CN103940522B - Polymeric form time-temperature indicator and application in military food of the same - Google Patents

Abstract

The invention belongs to the technical field of measurement and instruction, and especially relates to a polymeric form time-temperature indicator and application in military food time-temperature indicator of the polymeric form time-temperature indicator. The polymeric form time-temperature indicator comprises, by weight ratio, 6 : 1 - 1 : 6 between two toluidine formic acid-2, 4-diyne-1, 6-hexanedioic ester and two pair fluorine benzene sulfonic acid-2, 4- diyne-1, and 6-hexanedioic ester. According to the polymeric form time-temperature indicator, connection two alkyne class polymerization reaction activation energy generating in the component is matched with the military food quality change activation energy, and the reaction speed of the two activation energies are similar to each other. Meanwhile, the polymerization reaction color change is significant, and pink is turned into black. The indicator made of the polymeric form time-temperature indicator is attached to the military food outer package, the accumulated experience of time-temperature effect of the two activation energies is consistent, and food quality status can be indicated.

Description

A kind of aggretion type time-temperature indicator and its application in military food

Technical field

The invention belongs to measurement and instruction technical field, more particularly, to a kind of aggretion type Time-temperature instruction Agent and its application in military food Time-temperature indicateing arm.

Background technology

(1) food quality

Food quality refers to the edible performance of food and characteristic meets specifying and meeting consumer of relevant standard The degree requiring.Food quality is combined by multiple qualitative factors, mainly includes hygienic quality, nutrition Quality, aesthetic quality and other additional mass etc..Food quality is a kind of its Consumers' Acceptance of impact Dynamic complicated attribute, be at a dynamically continuous process declining after the process.Food matter Amount change includes color and luster, local flavor, quality structure, nutritive value, safe and sanitary etc..Due to most food All originate from animals and plants product, these raw materials do not contain only large quantity of moisture, and containing abundant nutrient substance. The unstable nutritional labeling of these physicochemical properties was both easily encroached on by microorganism, but easily environment because Occur chemically or physically to change in the presence of element, numerous food product also contains multiple enzymes, fit in environmental condition In the case of preferably, be susceptible to many plant enzymatic reaction, all these food quality all can be led to become Change.Food quality change is affected by food component and environmental factorss, and its rate of change can be with following Function representation：

DQ/dt=F (C_i,E_j)

Wherein Ci represents food product factor, the physiological change including fresh and alive food and microbiology turbidity, As Repiration and the after-ripening of vegetable, the stiff, after-ripening after death of poultry fish, self-dissolving and corruption, and food The various physicochemical change that product composition occurs, such as nutrient component damages, pigment are decomposed, hydrolysis changes etc., Internal factor is the particular attribute of food, determines the quality of raw material.For packaged food, environment because The change of element is then the leading factor of food quality change.Ej refers to environmental factorss, including temperature, relatively Humidity, gross pressure, gas pressure, illumination, microorganism pollution, the insect pest plague of rats, production, packaging and stream The negative effect to food quality such as the pollution in logical, mechanical damage.Wherein food quality is affected more Generally the fat oxidation caused by the composite factor such as temperature, photooxidation become sour, age of starch, albumen qualitative change Property, vitamin destroys and the evaporation of moisture, absorption, transfer, condensation etc..

(2) effective period of food quality

Shelf-life theory results from modern food technology and packing technique, comprises food in shelf-life concept Learn, packaging is learned, materialogy, many technological know-hows such as marketing.The length of shelf life of products, Depend primarily on quality, technology of the package and the material of product itself and the environment bar of products in circulation process Part etc., its influence factor is numerous, and formation mechenism is also complex with mutual relation.

Effective period of food quality is a time limit, that is, under specific storage requirement, food consumption safety, and quality The time limit that can be esthetically acceptable to the consumers.Ununified standard in society defines the shelf-life.The definition of shelf-life Change with food variety and purposes with assay method.

Different from civilian food, military food in production reserve at ordinary times, wartime or manoeuvre, outer instruction, oceangoing voyage And frontier defense patrol etc. just can use under special emergency, therefore military food must possess longer storage Deposit the phase, and color, smell, taste and shape and nutritional labeling are held essentially constant within storage period.For example, the 10 of the British army People and 4 people combination grain ration, are 3 years in the storage period of Temperate Region in China, in 2 DEG C of temperature, relative humidity 60% Relatively Cool Condition under, storage period was up to 5 years.General storage period all exists my army's military food at normal temperatures More than 2 years, to the military shelf-life of tinplate canned food and the regulation of storage life it is such as：Under the room temperature of ground storehouse, Meat, fowl, 30 months canned food shelf-lifves of aquatic product, storage life 36 months.The shelf-lifves such as fruits and vegetables class 24 Individual month, storage life 30 months.It is different for being stored in south and the military food shelf-life in the north, The shelf-life of the military food of north storage will be grown.Therefore, how accurately to indicate that food quality is military One important topic of food.

(3) time-temperature indicator technology

Time-temperature indicator (Time-Temperature Indicator, TTI) can be defined as a class letter Single easy quality record device, can the Partial key parameter in the whole shelf life to commodity be monitored And record, then indicate that food temperature changes course and remaining shelf by the accumulative effect of Time-temperature Information.TTI can show that continuous Time-temperature reaction, and in the measurements can be to whole time - temperature history is integrated, " effective mean temperature " of instruction sales process.

Earliest time-temperature indicator (Time-Temperature Indicator, TTI) can be traced back to During World War II, ice cube is placed in frozen food case for AUS quartermaster regiment, such as fruit ice Block disappears and means that the temperature control during shipping storage is improper, and the ice cube used here is exactly a kind of Simple TTI.1993, first TTI patent birth in the world.Subsequently, Honeywell company (Minneapolis, MN) develops first TTI used in business, but due to it Price is very high, volume is excessive, so always inreal use in business.

