CN103881001A - Preparation method and application of comb-type epoxy capacity-increasing chain extender for polymer material - Google Patents
Preparation method and application of comb-type epoxy capacity-increasing chain extender for polymer material Download PDFInfo
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- CN103881001A CN103881001A CN201410119139.8A CN201410119139A CN103881001A CN 103881001 A CN103881001 A CN 103881001A CN 201410119139 A CN201410119139 A CN 201410119139A CN 103881001 A CN103881001 A CN 103881001A
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Abstract
The invention discloses a preparation method and application of a comb-type epoxy capacity-increasing chain extender for a polymer material. The comb-type epoxy capacity-increasing chain extender for the polymer material is prepared from the following raw materials (in parts by mass): 60-95 parts of styrene substance, 5-40 parts of acrylic ester monomer and 0.1-10 parts of initiator. The comb-type epoxy capacity-increasing chain extender can be obtained by adopting mass polymerization and solution polymerization. The comb-type epoxy capacity-increasing chain extender can be widely applied to a polymer material with a polyester structure, branching degree of a molecular chain of the polymer material can be obviously improved, and melt strengthen and compatibility can be improved. The comb-type epoxy capacity increasing chain extender has the characteristics of simple manufacturing technique, low addition amount and wide application range.
Description
Technical field
The present invention relates to polymer materials field, be specifically related to preparation method and the application thereof of the pectination epoxy chain-expanding agent that a kind of polymer materials uses.
Background technology
At present, the materials such as poly-succinic ester, poly(lactic acid), polycaprolactone, poly-hexanodioic acid hexylene glycol ester, polyethylene glycol adipate are as single polymer materials, though there is the characteristics and advantages of himself material, but shortcoming is also very obvious: molecular weight is too low, easily water suction degraded in the course of processing, mechanical property defectiveness etc.In order to overcome above-mentioned shortcoming, can adopt chain extension or solve from the mode of different polymer materials blend.The chainextender of broad research is mainly both at home and abroad: acyl chloride, diisocyanates, bisoxazoline class etc., but these chainextenders can produce toxic substance in building-up process, use the polymer materials after these chainextenders also can have the shortcomings such as toxic residue.
Blend between different polymer materialss realizes the Composite of macromolecular material, is a kind of most effectual way of preparing novel high-performance polymer materials.In order to solve the way of this difficult problem of consistency between different polymer materialss, be to add expanding material in co-mixing system, at present for a certain specific co-mixing system, must select specific expanding material; Obtain good compatibilization effect, need to add certain amount just has corresponding effect; Expanding material itself is expensive, and the high price of expanding material and large addition can cause the cost of polymer composites to rise, and whole competitiveness declines.For this reason, new and effective, versatility expanding material is the long-term target of pursuing of industry always.
Publication number is the preparation method that 200710028945.4 Chinese patent is announced a kind of chain-expanding agent.This chain-expanding agent mainly comprises the feed composition of following massfraction proportioning: 1-99 part styrenic material, 0-60 part esters of acrylic acid material, 1-80 part epoxies material, 0.1-5.0 part initiator, 0.1-5.0 part chain-transfer agent class material, through solvent method, polymerization makes chain-expanding agent.
Publication number is the preparation method that 200710031573.0 Chinese patent has been announced a kind of chain-expanding agent in order to recycling engineering plastics.This chain-expanding agent mainly comprises the feed composition of following massfraction proportioning: in every liter of solution, contain 1～99 gram of vinylbenzene; 0～60 gram of methacrylic ester; 1～80 gram of glycidyl methacrylate; 0.1～5.0 gram of dicumyl peroxide; 0.1～5.0 gram of chain-transfer agent, through the free-radical polymerized chain-expanding agent that makes.
