CN102516947B - Degradable gel cool storage agent and preparation method thereof - Google Patents
Degradable gel cool storage agent and preparation method thereof Download PDFInfo
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- CN102516947B CN102516947B CN201110394447.8A CN201110394447A CN102516947B CN 102516947 B CN102516947 B CN 102516947B CN 201110394447 A CN201110394447 A CN 201110394447A CN 102516947 B CN102516947 B CN 102516947B
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Abstract
Provided is a degradable gel cool storage agent. Components of the cool storage agent comprise starch acrylic acid graft copolymer and a phase transition cool storage material. The starch acrylic acid graft copolymer serves as a base material of the cool storage agent, and the phase transition cool storage material is absorbed in the starch acrylic acid graft copolymer so as to prepare the transparent gel cool storage agent. Adjustable phase transition temperature of the cool storage agent ranges from -4 to 0 DEG C. The phase transition cool storage material is water or NaCl water solution with concentration ranging from 0.5 to 5%. The invention further provides a preparation method of the cool storage agent. The cool storage agent is non-toxic, free of smell, non-corrosive, gel-shaped, hard to flow out to contaminate packaged products and capable of being biologically degradable.
Description
Technical field
The present invention relates to temperature control packaging field, especially relate to a kind of cold storage agent and preparation method thereof.
Background technology
Current Cool Storage Technology is mainly used in the air-conditioning of buildings, along with the development of technology, is expected the range of application expanding it, and the application of research and development low-temperature cold accumulation technology in temperature control packaging has theory and Practical significance.Traditional cold storage agent is wet ice and dry ice mainly, and its transformation temperature is respectively 0 DEG C and-78 DEG C.Their transformation temperature is all non-adjustable, makes it apply and is restricted.And wet ice-out produces water, need additional water-absorbing material; Dry ice sublimation releases carbon dioxide, reaches finite concentration and can damage product and packaging.Inorganic salt solution is as cold storage agent, and transformation temperature is adjustable, but there is surfusion and occur being separated, and affects timely release and the utilization of heat, causes its cold-storage ability to reduce.
High molecular material coolant, as novel cold storage agent, has lot of advantages.But a lot of non-degradable, harm global environment.Along with the development of society, people will be more widely used to environment protection, more and more higher, multi-functional, degradable, high-efficiency the cold storage agent of requirement that is energy-saving and cost-reducing, decreasing pollution.The green phase change cold accumulating agent of environmental friendliness, convenient post-treatment, reusable, easy degraded is also badly in need of in the extensive employing of temperature control packaging.
Summary of the invention
For the problems referred to above that prior art exists, the applicant provides a kind of degradable gel cool storage agent and preparation method thereof.Cold storage agent prepared by the present invention is nontoxic, tasteless, non-corrosiveness, in gel, not easily reserves and pollutes packaged product, biodegradable.
Technical scheme of the present invention is as follows:
A kind of degradable gel cool storage agent, the composition of this cold storage agent comprises starch acrylic acid graft multipolymer and phase-change material for cold storage, starch acrylic acid graft multipolymer is as the base material of cold storage agent, and phase-change material for cold storage is attracted in starch acrylic acid graft multipolymer, makes transparent gel cold storage agent.The adjustable transition temperature range of described cold storage agent is-4 ~ 0 DEG C.Described phase-change material for cold storage to be water or concentration be 0.5 ~ 5% the NaCl aqueous solution.
The preparation method of degradable gel cool storage agent, concrete steps are as follows:
(1) be mixed with dry starch the starch solution that massfraction is 11 ~ 13%; Initiator is ammonium persulphate, and quality is 3 ~ 5% of dry starch quality, is mixed with the ammonium persulfate initiator solution of 10wt%; Linking agent is N, N '-methylene-bisacrylamide, quality is 0.5 ~ 1.5% of dry starch quality, is mixed with the N of 10wt%, N '-methylene-bisacrylamide cross-linking agent solution; NaOH solution with 25% regulates acrylic acid PH to 6 ~ 7, and the vinylformic acid before adjustment and the mass ratio of dry starch are 1.8 ~ 2.3:1;
(2) starch solution is poured into the reaction vessel with prolong, add ammonium persulfate initiator solution; Reaction vessel is warming up to 55 ~ 65 DEG C, stirring reaction 30 ~ 40 minutes;
(3) in reaction vessel, N is added, the vinylformic acid of N '-methylene-bisacrylamide cross-linking agent solution and modulated good PH, stirring reaction 50 ~ 70 minutes;
(4) product is dried to constant weight in 50 ~ 70 DEG C of baking ovens, filters, i.e. obtained Powdered starch acrylic acid graft multipolymer with pulverizer after pulverizing with 60 eye mesh screens;
(5) obtained starch acrylic acid graft multipolymer is mixed with phase-change material for cold storage, stir, namely obtained transparent degradable gel cool storage agent.