In nineteen fifty, exploitation has manufactured a bag that can be permeated by animal glue and oxygen to Ramstad et al. The TTI of pack composition.Colloid is contained within oxidase and colourless oxybenzene compound, once colloid dissolving, Colourless oxybenzene compound will react overstrike.Browning degree instruction food exposes under harmful temperatures Time length and food quality change situation.Browning rate can be by adding the vitamin of varying level C is controlling.At 4.4 DEG C, the time that this indicator brown stain needs is 6 hours, adds 0.1% dimension life 24 hours are needed after plain C.

At twentieth century beginning of the seventies, the research and development of TTI become a focus.AUS Natick Laboratory has invented a kind of TTI based on the variable color of oxidation system, and its principle is to be affected by temperature Through the amount of oxygen of thin film, and then lead to color change.Through on probation up to 2 years, show that they have Practical application may be put into.At present, the MRE grain ration that a new generation of U.S. army can preserve 10 years is currently in use " buphthalmos " label is aggretion type TTI developed according to this principle.

By 1976, have six TTI manufacturers：Artech company, Check Spot company, Tempil company, I-Point company, Bio-Medical Science company and 3M company.Wherein, I-Point That company produces is a kind of TTI based on enzyme reaction, and what 3M company produced is a kind of to be diffused as The TTI on basis.

The twentieth century early stage eighties, market exists I-Piont, 3M, Ambitemp and Tempchron Four kinds of business TTI systems.The operation principle of Ambitemp and Tempchron is in capillary using liquid Flowing in pipe, is produced by Andover Labs, for the marketing system of frozen food.

Singh in 1985 et al. research find the response time of I-Point label and the quality in freezing hamburger, It is stored in heat-resisting bacteria growing in the organoleptic attribute of Fructus Fragariae Ananssae and vitamin C, the fresh milk under the conditions of -12 DEG C The change such as demurrage, organoleptic feature of Fructus Lycopersici esculenti has good dependency.Wells in 1988 et al. research Find hardness and color and I-Point2340 type and Lifelines Freshness Monitor 57 type of Fructus Lycopersici esculenti The response value of two kinds of instruction cards is in significantly correlated；At a temperature of 5 DEG C and 10 DEG C, I-Point2340 type refers to Show that card can be good at indicating aesthetic quality's change of Caulis et Folium Lactucae sativae；Cake mixed with dry fruit and instruction card used Response value does not have dependency；The Cortex cocois radiciss taste of UHT sterilization milk and whiteness and Lifelines Freshness In significantly correlated between Monitor11, the response value of 21 type instruction cards.Cherng in 1989 et al. finds The response value of the TTI of Lifelines is significantly correlated with the taste of pasturising milk, low temperature bacterium number and acidity value, Mass change that can be with effective monitoring milk during transportation and sale.Nineteen ninety Labuza and Taoukis The product being provided using TTI at first remaining shelf life information in cold chain optimize circulation control and Inventory turnover.Shell in 1991 et al. monitors agriculture using I-Point4014 type and 4021 types instruction card The chemistry of family's cheese and microbiological indicator, research shows response value and the farmers' of I-Point4014 type instruction card The change of the chemistry of cheese and microbiological indicator has good dependency.Taoukis et al. 1999 is to TTI It is applied to Boque fish to be studied.This research is with two microbiological indicators of fish and an organoleptic indicator As evaluation index, it is analyzed using Arrhenius equation and Belehradek equation.2000, The Sock-In Hong of korean foods institute and Wan-Soo Park to monitor Chinese cabbage system with TTI Make the fermentation situation of Pickles, research finds that some TTI can be used to as a kind of intelligent packaging body System, the fermentation of monitoring Chinese cabbage.Through test, TTI product can also be applied to refrigerated vegetables, freezing Fructus Fragariae Ananssae, mushroom, the instant salad of cooling, Frozen Pork and Carnis Gallus domesticus, freezing sausage, cooling orange juice, Pasteur Sterilization butter etc..

Potassium triiodide, solvable starch and its amylase of mentioning hydration in patent US2553369 can be used Time-temperature instruction in frozen food.When the thaw point that environment temperature is higher than food, starch exists Hydrolyze in the presence of amylase, blueness is assumed due to the presence of potassium triiodide.Patent US2892798 The middle metal alkyl iodide solution that mercuric iodixde, Copper diiodide are mixed in liquid, when frozen food start solve During jelly, this mixed solution will assume the change of color.Patent US3545400 shows can be by a kind of dyestuff The device of filling is used for indicating freezing point and melting temperature.Mentioning in patent US3768976 can be by redness The aqueous solution of dyestuff aoxidize during oxygen gradually permeates become colourless indicating perishable commodity A very long time is had to be placed under higher temperature conditionss.In patent US3844718, when water or vapor The defrosting of food is may indicate that with the ink (this ink invests on hygroscopic substrate) of solubility when contacting Temperature.In patent US3078182, a kind of label of pressure sensibility color change instruction can be used to refer to Show the sterilization operation process of product.Research to conjugation diethyl acetylene compound shows to be conjugated diethyl acetylenic Compound can be used for the instruction of Time-temperature, and the continuous process of energy presentative time-temperature change.Mesh Front TTI has been applied to food, medical product (as vaccine, serum), Nicotiana tabacum L., pet food, change In the fields such as cosmetic, electronic product.