The method that above patent is announced comprises the material such as epoxies material, chain-transfer agent class, therefore the use of polymer materials is limited to some extent.Based on this, the object of the invention is to overcome the defect that prior art exists and the controlled chain-expanding agent that a kind of technique is simple, have pectination is provided.This chainextender has following feature: (1) this chain-expanding agent is pectination molecular structure, and a large amount of epoxy-functionals distributes in main chain both sides.By with polyester polymer material molecule chain on hydroxyl, carboxyl reaction, make the non-linear prolongation of polymer materials molecular chain, thereby can improve the molecular weight of polymer materials.(2) this chainextender is under the addition of 0.1%-2.0%, can play the chain extension effect arriving very much to polymer materials, when addition reaches 2.0% when above, except playing the effect of chainextender, can also in polymer composites, play the effect of compatilizer.(3) this chainextender has controllability, for different polymer materialss, can pass through to change chainextender molecular backbone chain construct, and play the effect of compatilizer.
The molecular structural formula of pectination epoxy chain-expanding agent.
Pectination epoxy chain-expanding agent of the present invention has good thermostability, and chain extension effect is fine.The equal safety non-toxic of the starting material that use, and can well solve in polyester polymer material processing the compatible problem in easily degraded and Blending Processes, make this base polymer material can and not cause polymer performance to decline because water suction degraded in processing, reprocessing and reclaiming product process.Simultaneously, can be applicable to the chain extension tackify of the polymer materialss such as poly-succinic ester, poly(lactic acid), polycaprolactone, poly-hexanodioic acid hexylene glycol ester, polyethylene glycol adipate, improve to greatest extent molecular weight and the degree of branching to realize the desirable balance of rheological property and mechanical property by branching reaction, will widen the processed and applied of these polymer materialss in blown film, extrusion sheet and the field such as low-density foamed.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of safety non-toxic, easy to use, consumption is few and high performance pectination epoxy chain-expanding agent, and to solve, the polyester polymer materials processings such as poly-succinic ester, poly(lactic acid), polycaprolactone, poly-hexanodioic acid hexylene glycol ester, polyethylene glycol adipate are easily degraded, melt strength is low, be difficult to the shortcomings such as foaming and blowing.
In order to solve above-mentioned technical barrier, the technical solution used in the present invention is a kind of pectination epoxy macromole chain-expanding agent, and each component and massfraction are:
Styrenic material: 60～95
Acrylic ester monomer: 5～40
Class of initiators: 0.1～10
Described styrenic material is selected from the one in vinylbenzene, vinyl toluene, ethyl styrene, Benzene Chloride ethene.
Described acrylic ester monomer is selected from the one in glycidyl acrylate, glycidyl methacrylate, diacrylate glycidyl ester.
Described class of initiators material is selected from the one in dibenzoyl peroxide, Diisopropyl azodicarboxylate, di-tert-butyl peroxide, the different heptyl nitrile of azo.
The present invention also provides the preparation method of above-mentioned epoxy chain-expanding agent, comprises the following steps:
The temperature of polymerization process described in step 1 is 60-100 ℃.
The reaction times of polymerization process described in step 1 is 2-12 hour.
Embodiment
Shear field flow measurement adopts the MCR302 model rotational rheometer of Austrian Anton Paar company.Parallel plate mode, parallel plate diameter 25mm, upper and lower plates gap 0.75mm, 170 ℃ of temperature, radian frequency (ω) is 0.01～100rad/s, carries out frequency sweeping when strain (γ) is 5%, the linear viscoelastic region of all samples is 0～10%.
Uniaxial tensile test
Sheet material is cut into the rectangular of 10mm × 15mm, uses the SER-2 fixture of Xpansion instrument company of the U.S., 165 ℃ of probe temperatures, rate of extension is respectively 0.05s
-1, 0.1s
-1, 0.5s
-1.In the time that rotor torque reaches 20 μ Nm, start record data.
First by distillation under vacuum, vinylbenzene, glycidyl methacrylate are carried out to refinement treatment, by recrystallization, Diisopropyl azodicarboxylate is carried out to refinement treatment.
Prepare raw material in following ratio, polymerization process is solution polymerization
Vinylbenzene: 80
Glycidyl methacrylate: 20
Diisopropyl azodicarboxylate: 0.5
(1), 40ml toluene is put into flask, add a certain amount of anhydrous magnesium sulfate to be dried two hours.
(2), ratio as requested measures respectively vinylbenzene, glycidyl methacrylate monomer, Diisopropyl azodicarboxylate, Diisopropyl azodicarboxylate is dissolved in vinylbenzene, then add glycidyl methacrylate, mix in rear importing 500ml there-necked flask.
