本文選題：塑料復(fù)合膜 + 甲苯　； 參考：《沈陽(yáng)農(nóng)業(yè)大學(xué)》2017年博士論文

【摘要】：食品用塑料復(fù)合包裝膜是將兩種或者兩種以上材質(zhì)的塑料薄膜通過(guò)膠黏劑復(fù)合在一起,同時(shí)具有各層薄膜的優(yōu)良性質(zhì),是目前市場(chǎng)上最為理想的軟包裝材料。低密度聚乙烯(LDPE)和流延聚丙烯(CPP)具有獨(dú)特的防潮性和熱封性,常作為復(fù)合膜的內(nèi)層膜基材,與食品直接接觸。在生產(chǎn)過(guò)程中,油墨、膠黏劑及其稀釋劑等有機(jī)溶劑夾在復(fù)合膜的中間層,如果含量較高或揮發(fā)不充分,可能會(huì)發(fā)生殘留并遷移到食品中。殘留溶劑通常是幾種有機(jī)溶劑的混合體,其中主要為甲苯和乙酸乙酯等,而甲苯是公認(rèn)的致癌物質(zhì),且吸附性較高、易發(fā)生殘留。因此,本研究以食品用塑料復(fù)合包裝膜為試驗(yàn)材料,系統(tǒng)研究了普通塑料復(fù)合膜和耐蒸煮塑料復(fù)合膜中殘留甲苯向食品模擬液中的遷移規(guī)律,進(jìn)一步研究了耐蒸煮塑料復(fù)合膜中殘留甲苯向豬肉中遷移效果,探討蒸煮條件對(duì)膜阻隔性能和機(jī)械性能的影響;建立遷移數(shù)學(xué)模型并對(duì)模型預(yù)測(cè)效果進(jìn)行評(píng)價(jià);采用紅外吸收光譜、掃描電鏡、差式掃描量熱分析、熱重分析等技術(shù)手段,研究遷移條件對(duì)塑料復(fù)合膜內(nèi)層膜微觀結(jié)構(gòu)的影響,從而探討甲苯遷移機(jī)理,為保障食品安全及建立相關(guān)法律法規(guī)提供理論依據(jù)。主要研究結(jié)果如下:(1)溫度越高,塑料復(fù)合膜中殘留甲苯向模擬液中的遷移率越高。遷移時(shí)間越長(zhǎng),甲苯遷移率越高,并最終趨于穩(wěn)定值;模擬液對(duì)甲苯遷移率影響較為顯著。普通塑料復(fù)合膜中甲苯向不同食品模擬液中的遷移率大小依次為:異辛烷50%乙醇3%乙酸10%乙醇。耐蒸煮塑料復(fù)合膜中甲苯向不同食品模擬液和調(diào)味品模擬液中遷移率大小依次分別為:橄欖油3%乙酸超純水;3g/100mL氯化鈉0.1g/100mL谷氨酸鈉5g/100mL蔗糖;內(nèi)層膜厚度越大阻隔性越好,甲苯向模擬液中的遷移率越低。普通塑料復(fù)合膜中,甲苯透過(guò)不同材質(zhì)內(nèi)層膜向模擬液中遷移率大小依次為:LDPE30LDPE50CPP30CPP50;不同微波加熱條件對(duì)耐蒸煮塑料復(fù)合膜中甲苯遷移率產(chǎn)生一定影響。微波功率越大、加熱時(shí)間越長(zhǎng),甲苯遷移率越高。無(wú)論是使用哪種功率進(jìn)行微波加熱,當(dāng)模擬液加熱到大約80℃時(shí),甲苯遷移率差異不顯著。(2)豬肉中甲苯的適宜提取條件為:異辛烷作為萃取溶劑,振蕩萃取40 min,該條件下甲苯的回收率在80.3%～88.7%之間,相對(duì)標(biāo)準(zhǔn)偏差(RSD)在3.2%～6.1%之間;蒸煮溫度越高、時(shí)間越長(zhǎng),甲苯遷移率越大,但在121℃和135℃溫度下,蒸煮20 min后甲苯遷移率變化不顯著;豬肉中脂肪含量越高,甲苯遷移率越大;接觸食品的塑料表面積與豬肉體積之比(表面積-體積比)對(duì)甲苯遷移影響較小;高溫蒸煮可使膜阻隔性能降低,蒸煮時(shí)間越長(zhǎng),膜的阻隔性能相對(duì)越弱。