Military food, in transport and storage, is affected by ambient temperature, food quality constantly declines Or deterioration, or even can not eat.Judge that food quality relies primarily on date of manufacture and shelf-life at present.By In not knowing that between Storage period, ambient temperature is high or low, rely solely on storage time it is difficult to accurately judge food Quality state.The time-temperature indicator of prior art is primarily referred to as things shelf-life shorter fresh food Product, longer tinned food and military food for the shelf-life, research is fewer at present, the technology of maturation Even more it is difficult to see with product.

Content of the invention

For solving the deficiencies in the prior art the invention provides a kind of aggretion type time-temperature indicator, its The company's diyne type of polymerization activation energy occurring in component and the activation energy of military food mass change Join, the two response speed is close.Meanwhile, secondary response color change is notable, is changed into black from pink. It is pasted onto in military food outer package with the indicateing arm that it makes, the Time-temperature effect one of accumulation experience Cause, can indicate that food quality state.

A kind of aggretion type time-temperature indicator, including weight than for 6：1～1：6 two meta-aminotoluenes The own diester of base formic acid -2,4- diine -1,6- and the own diester of the two couples of fluorobenzene sulfonic acid -2,4- diine -1,6-.

Preferably, described aggretion type time-temperature indicator, wherein two meta-aminotoluene base formic acid -2,4- The weight of the own diester of diine -1,6- and the own diester of the two couples of fluorobenzene sulfonic acid -2,4- diine -1,6- is than for 3：1～1：3.

Diethyl acetylene compound (RC ≡ CC ≡ CR, R is substituted radical) is in heating or energy-rich radiation bar Solid-state Isosorbide-5-Nitrae-polyaddition reaction can be carried out, reaction expression is as follows under part：

Generally, monomer is all colourless, and partially polymerized monomer then shows blue or red, complete The diethyl alkine compounds of full polymerization then assume metallic luster.Chain polymer has color to be because that pi-electron exists Delocalization in conjugation chain structure causes, and the color of polymer is then by the length of conjugated chain and polymer The plane degree of skeleton is determined.Same two acetylene compounds whether under colourless free state, Under partially polymerized blue color states still completely under the red status of polymerization, their composition, molecular weight and NMR spectra is identical.There are some researches show, the compound of blue color states is that free radical causes.Three Between the acetylene compound of the state of kind, the mechanism of conversion is as follows：The monomer of white forms blueness under light illumination Cumulene free radical, then changes into the acetylene compound of red status in case of heating.

Conjugation acetylene class TTI can be changed using irreversible, the obvious color of its m- temperature at any time Change process is indicating whether easily corrupt deteriorating item is in the deterioration mistake of Time-temperature undesirably Cheng Zhong.This kind of compound either ring-type, chain, symmetrical, asymmetric, diine, three alkynes, Four alkynes ... all comprise two or more conjugation acetylene groups, the change of its color be by temperature or Solid-state 1,4- polyaddition reaction in the case of light radiation causes.

Property research to conjugation acetylene compound shows, these compounds except for making in addition to TTI, Can be also used for other side.In patent US3923622, this kind of compound is used for synthesis of cyclic notch cuttype Polymer；These compounds also can be used for the synthesis of reaction as cross-linking agent；In patent US4788151 In it is also mentioned that the material that acetylene metalloid complex can be indicated as environment.And this kind of compound is ground Study carefully most, be also based on the color change of its m- temperature at any time.

In patent US4737363, conjugation diethyl acetylenic salt compound can as photoactive when m- Temperature indicating labels.Conjugation diethyl acetylenic salt compound forms conjugation diethyl acetylenic carboxylic under the conditions of light radiation Acid, thus being activated, the change of over time-temperature and there is corresponding color change, this kind of chemical combination Thing is mainly used in indicating the deterioration process of frozen food m- temperature at any time.

Patent US3999946 is explained in detail for TTI to this kind of compound.But this type TTI must be stored under very low cryogenic temperature before the use, and the radiation of light to be avoided, because For it, once finished product, just oneself, through being activation, has polymerization metachromasia.Such a condition of storage will increase Plus the cost of TTI, and some uncertain factors can be attracted, thus leading to finally indicate result not Accuracy.

Patent US4228126 has been made to improve to the TTI research of US3999946.Conjugation diethyl acetylenic TTI Compound has two stable and unstable class forms.In patent US4228126, existed with stable form Acetylene compound can use as TTI, its maximum advantage is exactly stable conjugation diethyl acetylenic Compound can be in general at room temperature in daylight preservation, only need to be through letter before using as TTI The recrystallization process of single quickly melting cooling or solvent can be changed into the TTI compound of activity, carries out The instruction of Time-temperature.Indicate inside this patent same conjugation diethyl acetylene compound unstable and The acetylene compound of the reason two kinds of stable form color changes are different and two kinds of forms mutually converts Condition.

Amido formate and sulfonic acid esters conjugation diacetylene type TTI compound are the most typical second of two classes Acetylenic TTI compound.Wherein representational compound is：Two meta-aminotoluene base formic acid -2,4- diine -1,6- Own diester, english abbreviation is HDmTU, and the structural formula of HDmTU and PFBS is as follows.

Two pairs of fluorobenzene sulfonic acid -2,4- diine -1, the own diester of 6-, can be longer through one section used as TTI compound The polymerisation induced process of time, the blast polyreaction eventually passing through interlock type produces color change.Permissible Utilize this feature that it is used for foodsafety to instruct, will give people before being eaten in food Prompting；Can also reduce the waste of food resource on the other hand, effective Instructing manufacture, sell and disappear Take.

These compounds each have the induction period in polymerization of different time length, can be respectively used to instruction therewith The quality comparison course of the consistent perishable farm products of color change process m- temperature at any time.