(3), pour the dried toluene of 20ml～30ml into, add magneton, connect spherical condensation tube, connect with the Y-tube that is full of nitrogen balloon, seal each glass interface with unsintered tape.Vacuumize with circulating water pump, put into nitrogen in the time that pressure drops to-900, so circulation repeatedly guarantees that reaction system is by nitrogen protection.
(4), control temperature of reaction be 90 ℃, note keep stir, speed is 20rpm, passes into water of condensation, start reaction, the reaction times is 12h.
(5), stop stirring, close oil bath, take out reaction unit and be cooled to room temperature, get 4～8 times of ethanol to reaction soln and precipitate, reaction soln is slowly splashed in ethanol, obtain rapidly white flocks, after precipitation leaves standstill, remove supernatant liquid, obtain bottom precipitation, product is put into vacuum drying oven dry, temperature setting is set to 50 ℃.
Embodiment 2
First carry out refinement treatment by distillation under vacuum p-methylstyrene, glycidyl acrylate, by recrystallization, dibenzoyl peroxide is carried out to refinement treatment.
Prepare raw material in following ratio, polymerization process is mass polymerization
Vinyl toluene: 90
Glycidyl acrylate: 10
Dibenzoyl peroxide: 5
Vinylbenzene, glycidyl methacrylate, dibenzoyl peroxide are weighed up in proportion, mix and pour in three-necked bottle, vacuumize and pass into nitrogen protection; logical water of condensation, oil bath is heated to 80 ℃, reaction 2h; in the water-bath that proceeds to 50 ℃, react 12h, obtain polymkeric substance.
Embodiment 3
First by distillation under vacuum, vinylbenzene, glycidyl methacrylate are carried out to refinement treatment, by recrystallization, dibenzoyl peroxide is carried out to refinement treatment.
Prepare raw material in following ratio, polymerization process is mass polymerization
Vinylbenzene: 75
Glycidyl methacrylate: 25
Dibenzoyl peroxide: 3
Vinylbenzene, glycidyl methacrylate, dibenzoyl peroxide are weighed up in proportion, mix and pour in three-necked bottle, vacuumize and pass into nitrogen protection; logical water of condensation, oil bath is heated to 90 ℃, reaction 1h; in the water-bath that proceeds to 50 ℃, react 12h, obtain polymkeric substance.
Embodiment 4
In embodiment 1, the application of pectination epoxy chain-expanding agent in the poly(lactic acid) (PLA) (trade mark: 3001D) of Natureworks carried out banburying by the poly(lactic acid) of the pectination epoxy chain-expanding agent of 1.0% embodiment 1 and 99% on torque rheometer.Condition is as follows: time 10min, rotating speed 60r/min, 170 ℃ of temperature.Then gained banburying thing is carried out to rheometer test on rotational rheometer.Can be found out by accompanying drawing 1, its complex viscosity of the PLA after chain extension is apparently higher than pure PLA.
Embodiment 5
In embodiment 2, the application of pectination epoxy chain-expanding agent in the poly(lactic acid) (PLA) (trade mark: 6202D) of Natureworks company of the U.S. carried out banburying by the poly(lactic acid) of the pectination epoxy chain-expanding agent of 1.5% embodiment 2 and 98.5% on torque rheometer.Condition is as follows: time 10min, rotating speed 60r/min, 170 ℃ of temperature.Then gained banburying thing is carried out to rheometer test on rotational rheometer.Can be found out by accompanying drawing 2 and accompanying drawing 3, its complex viscosity of the PLA after chain extension, extensional viscosity be apparently higher than pure PLA, and have obvious strain hardening phenomenon.
Embodiment 6
Pectination epoxy chain-expanding agent and the German BASF ADR4370-F chainextender chain extension effect in the poly(lactic acid) to Natureworks company of the U.S. (PLA) (trade mark: 3052D) under same amount in comparative example 3.The pectination epoxy chain-expanding agent of 0.5% embodiment 3,0.5% BASF ADR4370-F chainextender are carried out to banburying with 99.5% poly(lactic acid) respectively on torque rheometer.Condition is as follows: time 10min, rotating speed 60r/min, 170 ℃ of temperature.Then gained banburying thing is carried out to rheometer test on rotational rheometer.Can be found out by accompanying drawing 4 and accompanying drawing 5, its complex viscosity of the PLA after chain extension, extensional viscosity be apparently higher than pure PLA, and have obvious strain hardening phenomenon.
