole original monomer volumes to be distilled about 10%).The cut of distillation part in mid-term is the highly purified MMA monomer that polyreaction needs.The cut of getting distillation part in mid-term is the highly purified MMA monomer that polyreaction needs.
Specific embodiments of the invention are as follows:
Embodiment 1: adding the MMA of 20mL through purifying in the Florence flask of 100mL, add 1g (MMA monomer mass 5%) PMMA pellet dissolving again, is 0.25W/cm in sound power density
2Frequency is to add cold water (0～5 ℃) as coupling liquid in the ultrasound reactor of 20kHz, the consumption of coupling liquid is for being higher than reaction solution 1～5cm the best, place ultrasound reactor to be adjusted to the most violent position of acoustic cavitation up and down in flask and (, open ultrasonic wave the MMA irradiation 2h in the flask approximately apart from container bottom 2～3mm) unsettled fixing; After irradiation finishes the flask transfer is put in the baking oven, be incubated 12h down, be warmed up to 85 ℃ of insulation 2h, be warmed up to 100 ℃ of insulation 2h again, obtain product at 70 ℃.
Embodiment 2: adding the MMA of 20mL through purifying in the Florence flask of 100mL, add 2g (MMA monomer mass 10%) PMMA pellet dissolving again, is 0.25W/cm in sound power density
2Frequency is to add cold water (0～5 ℃) as coupling liquid in the ultrasound reactor of 30kHz, the consumption of coupling liquid is for being higher than reaction solution 1～5cm the best, place ultrasound reactor to be adjusted to the most violent position of acoustic cavitation up and down in flask and (, open ultrasonic wave the MMA irradiation 2h in the flask approximately apart from container bottom 2～3mm) unsettled fixing; After irradiation finishes the flask transfer is put in the baking oven, be incubated 20h down, be warmed up to 85 ℃ of insulation 2h, be warmed up to 100 ℃ of insulation 2h again, obtain product at 70 ℃.
Embodiment 3: adding the MMA of 20mL through purifying in the Florence flask of 100mL, add 3g (MMA monomer mass 15%) PMMA pellet dissolving again, is 0.50W/cm in sound power density
2Frequency is to add cold water (0～5 ℃) as coupling liquid in the ultrasound reactor of 50kHz, the consumption of coupling liquid is for being higher than reaction solution 1～5cm the best, place ultrasound reactor to be adjusted to the most violent position of acoustic cavitation up and down in flask and (, open ultrasonic wave the MMA irradiation 1h in the flask approximately apart from container bottom 2～3mm) unsettled fixing; After irradiation finishes the flask transfer is put in the baking oven, be incubated 14h down, be warmed up to 90 ℃ of insulation 2h, be warmed up to 110 ℃ of insulation 2h again, obtain product at 65 ℃.
Embodiment 4: adding the MMA of 20mL through purifying in the Florence flask of 100mL, add 4g (MMA monomer mass 20%) PMMA pellet dissolving again, is 0.50W/cm in sound power density
2Frequency is to add cold water (0～5 ℃) as coupling liquid in the ultrasound reactor of 1MHz, the consumption of coupling liquid is for being higher than reaction solution 1～5cm the best, place ultrasound reactor to be adjusted to the most violent position of acoustic cavitation up and down in flask and (, open ultrasonic wave the MMA irradiation 2h in the flask approximately apart from container bottom 2～3mm) unsettled fixing; After irradiation finishes the flask transfer is put in the baking oven, be incubated 24h down, be warmed up to 95 ℃ of insulation 2h, be warmed up to 105 ℃ of insulation 2h again, obtain product at 75 ℃.
Embodiment 5: adding the MMA of 20mL through purifying in the Florence flask of 100mL, add 2g (MMA monomer mass 10%) PMMA pellet dissolving again, is 0.75W/cm in sound power density
2Frequency is to add cold water (0～5 ℃) as coupling liquid in the ultrasound reactor of 1MHz, the consumption of coupling liquid is for being higher than reaction solution 1～5cm the best, place ultrasound reactor to be adjusted to the most violent position of acoustic cavitation up and down in flask and (, open ultrasonic wave the MMA irradiation 1.5h in the flask approximately apart from container bottom 2～3mm) unsettled fixing; After irradiation finishes the flask transfer is put in the baking oven, be incubated 8h down, be warmed up to 100 ℃ of insulation 2h, be warmed up to 110 ℃ of insulation 2h again, obtain product at 80 ℃.