The colour developing cycle of PFBS with HDmTU is different, if making TTI only use a kind of monomer, produces TTI instruction the cycle fix, the scope of application is narrower.Can be made by mutually mixing two kinds of monomers The TTI going out the different colour developing cycles, to expand its range of application, is simultaneously facilitated screening and is thought with food shelf model The TTI formula of coupling.

Present invention also offers a kind of food Time-temperature indicateing arm, it at least includes marker and carrying The base version of described marker, the component of described marker and the weight/mass percentage composition of each component are： 0.001%～0.006% own diester of two meta-aminotoluene base formic acid -2,4- diine -1,6-, 0.001%～0.006% Two pairs of fluorobenzene sulfonic acid -2,4- diine -1, the own diester of 6-, 8.100%～10.000% bonding agent, balance of Auxiliary agent.

Preferably, the component of described marker and the weight/mass percentage composition of each component are：0.001%～ The 0.003% own diester of two meta-aminotoluene base formic acid -2,4- diine -1,6-, 0.001%～0.003% two pairs of fluorine Benzenesulfonic acid -2,4- diine -1, the own diester of 6-, 8.100%～10.000% bonding agent, balance of auxiliary agent.

Preferably, the described bonding agent of described marker is selected from polystyrene, polyurethanes or polychlorostyrene The mixing of one or more of vinyl.

Preferably, the described auxiliary agent of described marker is dichloromethane.

Food Time-temperature indicateing arm provided by the present invention can indicate as military food Time-temperature Mark.

Present invention also offers a kind of Time-temperature indicateing arm of compressed foods, it at least includes marker With base version, the component of described marker and the weight/mass percentage composition of each component carrying described marker For：The 0.001% own diester of two meta-aminotoluene base formic acid -2,4- diine -1,6-, 0.003% two pairs of fluorobenzene sulphurs Acid -2,4- diine -1, the own diester of 6-, 9.100% bonding agent, balance of auxiliary agent, the terminal face of its reference colour The OD value of color is set to 2.0.This Time-temperature indicateing arm is particularly suited for military 09 formula compacted ration.

Wherein, described bonding agent is selected from polystyrene, polyurethanes or Corvic Plant or multiple mixing, described auxiliary agent is dichloromethane.

Brief description

Fig. 1 is the aggretion type TTI color change trendgram of 2.5 years formula.

Fig. 2 is the aggretion type TTI color change trendgram of 4 years formula.

Fig. 3 is PFBS monomer and HDmTU grey scale change curve chart under 100 degree respectively.

Fig. 4 is the graph of a relation of PFBS proportion and Mean Value value.

Fig. 5 changes over curve chart for different formulations Mean Value under 100 degree.

Fig. 6 is that Mean Value value changes over curve chart to formula 7 at each temperature.

Fig. 7 is that Mean Value value changes over curve chart to formula 4 at each temperature.

Fig. 8 be different temperatures under TTI-A label OD value with period of storage variation diagram.

Fig. 9 is the time dependent matched curve of OD value at 48 DEG C.

Figure 10 is the time dependent matched curve of OD value at 58 DEG C.

Figure 11 is the time dependent matched curve of OD value at 68 DEG C.

Figure 12 is the linear relationship chart with 1/T for the logarithm of reaction rate constant.

Figure 13 be different temperatures under TTI-B label OD value with period of storage variation diagram.

Figure 14 is the time dependent matched curve of OD value at 48 DEG C.

Figure 15 is the time dependent matched curve of OD value at 58 DEG C.

Figure 16 is the time dependent matched curve of OD value at 68 DEG C.

Figure 17 is the linear relationship chart with 1/T for the logarithm of reaction rate constant.

Figure 18 be different temperatures under TTI-B label OD value with period of storage variation diagram.

Figure 19 is the time dependent matched curve of OD value at 48 DEG C.

Figure 20 is the time dependent matched curve of OD value at 58 DEG C.

Figure 21 is the time dependent matched curve of OD value at 68 DEG C.

Figure 22 is the linear relationship chart with 1/T for the logarithm of reaction rate constant.

Specific embodiment

Hereinafter the principle and feature of the present invention is described, example is served only for explaining the present invention, and Non- for limiting the scope of the present invention.

Embodiment

1. experimental apparatus and experimental drug

1.1 sign instruments

1.1.1 infrared spectrum：Shimadzu IR-208 infrared spectrometer (KBr tabletting).

1.1.21HNMR：Varian Mercury VX 300 nuclear magnetic resonance analyser (TMS makees internal standard).

1.1.3 fusing point：X-4 type digital micro-analysis melting point apparatus (thermometer does not correct).

1.2 experimental drug

Cu-lyt., propilolic alcohol, methanol, pyridine, concentrated hydrochloric acid (37%), oxolane, triethylamine, Fluorobenzene, sulfonic acid chloride, a toluene diisocyanate, dichloromethane, petroleum ether (30～60 DEG C), ethyl acetate, Potassium hydroxide, dioxane, p- N, N dimethylamine yl pyridines, acetone etc. are ommercially available AR.

Oxolane, processes through sodium, steams again.Triethylamine, is dried overnight with potassium hydroxide, filters.

The synthesis of 2.TTI monomer

2.1 2,4- diine -1,6- two hexanol

Cu-lyt. 2.4g (0.024mol), propilolic alcohol 24ml is sequentially added in 100mL there-necked flask (0.4mol), methanol 40mL, pyridine 12mL, is passed through air, stirs 7h.By mixture with ice-cold But, and add 20mL concentrated hydrochloric acid, then add 100mL saturated sodium-chloride water solution, mixture is put In refrigerator overnight.The solid sucking filtration that will separate out, filter cake frozen water is washed, and is dried, and obtains yellow crude 11.6g, yield 52.7%.With dichloromethane, recrystallizing methanol, obtain white crystal.111-112 DEG C of fusing point.