Claims (10)
1. preparation method and the application thereof of the pectination epoxy chain-expanding agent that polymer materials is used, is characterized in that, described chainextender be by styrenic material, acrylic ester monomer, class of initiators by mass polymerization, the multipolymer that solution polymerization obtains.
2. preparation method and the application thereof of the pectination epoxy chain-expanding agent that polymer materials is used, is characterized in that, each component and massfraction are:
Styrenic material: 60～95
Acrylic ester monomer: 5～40
Class of initiators: 0.1～10.
3. preparation method and the application thereof of the pectination epoxy chain-expanding agent that a kind of polymer materials according to claim 1 is used, is characterized in that, described styrenic material is selected from the one in vinylbenzene, vinyl toluene, ethyl styrene, Benzene Chloride ethene.
4. preparation method and the application thereof of the pectination epoxy chain-expanding agent that a kind of polymer materials according to claim 1 is used, it is characterized in that, described acrylic ester monomer is selected from the one in glycidyl acrylate, glycidyl methacrylate, diacrylate glycidyl ester.
5. preparation method and the application thereof of the pectination epoxy chain-expanding agent that a kind of polymer materials according to claim 1 is used, is characterized in that, described class of initiators material is selected from the one in dibenzoyl peroxide, Diisopropyl azodicarboxylate, the different heptyl nitrile of azo.
6. preparation method and the application thereof of the pectination epoxy chain-expanding agent that a kind of polymer materials according to claim 1 is used, is characterized in that, the solvent using in described solution polymerization is toluene, and extraction liquid is ethanol.
7. preparation method and the application thereof of the pectination epoxy chain-expanding agent that a kind of polymer materials according to claim 1 is used, is characterized in that, described body, and the temperature control of solution polymerization adopts the method for oil bath heated for controlling temperature to carry out.
8. preparation method and the application thereof of the pectination epoxy chain-expanding agent that a kind of polymer materials according to claim 1 is used, is characterized in that, described body, and the range of reaction temperature of solution polymerization is 60-100 ℃.
9. preparation method and the application thereof of the pectination epoxy chain-expanding agent that a kind of polymer materials according to claim 1 is used, is characterized in that, described body, and the reaction time range of solution polymerization is 2-12 hour.
10. the application of pectination epoxy chain-expanding agent according to claim 1, is characterized in that, described chainextender is in the application that improves poly(lactic acid) etc. and have aspect complex viscosity, modulus and the melt strength of polyester polymer material.
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Cited By (5)
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| CN106065043A (en) * | 2016-07-28 | 2016-11-02 | 王金明 | A kind of preparation method of the Organic fluoride hydrophobic type chain extender containing ionic liquid |
| CN107118309A (en) * | 2017-06-26 | 2017-09-01 | 浙江海轩科技有限公司 | A kind of biodegradable polyesters alloy and preparation method thereof |
| CN110452325A (en) * | 2019-07-26 | 2019-11-15 | 广州华新科智造技术有限公司 | Terpolymer and preparation method thereof |
| CN111499789A (en) * | 2020-04-17 | 2020-08-07 | 佳易容聚合物(上海)有限公司 | Solvent-free tackifying chain extender and preparation method and application thereof |
| CN116444740A (en) * | 2023-06-20 | 2023-07-18 | 广东省科学院生物与医学工程研究所 | Chain extender, preparation method and application thereof |
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Cited By (8)
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| CN106065043A (en) * | 2016-07-28 | 2016-11-02 | 王金明 | A kind of preparation method of the Organic fluoride hydrophobic type chain extender containing ionic liquid |
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| CN116444740B (en) * | 2023-06-20 | 2023-09-12 | 广东省科学院生物与医学工程研究所 | Chain extender, preparation method and application thereof |
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Application publication date: 20140625 |