During using water as phase-change material for cold storage, the mass ratio of starch acrylic acid graft multipolymer and water is 0.5 ~ 1.5:100.Using concentration be 0.5 ~ 5% the NaCl aqueous solution as phase-change material for cold storage time, starch acrylic acid graft multipolymer will adsorb the NaCl aqueous solution of saturation capacity, and the quality of the NaCl aqueous solution of described saturation capacity is 13 ~ 50 times of starch acrylic acid graft copolymer quality.
The water-intake rate recording the starch acrylic acid graft multipolymer of preparation by screen filtration method is 280g/g.In order to reach the adjustable object of transformation temperature, when described cold storage agent uses NaCl solution as phase-change material for cold storage, the NaCl solution that enough concentration is 0.5 ~ 5% is added in starch acrylic acid graft multipolymer, stirring makes Powdered starch acrylic acid graft multipolymer fully dissolve, unabsorbed NaCl solution is filtered out with 100 eye mesh screens, starch acrylic acid graft multipolymer adsorbs saturated NaCl solution as cold storage agent, and the saturated extent of adsorption of starch acrylic acid graft multipolymer to different N aCl strength of solution is shown in Table 1.
Table 1
The technique effect that the present invention is useful is:
Cold storage agent of the present invention is applicable to the packed and transported that temperature requirement is-4 DEG C ~ 0 DEG C of product, have preparation technology simple, easy to operate, cost is low, transformation temperature is adjustable, latent heat of phase change is large, without condensate depression or condensate depression minimum, not easily flow, repeatedly used feature, overcome inorganic salt solution simultaneously and there is surfusion and the shortcoming occurring being separated, be a kind of phase change cold accumulating agent that can degrade, meet the requirement of environmental protection.It may be used for temperature sensitivity product, and as the Transport Package of medicine, seafood, poultry, fresh agricultural-food, milk-product etc., cold storage agent is as temperature control medium, when transport package experience hot environment, the heat of Balance Absorption, can maintain low temperature, avoids product damaged by heating power.
Accompanying drawing explanation
Fig. 1 is starch acrylic acid graft multipolymer and water is 1.5:100 as the mass ratio that the mass ratio that temperature lowering curve figure: the a-starch acrylic acid graft multipolymer of cold storage agent and the mass ratio of water are 0.5:100, b-starch acrylic acid graft multipolymer and water is 1:100, c-starch acrylic acid graft multipolymer and water;
Fig. 2 be starch acrylic acid graft multipolymer and NaCl solution as cold storage agent temperature lowering curve figure: a-starch acrylic acid graft multipolymer adsorbs saturated 1%NaCl solution, b-starch acrylic acid graft multipolymer adsorbs saturated 3%NaCl solution, c-starch acrylic acid graft multipolymer adsorbs saturated 5%NaCl solution.
Embodiment
Embodiment 1:
Starting material: be mixed with the starch solution that massfraction is 11% with dry starch; Initiator is ammonium persulphate, and quality is 3% of dry starch quality, is mixed with the ammonium persulfate initiator solution of 10wt%; Linking agent is N, N '-methylene-bisacrylamide, quality is 0.5% of dry starch quality, is mixed with the N of 10wt%, N '-methylene-bisacrylamide cross-linking agent solution; NaOH solution with 25% regulates acrylic acid PH to 6, and the vinylformic acid before adjustment and the mass ratio of dry starch are 1.8:1.
Preparation process: after the temperature of water bath with thermostatic control is raised to 55 DEG C, the starch solution prepared is added in four-hole boiling flask, add ammonium persulfate initiator solution, stir initiation adds modulated good PH acrylic acid solution and N after 40 minutes, N '-methylene-bisacrylamide cross-linking agent solution, stirs and carries out graft copolymerization 70 minutes.Be dried to constant weight in 50 DEG C of baking ovens, pulverize with pulverizer.The starch acrylic acid graft multipolymer prepared and water in mass ratio 1.5:100 mix, and stir, i.e. the gel cold storage agent of obtained graft starch and water.
Cold storage agent performance test: obtained cold storage agent and dehydrated alcohol are put in respectively in two test tubes, the inside is each plugs in a thermoprobe, is put in the freezer compartment of refrigerator of-20 DEG C and freezes about 6 hours, utilizes moisture recorder to measure temperature over time.According to the temperature lowering curve recorded, the transformation temperature obtaining this cold storage agent is 0 DEG C.Utilize reference temperature curve method to calculate the latent heat of phase change of this cold storage agent for 230kJ/kg, liquid specific heat is 3.14kJ/ (kg DEG C).