1HMNR(DMSO-d6,ppm)：5.43(1H,t,J 6Hz,CH2OH),4.17(2H,d,J 6Hz, CH2OH).

FT-IR(KBr,cm-1):3500-2600,2363,1618,1478,1351,1032,914,663.

2.2 pairs of fluorophenylsulfonyl chloride

In 250mL there-necked flask, fluorobenzene 46.6mL (0.5mol) is added dropwise over 100mL (1.5mol) In chlorosulfonic acid, about 1h, keep temperature in reaction bulb to be 20-25 DEG C.Completion of dropping, continues reaction 2h.. Reactant liquor is poured in frozen water, has solid to separate out.Filter, filter cake frozen water is washed, yield 90%.Solid Put refrigerator stand-by.

2.3 2,4- hexadiine -1,6- glycol-two-meta-aminotoluene carbamate (HDmTU)

The nothing of 2,4- diine -1,6- two hexanol 1.3g (0.012mol) is sequentially added in 100mL there-necked flask Water tetrahydrofuran solution, the anhydrous tetrahydrofuran solution of a toluene diisocyanate 3.2g (0.024mol), Stirring, is added dropwise over triethylamine 4mL.According to TLC measured reaction progress.After reaction terminates, will react Liquid is added dropwise in 200mL petroleum ether.Completion of dropping, static several minutes.Precipitation is leached, is used in combination Petroleum ether is washed, and is filtrated to get white solid.

1HMNR(CDCl3,ppm)：9.83 (1H, s, NH), 7.27-7.14 (3H, m, aryl H), 6.84 (1H, d, J 6.9Hz, 2-aryl H), 4.9 (2H, s, CH2), 2.26 (3H, s, CH3).

FT-IR(KBr,cm-1):3300,2360,1715,1617,1557,1426,1224,1076, 617.

2.42,4- hexadiine -1,6- glycol-two-to fluorobenzene sulphonic acid ester (PFBS)

Under ice bath, (0 DEG C) sequentially adds 2,4- diine -1,6- two hexanol 0.5g (0.045mol), tetrahydrochysene furan Mutter 30mL, to fluorophenylsulfonyl chloride 2.53g (0.013mol), stir.Potassium hydroxide 0.8g (0.014mol) It is dissolved in 15mL water, dropwise add potassium hydroxide solution in reaction bulb (0 DEG C), continue stirring, TLC Point plate measured reaction progress.After reaction completely, reaction mixture adds appropriate frozen water, stirring.Standing, Discovery has pink insoluble matter to be occurred.It is filtrated to get pink solid 1.9g, yield 90%.

1HMNR(CDCl3,ppm)：7.95 (2H, m, aryl H), 7.25 (2H, m, aryl H), 4.79(2H,s,CH2O).

FT-IR(KBr,cm-1):3500,2800-3000,1494,1383,950,840,550.

3. aggretion type TTI basic performance tests

3.1 test materials and equipment

3.1.1 test drug and reagent

PFBS, HDmTU, polyethylene, polystyrene, dichloromethane

3.1.2 test key instrument and equipment

JC101 type electric drying oven with forced convection, IKA C-MAG HS 7 heating stirrer, Shimadzu IR-208 infrared spectrometer, Varian Mercury VX 300 nuclear magnetic resonance analyser, X-4 type digital micro-analysis melt Point instrument.Miscellaneous equipment is laboratory conventional equipment.

3.2 content of the test and method

3.2.1 color composition performance

With PFBS and HDmTU that synthesize as object of study, analyze it respectively under the conditions of 85 degree, The situation of change colour developing over time, and the Chomogenic activity of two kinds of colour developing monomers has been carried out tentatively general Condition.

Fig. 3 is PFBS monomer and HDmTU grey scale change curve chart under 100 degree respectively.

From figure 3, it can be seen that at the same temperature, prolongation over time, respectively with PFBS monomer, The gray value of the colour developing label that HDmTU monomer makes also is gradually increased, and PFBS monomer colour developing speed Hurry up, colour developing terminal is short.By exponential equation, regression analyses are carried out to surveyed experimental data, when obtaining 85 degree The gray value of two kinds of TTI is respectively with the kinetic model that developing time changes：

The grey scale change kinetic model of 1 100 degree of polymerization type monomer TTI of table

Through linear regression analyses number it has been found that the R of two kinds of TTI model²It is all higher than 0.9, the phase of matching Closing property is higher, may infer that the variable color of both TTI changes for first order kineticss, monomer polyreaction is First order kineticss react.

3.2.2 Monomer Formations are analyzed to aggretion type TTI color developing

The colour developing cycle of PFBS with HDmTU is different, if making TTI only use a kind of monomer, produces TTI instruction the cycle fix, the scope of application is narrower.Can be made by mutually mixing two kinds of monomers The TTI going out the different colour developing cycles expands its range of application, simultaneously facilitates screening and thinks with food shelf model The TTI formula joined.

To the TTI being fabricated to the mixture of HDmTU and PFBS different proportion, tentatively pass through index Mean Value INT and the corresponding relation of color, judge the relationship of the two, scanned picture is through Quantity one Software processes, the data obtained is as shown in Figure 4 after Origin software processes.

Fig. 4 is the graph of a relation of PFBS proportion and Mean Value value.

It can be seen that increasing with PFBS proportion, Mean Value value is gradually lowered, and warp The process of 100 degree of 4h, the incrementss of Mean Value also increase with the increase of PFBS proportion, By can illustrate can by adjust HDmTU and PFBS ratio control TTI color change.