Referring to Fig. 1, utilize ultrasonic irradiation to cause the product second-order transition temperature (Tg) that obtains as can be seen among five kinds of embodiment of the present invention and all be about 123 ℃, cause products therefrom second-order transition temperature (Tg) than conventional initiator and be about 119 ℃ slightly high, thereby the thermotolerance of this product increases.
Referring to Fig. 2, wherein curve A causes products obtained therefrom for adopting ultrasonic irradiation among five kinds of embodiment of the present invention, and curve B is that conventional initiator causes products obtained therefrom, the PMMA pellet that curve C adds when being ultrasonic polymerization.
The gpc analysis result of three kinds of PMMA samples of table 1
From Fig. 2 and table 1 as can be seen, although the molecular-weight average maximum of curve A (bigger more than 4 times than curve B, bigger near 3 times) than curve C, the σ minimum of curve A, molecular weight distribution is the narrowest, and the regularity of molecule is best.
Claims (6)
1. method of utilizing inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation, it is characterized in that: this method may further comprise the steps:
1) the MMA monomer is purified;
2) dissolve PMMA in the MMA monomer after purification, the PMMA consumption is 3%～20% of a monomer M MA mass fraction;
3) the MMA monomer that will dissolve behind the PMMA is that ultrasonic intensity is that sound power density is at 0.1～2w/cm in condition
2, ultrasonic frequency is ultrasonic irradiation 1～5h in the ultrasonic wave field of 20kHz～1MHz;
4) with the monomer behind the irradiation be insulation reaction 10～36h under 65～110 ℃ the condition in temperature.
2. the method for utilizing inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation according to claim 1 is characterized in that: the concrete steps in the described step 1) are as follows:
1.1) at first clean the MMA monomer repeatedly with isopyknic 10%NaOH solution, till washings is colourless;
1.2) secondly be washed till neutrality with deionized water;
1.3) use anhydrous sodium sulfate dehydration then;
1.4) last underpressure distillation.
3. the method for utilizing inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation according to claim 2, it is characterized in that: underpressure distillation is divided into the collection of three parts described step 1.4), collects distillation cut in early stage, distillation cut in mid-term respectively and distills the later stage cut; The small amount of liquid that steam when cut is meant the distillation beginning described early stage accounts for 5%～15% of whole original monomer volumes to be distilled; Described later stage cut is meant small amount of liquid remaining when distillation is finished nearly, accounts for 5%～15% of whole original monomer volumes to be distilled.
4. the method for utilizing inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation according to claim 3 is characterized in that: the condition of underpressure distillation is that vacuum tightness is 0.03～0.1Mpa described step 1.4), and distillation temperature is 45～65 ℃.
5. according to claim 2 or the 3 or 4 described methods of utilizing inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation, it is characterized in that: vacuum distillation process is twice described step 1.4).
6. the method for utilizing inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation according to claim 1, it is characterized in that: the monomer in the described step 4) behind the irradiation is to be incubated 6～24h down at 65～80 ℃, be warmed up to 80～90 ℃ of insulation 2～6h, be warmed up to 100～110 ℃ of insulation 2～6h again.
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| CN102807641B (en) * | 2012-08-29 | 2014-07-23 | 西华大学 | Body polymerization method of methyl methacrylate |
| CN103030098B (en) * | 2012-12-21 | 2015-08-05 | 西安交通大学 | A kind of large-area nano gap electrod-array walk abreast manufacture method |
| CN106146695B (en) * | 2016-07-01 | 2017-12-26 | 中山大学 | A kind of method of room temperature rapid polymerization methyl methacrylate |
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Application publication date: 20101027 Assignee: Jiangxi well plastic optical fiber technology co Innovation Co., Ltd. Assignor: Jiangxi Daishing POF Co., Ltd. Contract record no.: 2019360000001 Denomination of invention: Method for inducing polymerization of methyl methacrylate body by low-intensity ultrasonic radiation Granted publication date: 20110817 License type: Exclusive License Record date: 20190411 |
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