Embodiment 2:
Starting material: be mixed with the starch solution that massfraction is 11.76% with dry starch; Initiator is ammonium persulphate, and quality is 4% of dry starch quality, is mixed with the ammonium persulfate initiator solution of 10wt%; Linking agent is N, N '-methylene-bisacrylamide, quality is 0.83% of dry starch quality, is mixed with the N of 10wt%, N '-methylene-bisacrylamide cross-linking agent solution; NaOH solution with 25% regulates acrylic acid PH to 6.5, and the vinylformic acid before adjustment and the mass ratio of dry starch are 2:1.
Preparation process: after the temperature of water bath with thermostatic control is raised to 60 DEG C, the starch solution prepared is added in four-hole boiling flask, add ammonium persulfate initiator solution, stir initiation and after 35 minutes, add vinylformic acid and the N that PH is adjusted to 6.50, N '-methylene-bisacrylamide cross-linking agent solution, stirs and carries out graft copolymerization 1h.Be dried to constant weight in 60 DEG C of baking ovens, pulverize with pulverizer.Take a certain amount of starch acrylic acid graft multipolymer, toward the 3%NaCl solution wherein adding starch acrylic acid graft copolymer quality 50 times, filter unnecessary unabsorbed NaCl solution with 100 object screen clothes, obtain adsorbing 3% saturated NaCl gel cold storage agent.
Cold storage agent performance test: obtained cold storage agent and dehydrated alcohol are put in respectively in two test tubes, the inside is each plugs in a thermoprobe, is put in the freezer compartment of refrigerator of-20 DEG C and freezes about 6 hours, utilizes moisture recorder to measure temperature over time.According to the temperature lowering curve recorded, the transformation temperature obtaining this cold storage agent is-2.2 DEG C, without surfusion.Utilize reference temperature curve method to calculate the latent heat of phase change of this cold storage agent for 190kJ/kg, liquid specific heat is 2.52kJ/ (kg DEG C).
Embodiment 3:
Starting material: be mixed with the starch solution that massfraction is 13% with dry starch; Initiator is ammonium persulphate, and quality is 5% of dry starch quality, is mixed with the ammonium persulfate initiator solution of 10wt%; Linking agent is N, N '-methylene-bisacrylamide, quality is 1.5% of dry starch quality, is mixed with the N of 10wt%, N '-methylene-bisacrylamide cross-linking agent solution; NaOH solution with 25% regulates acrylic acid PH to 7, and the vinylformic acid before adjustment and the mass ratio of dry starch are 2.3:1.
Preparation process: after the temperature of water bath with thermostatic control is raised to 65 DEG C, the starch solution prepared is added in four-hole boiling flask, add ammonium persulfate initiator solution, stir initiation adds modulated good PH acrylic acid solution and N after 30 minutes, N '-methylene-bisacrylamide cross-linking agent solution, stirs and carries out graft copolymerization 50 minutes.Be dried to constant weight in 70 DEG C of baking ovens, pulverize with pulverizer.Take a certain amount of starch acrylic acid graft multipolymer, toward the 5%NaCl solution wherein adding starch acrylic acid graft copolymer quality 50 times, filter unnecessary unabsorbed with 100 object screen clothes, obtain adsorbing 5% saturated NaCl gel cold storage agent.
Cold storage agent performance test: obtained cold storage agent and dehydrated alcohol are put in respectively in two test tubes, the inside is each plugs in a thermoprobe, is put in the freezer compartment of refrigerator of-20 DEG C and freezes about 6 hours, utilizes moisture recorder to measure temperature over time.According to the temperature lowering curve recorded, the transformation temperature obtaining this cold storage agent is-3.6 DEG C, condensate depression 0.4 DEG C, in the scope that condensate depression requires.Utilize reference temperature curve method to calculate the latent heat of phase change of this cold storage agent for 162kJ/kg, liquid specific heat is 2.63kJ/ (kg DEG C).
Fig. 1 is starch acrylic acid graft multipolymer and the water temperature lowering curve figure as cold storage agent, and in figure, c curve is embodiment 1 content measurement, and a, b curve is the mass ratio of starch acrylic acid graft multipolymer and water is the situation of 0.5:100,1:100.As can be seen from the figure: starch acrylic acid graft multipolymer and water are as cold storage agent, transformation temperature is 0 DEG C, identical with the transformation temperature of water, do not change with the change of quality ratio with starch acrylic acid graft multipolymer, illustrate that the transformation temperature of starch acrylic acid graft multipolymer to cold storage agent does not have an impact.