Fig. 5 changes over curve chart for different formulations Mean Value under 100 degree.

As shown in figure 5, colour test, the number of each formula are carried out to the TTI of 11 kinds of deployed formula According to as shown in Figure 5 after Origin software processes.From fig. 5, it can be seen that growth over time, Mean Value desired value, at 100 degree, initially sharply increases, is subsequently gradually increased and progressively tends towards stability, And it is seen that the TTI instruction cycle of different formulations is different, surveyed data is entered according to exponential equation Row linear regression analyses, obtain the change of Mean Value value of different formulations TTI when 100 degree at any time Between change kinetic model be respectively table 2 below shown in：

Table 2 different formulations TTI is in the time dependent kinetic model of change of 100 degree of Mean Value values

Through regression analyses data, each model R²It is all higher than 0.91, the dependency of matching is higher, can push away Break aggretion type TTI color change meet first order kineticss change, monomer polymerization reactions are first order kinetics Learn reaction.By by various formula when 100 degree kinetic model and military food quality comparison model phase Coupling, result shows that formula 2, formula 4, formula 7 can be mated with food model.

At 100 degree, 85 degree, 45 degree, colour developing examination is carried out respectively to formula 2, formula 7 aggretion type TTI Test, the data of various formula after Origin software processes as shown in Figure 6, Figure 7.

Fig. 6 is that Mean Value value changes over curve chart to formula 7 at each temperature.

Fig. 7 is that Mean Value value changes over curve chart to formula 4 at each temperature.

As shown in Figure 6, Figure 7, growth over time, Mean Value value gradually rises first quick and back slow. Two kinds of formula of contrast find, formula 4 variable color terminal time is longer compared with formula 7.Index is pressed to surveyed data Equation carries out regression analyses, obtain 45 degree, 85 degree, 100 degree when aggretion type TTI Mean Value The time dependent kinetic model of value changes is respectively：

The change kinetics model of table 3 formula 7Mean Value value

The change kinetics model of table 4 formula 4Mean Value value

Through regression analyses number it has been found that the R2 of various model is all higher than 0.90, the dependency of matching is relatively Height, can be inferred that the color change of aggretion type TTI meets first order kineticss change, monomer polymerization reactions It is first order kineticss reaction.

4 aggretion type indicateing arm preparation methoies

4.1 test materials and equipment

4.1.1 test drug and reagent

PFBS, HDmTU, polyethylene, polystyrene foam plastics, dichloromethane, ethyl acetate, Valve bag, preservative film, freshness protection package

4.1.2 test key instrument and equipment

JC101 type electric drying oven with forced convection, IKA C-MAG HS 7 heating stirrer, Shimadzu IR-208 infrared spectrometer, Varian Mercury VX 300 nuclear magnetic resonance analyser, X-4 type digital micro-analysis melt Point instrument, X-rite 528 light splitting Density Measuring Instrument, white wool brush

Miscellaneous equipment is laboratory conventional equipment.

4.2 experiment content and method

4.2.1 the selection of adhesive

Based on the fact foam plasticss can be dissolved by some organic solvents, we are with dichloromethane by chemical combination Thing monomer and foam plasticss dissolve simultaneously, and then organic solvent volatilizees and film forming naturally, use after pruning size In the research of colour developing experiment, can be by controlling the amount of foam plasticss and the amount of compound monomer, research Its situation that develops the color.Therefore, we determined that aggretion type TTI most suitable be adhesive foam plasticss.

4.2.3 dissolving-volatility process

4.2.3.1 aggretion type TTI formula

Table 5 aggretion type TTI formula

4.2.3.2 preparation process

Control M total=0.0090g, 6cm culture dish presses following form and weighs PFBS and HDmTU, then Mixing.

Claim 9.6g foam plasticss, with the dissolving of 48mL dichloromethane, prepare 0.2g/mL foam plasticss dichloro Methane liquid.

Gradually load weighted mixture 2mL dichloromethane is dissolved respectively, plus 2mL brand-new 0.2g/mL Foam plasticss dichloromethane solution, after stirring, dries, the demoulding, 6 groups of data of plastic packaging film-making one.

4.2.3.3 information record and process

By the good film of plastic packaging be respectively placed in 45 DEG C, 85 DEG C, under the conditions of 100 DEG C, color change is observed in timing, And use scanner scanning picture, record gray scale, OD, Mean value information.

Recorded data all is analyzed processing with Origin.

4.2.4 dissolving-rubbing method

4.2.4.1 aggretion type TTI formula

Table 6 aggretion type TTI formula

4.2.4.2 preparation process

Control M total=0.0090g, 6cm culture dish presses following form and weighs PFBS and HDmTU, then Mixing.

Claim 9.6g foam plasticss, with the dissolving of 48mL dichloromethane, prepare 0.2g/mL foam plasticss dichloro Methane liquid.

Gradually load weighted mixture 2mL dichloromethane is dissolved respectively, plus 2mL brand-new 0.2g/mL Foam plasticss dichloromethane solution, after stirring, dries, the demoulding, 6 groups of data of plastic packaging film-making one.

4.2.4.3 information record and process

By the good film of plastic packaging be respectively placed in 45 DEG C, 85 DEG C, under the conditions of 100 DEG C, color change is observed in timing, And use scanner scanning picture, the information such as record gray scale, OD, Mean value.

Recorded data all is analyzed processing with Origin.

4.3 test results and analysis

4.3.1 dissolving-volatility process prepares material property analysis

The aggretion type TTI label film advantage of dissolving-volatility process preparation is that thickness controllability is strong, quantitative analyses Error is little.It is both and also have a disadvantage that：The solvent volatilization time is long, easy bubble, die edge waste of material, Cutting difficulty (mould has obstruction), inefficiency.

4.3.2 dissolving-rubbing method prepares material property analysis

With solvent, colour developing mixture dissolving in formula is configured to certain concentration solution, with wide brush brush in glass In glass plate, brushed one layer after drying the brush second layer till solution brush is complete, such TTI label film The smooth bubble-free of interior surface, cuts out conveniently, can be applicable to make in a large number.But, the film that this method is made Can be due to the uneven but colour development material skewness of exerting oneself.

5. aggretion type storage period indicateing arm Time-temperature model determination

First pass through colour developing week by making aggretion type TTI containing different ratio colour developing monomer in high temperature Phase goes out f with military food storage cycle match degree preliminary screening, measures its color change over time Change situation.

5.1 TTI-A labels

TTI-A label OD value is with storage temperature change as shown in figure 8, the formula of wherein TTI-A label Corresponding to the formula 1 in " table 5 aggretion type TTI formula "：

Fig. 8 be different temperatures under TTI-A label OD value with period of storage variation diagram.

With the prolongation of period of storage, the OD value of TTI-A label is continuously increased, and temperature is higher, The speed that OD value increases is faster.Using Origin software to TTI-A label OD value under different temperatures with The change of period of storage carries out regression analyses by exponential equation, its matched curve such as Fig. 8, Fig. 9, Figure 10 Shown：

Fig. 9 is the time dependent matched curve of OD value at 48 DEG C.

Figure 10 is the time dependent matched curve of OD value at 58 DEG C.

Figure 11 is the time dependent matched curve of OD value at 68 DEG C.

Obtain TTI-A label OD value changes kinetic model as shown in the table：

Table 7 TTI-A label OD value changes kinetic model

From three above linear regression model (LRM), regression coefficient is higher, the good matching of each model OD value changes trend.

The logarithm of speed constant and the linear relationship of 1/T are as shown in figure 12 at each temperature：

Figure 12 is the linear relationship chart with 1/T for the logarithm of reaction rate constant.

The regression coefficient of this matched curve is 0.9064, and equation is for y=-9617.59x+27.66 dependency relatively Good.Fitting data is processed, trying to achieve reaction activity for 80KJ/mol. pre-exponential factor is 1.029 ×1012D-1.Therefore, the Arrhenius equation of OD value is：

$k_a=k_{a0}{e}^{-\frac{E_A}{RT}}=1.029\×1012e^{-79.96\×1000/RT}$

It is further known that TTI-A material OD value kinetic model is：

$1.6599-A=A_0{e}^{k_{a}t}=A_0{e}^{k_{a0}{e}^{-E_a/{\mathrm{RT}}_t}}=0.70e^{-(1.029\×{10}^{12}{e}^{-79.96\×1000/RT})t}$

5.2 TTI-B labels

TTI-B label OD value with storage temperature change as shown in figure 13, wherein the joining of TTI-B label Side corresponds to the formula 9 in " table 5 aggretion type TTI formula "：

Figure 13 be different temperatures under TTI-B label OD value with period of storage change.

Knowable to Fig. 5-16, with the prolongation of period of storage, the OD value of TTI-B label is continuously increased, And temperature is higher, the speed that OD value increases is faster.Using Origin software to TTI-B under different temperatures Label OD value carries out regression analyses with the change of period of storage by exponential equation, its matched curve below figure Shown：

Figure 14 is the time dependent matched curve of OD value at 48 DEG C.

Figure 15 is the time dependent matched curve of OD value at 58 DEG C.

Figure 16 is the time dependent matched curve of OD value at 68 DEG C.

Obtain TTI-B label OD value changes kinetic model as shown in the table：

Table 8 TTI-B label OD value changes kinetic model

From three above linear regression model (LRM), regression coefficient is higher, the good matching of each model OD value changes trend.

The logarithm of speed constant and the linear relationship of 1/T are as shown in figure 17 at each temperature：

Figure 17 is the linear relationship chart with 1/T for the logarithm of reaction rate constant.

The regression coefficient of this matched curve is 0.9866, and equation is for y=-11258.39x+32.95 dependency relatively Good.Fitting data is processed, trying to achieve reaction activity for 93.6KJ/mol. pre-exponential factor is 2.042 ×1014D-1.Therefore, the Arrhenius equation of OD value is：

$k_a=k_{a0}{e}^{-\frac{E_A}{RT}}=2.042\×1014e^{-93.6\×1000/RT}$

It is further known that kinetic model is：

$1.8442-A=A_0{e}^{k_{a}t}=A_0{e}^{k_{a0}{e}^{-E_a/{\mathrm{RT}}_t}}=0.76e^{-(2.042\×{10}^{14}{e}^{-93.6\×1000/RT})t}$

5.3TTI-C label

TTI-C label OD value with storage temperature change as shown in figure 18, wherein the joining of TTI-C label Side corresponds to the formula 3 in " table 5 aggretion type TTI formula "：

Figure 18 be different temperatures under TTI-B label OD value with period of storage variation diagram.

With the prolongation of period of storage, the OD value of TTI-C label is continuously increased, and temperature is higher, The speed that OD value increases is faster.Using Origin software to TTI-C label OD value under different temperatures with The change of period of storage carries out regression analyses by exponential equation, and its matched curve is as shown below：

Figure 19 is the time dependent matched curve of OD value at 48 DEG C.

Figure 20 is the time dependent matched curve of OD value at 58 DEG C.

Figure 21 is the time dependent matched curve of OD value at 68 DEG C.

Obtain TTI-A label OD value changes kinetic model as shown in the table：

Table 9 TTI-A label OD value changes kinetic model

From three above linear regression model (LRM), regression coefficient is higher, the good matching of each model OD value changes trend.