Fig. 2 is starch acrylic acid graft multipolymer and the NaCl solution temperature lowering curve figure as cold storage agent, in figure, b curve is embodiment 2 content measurements, in figure, c curve is embodiment 3 content measurements, and a curve is the 1%NaCl solution of 1g starch acrylic acid graft multipolymer absorption 25.42g.As can be seen from the figure: along with the increase of NaCl solution concentration, the transformation temperature of cold storage agent declines, and this satisfies the requirement that transformation temperature is adjustable; Meanwhile, along with the increase of NaCl solution concentration, condensate depression also occurs thereupon, occurs 0.4 DEG C excessively cold during NaCl solution concentration 5%, but still in the scope that condensate depression requires.
Claims (3)
1. a degradable gel cool storage agent, it is characterized in that, the composition of this cold storage agent comprises starch acrylic acid graft multipolymer and phase-change material for cold storage, starch acrylic acid graft multipolymer is as the base material of cold storage agent, phase-change material for cold storage is attracted in starch acrylic acid graft multipolymer, makes transparent gel cold storage agent;
The NaCl aqueous solution of described phase-change material for cold storage to be water or concentration be 0.5 ~ 5wt%; The adjustable transition temperature range of described cold storage agent is-4 ~ 0 DEG C;
When cool storage material is water, transformation temperature is 0 DEG C;
Preparation method's concrete steps of described degradable gel cool storage agent are as follows:
(1) be mixed with dry starch the starch solution that massfraction is 11 ~ 13%; Initiator is ammonium persulphate, and quality is 3 ~ 5% of dry starch quality, is mixed with the ammonium persulfate initiator solution of 10wt%; Linking agent is N, N '-methylene-bisacrylamide, quality is 0.5 ~ 1.5% of dry starch quality, is mixed with the N of 10wt%, N '-methylene-bisacrylamide cross-linking agent solution; Regulate acrylic acid pH to 6 ~ 7 by the NaOH solution of 25wt%, the vinylformic acid before adjustment and the mass ratio of dry starch are 1.8 ~ 2.3:1;
(2) starch solution is poured into the reaction vessel with prolong, add ammonium persulfate initiator solution; Reaction vessel is warming up to 55 ~ 65 DEG C, stirring reaction 30 ~ 40 minutes;
(3) in reaction vessel, N is added, the vinylformic acid of N '-methylene-bisacrylamide cross-linking agent solution and modulated good pH, stirring reaction 50 ~ 70 minutes;
(4) product is dried to constant weight in 50 ~ 70 DEG C of baking ovens, filters, i.e. obtained Powdered starch acrylic acid graft multipolymer with pulverizer after pulverizing with 60 eye mesh screens;
(5) obtained starch acrylic acid graft multipolymer is mixed with phase-change material for cold storage, stir, namely obtained transparent degradable gel cool storage agent.
2. degradable gel cool storage agent according to claim 1, is characterized in that, during using water as phase-change material for cold storage, the mass ratio of starch acrylic acid graft multipolymer and water is 0.5 ~ 1.5:100.
3. degradable gel cool storage agent according to claim 1, it is characterized in that, using concentration be the NaCl aqueous solution of 0.5 ~ 5wt % as phase-change material for cold storage time, starch acrylic acid graft multipolymer will adsorb the NaCl aqueous solution of saturation capacity, and the quality of the NaCl aqueous solution of described saturation capacity is 13 ~ 50 times of starch acrylic acid graft copolymer quality.
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| CN103965837A (en) * | 2014-05-07 | 2014-08-06 | 杭州电子科技大学 | Preparation method of shape plastic macromolecule coolant |
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| CN105601819A (en) * | 2016-01-29 | 2016-05-25 | 深圳职业技术学院 | Low-temperature gel-state phase-changing cold storage agent and preparation method thereof |
| CN106478885A (en) * | 2016-10-11 | 2017-03-08 | 常州市鼎升环保科技有限公司 | A kind of preparation method of environment-friendly type agent for storage of coldness |
| CN106750036B (en) * | 2016-11-25 | 2020-02-04 | 苏州安特实业有限公司 | Lignin series super absorbent resin gel low-temperature phase change material |
| CN106543975A (en) * | 2016-12-11 | 2017-03-29 | 戴琪 | A kind of preparation method of low-cost bio matter composite phase-change agent for storage of coldness |
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| CN110734745B (en) * | 2019-11-28 | 2021-08-17 | 浙江海洋大学 | Cold chain coolant for tuna and preparation method thereof |
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| CN115368877A (en) * | 2022-09-15 | 2022-11-22 | 浙江大学 | Cold compress material and cold compress assembly based on same |
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| CN1570015A (en) * | 2003-07-16 | 2005-01-26 | 中国科学院大连化学物理研究所 | Na2HPO4.12H2O heat storage material and its making method |
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