The logarithm of speed constant and the linear relationship of 1/T are as shown in figure 22 at each temperature：

Figure 22 is the linear relationship chart with 1/T for the logarithm of reaction rate constant.

The regression coefficient of this matched curve is 0.9597, and equation is for y=-9635.45x+27.72 dependency relatively Good.Fitting data is processed, trying to achieve reaction activity for 80.1KJ/mol. pre-exponential factor is 1.093 ×1012D-1.Therefore, the Arrhenius equation of OD value is：

$k_a=k_{a0}{e}^{-\frac{E_A}{RT}}=1.093\×1012e^{-80.1\×1000/RT}$

It is further known that kinetic model is：

$1.8690-A=A_0{e}^{k_{a}t}=A_0{e}^{k_{a0}{e}^{-E_a/{\mathrm{RT}}_t}}=0.98e^{{}^{-(1.093\×{10}^{12}{e}^{-80.1\×1000/RT})t}}$

6. the matching of aggretion type storage period indicateing arm

Through the screening to lot of materials, having picked out three kinds of formula aggretion type TTI labels can be used as army With food storage phase indicateing arm, the time-temperature-OD value changes kinetic simulation of this several formula materials Type is as follows：

Table 10 time-temperature-OD value changes kinetic model

According to TTI response theory, when the activation energy causing food that the main chemical reactions of qualitative change occur When consistent with the activation energy of TTI, this indicateing arm may be used in this kind of product.

So, the kinetic model of TTI：F (X)=k₁exp(-E₁/RT_eff) t must be with military food quality The kinetic model of change：There is identical activation energy.That is：

Research in conjunction with 09 compacted ration mass change understands, its time-temperature-mass change dynamic Mechanical model can be expressed as：

$A=0.025e^{(6.79\×{10}^{10}{e}^{-77.93\×1000/RT})t}$

Contrast 09 compacted ration mass change kinetic model and thermo-sensitive material kinetics model of color It is seen that, formula TTI-B is closer to, and the military food storage period indicateing arm that it is prepared into can be relatively It is the quality change situation of close instruction 09 compacted ration, if being adjusted further to its formula, The on all four material of activation energy should be prepared.

According to research above, when storage temperature for 25 DEG C is, 09 compacted ration shelf life is 1600 My god.This two parameters are substituted into the kinetic model of TTI-B color changes so that it may when calculating its terminal Between OD value be 2.0.Therefore, when the terminal colour OD value of setting reference colours is 2.0, you can by TTI-A Storage period indicateing arm as 09 compacted ration uses.

Aggretion type TTI color change trendgram provided by the present invention is as shown in Figure 1, 2：

Fig. 1 is the aggretion type TTI color change trendgram of 2.5 years formula, from left to right, the face of color lump Color as：RGB (238,208,182), RGB (231,163,126), RGB (146, 71,52), RGB (122,47,42), RGB (109,52,43), RGB (114,69,50).

Fig. 2 is the aggretion type TTI color change trendgram of 4 years formula, from left to right, the color of color lump As：RGB (235,205,177), RGB (237,152,111), RGB (178,80, 53), RGB (154,53,43), RGB (179,53,39), RGB (139,44,42).

The foregoing is only the better embodiment of the present invention, not in order to limit the present invention, all at this Within bright spirit and principle, any modification, equivalent substitution and improvement made etc., should be included in this Within the protection domain of invention.

Claims (7)

1. a kind of aggretion type time-temperature indicator, including weight than for 6：1～1：6 two toluene The own diester of amidocarbonic acid -2,4- diine -1,6- and the own diester of the two couples of fluorobenzene sulfonic acid -2,4- diine -1,6-.

2. aggretion type time-temperature indicator according to claim 1, described two meta-aminotoluene bases The weight of the own diester of formic acid -2,4- diine -1,6- and the own diester of the two couples of fluorobenzene sulfonic acid -2,4- diine -1,6- is than for 3： 1～1：3.

3. a kind of food Time-temperature indicateing arm, it at least includes marker and carries described marker Base version, the component of described marker and the weight/mass percentage composition of each component are：0.001%～0.006% The own diester of two meta-aminotoluene base formic acid -2,4- diine -1,6-, 0.001%～0.006% two pairs of fluorobenzene sulfonic acid - 2,4- diine -1, the own diester of 6-, 8.100%～10.000% bonding agent, balance of auxiliary agent.

4. food Time-temperature indicateing arm according to claim 3, the component of described marker and The weight/mass percentage composition of each component is：0.001%～0.003% two meta-aminotoluene base formic acid -2,4- diines The own diester of -1,6-, 0.001%～0.003% own diester of two couples of fluorobenzene sulfonic acid -2,4- diine -1,6-, 8.100%～10.000% bonding agent, balance of auxiliary agent.

5. the food Time-temperature indicateing arm according to claim 3 or 4 it is characterised in that：Institute The described bonding agent stating marker is selected from polystyrene, polyurethanes or Corvic one Plant or multiple mixing.

6. the food Time-temperature indicateing arm according to claim 3 or 4 it is characterised in that：Institute The described auxiliary agent stating marker is dichloromethane.

7. the Time-temperature indicateing arm of a kind of compressed foods, it at least includes marker and carries described finger Show that the base version of layer, the component of described marker and the weight/mass percentage composition of each component are：The two of 0.001% The own diester of meta-aminotoluene base formic acid -2,4- diine -1,6-, 0.003% two couples of fluorobenzene sulfonic acid -2,4- diine -1,6- Own diester, 9.100% bonding agent, balance of auxiliary agent, the terminal colour of the reference colours of described marker OD value is set to 2.0.