隨著蒸煮溫度的升高和時(shí)間的延長(zhǎng),膜的拉斷力和斷裂伸長(zhǎng)率下降,尤其是斷裂伸長(zhǎng)率變化更為明顯。(3)采用Brandsch經(jīng)驗(yàn)?zāi)Ｐ秃虵ick定律推算模型計(jì)算塑料復(fù)合膜中甲苯遷移擴(kuò)散系數(shù)經(jīng)驗(yàn)值(Dexp)和Fick定律推算值(DFick)。結(jié)果表明,甲苯擴(kuò)散系數(shù)Dexp和DFick均隨著溫度的升高而增大。大多數(shù)情況下,塑料復(fù)合膜中甲苯擴(kuò)散系數(shù)經(jīng)驗(yàn)值高于Fick定律推算值(Dexp㧐Dfick),僅CPP30樣品在4℃～20℃遷移溫度下,甲苯向異辛烷中遷移時(shí)的Dexp㩳DFick;無(wú)論選用何種模擬液,相同溫度下甲苯擴(kuò)散系數(shù)經(jīng)驗(yàn)值(Dexp)均相同;利用分配系數(shù)定義式來(lái)計(jì)算遷移過(guò)程中塑料復(fù)合膜中甲苯分配系數(shù)(KP.F),KP.F 越小表明甲苯向模擬液中的遷移量越大。溫度越高,甲苯向同種模擬液中遷移KP.F值越小。普通塑料復(fù)合膜中甲苯向不同模擬液中遷移的KP.F值大小依次為:3%乙酸10%乙醇50%乙醇異辛烷。耐蒸煮塑料復(fù)合膜中甲苯向模擬液中遷移的KP.F值大小依次為:超純水3%乙酸橄欖油;建立單層遷移數(shù)學(xué)模型并對(duì)其簡(jiǎn)化,以Dexp和KP.F作為模型中重要參數(shù),并將甲苯遷移量的模型推算值與試驗(yàn)值進(jìn)行比較。結(jié)果表明,模型可以較好的預(yù)測(cè)甲苯遷移量的變化趨勢(shì)。除了在4℃和20℃條件下,CPP30樣品中甲苯向異辛烷中遷移量的模型值略小于試驗(yàn)值外,其他條件下,LDPE30、CPP30和RCPP70三種樣品中甲苯遷移量的模型值均大于或約等于試驗(yàn)值。(4)經(jīng)遷移條件處理后,普通塑料復(fù)合膜(LDPE、CPP)和耐蒸煮塑料復(fù)合膜(RCPP)三種樣品紅外吸收光譜中部分吸收峰均向低波長(zhǎng)方向移動(dòng),說(shuō)明膜內(nèi)部分子間作用力下降;掃描電鏡顯示經(jīng)處理后的樣品斷面微觀結(jié)構(gòu)出現(xiàn)褶皺、扭曲等現(xiàn)象,CPP膜微觀結(jié)構(gòu)變化略小于LDPE膜,異辛烷和橄欖油分別對(duì)普通膜和蒸煮膜微觀結(jié)構(gòu)影響較大;DSC分析表明樣品經(jīng)處理后膜的熔點(diǎn)和熱焓值均下降,說(shuō)明膜的熱穩(wěn)定性變差,結(jié)晶度降低,CPP膜變化幅度小于LDPE膜。未接觸模擬液的RCPP樣品在高溫蒸煮后,膜的結(jié)晶度降低,但熱穩(wěn)定性變化較小;TG曲線顯示經(jīng)處理后的LDPE和CPP樣品熱分解溫度降低,熱穩(wěn)定性下降,RCPP樣品在高溫蒸煮后,膜的熱穩(wěn)定性變化較小。
[Abstract]:Plastic composite packaging film for food is combined with two or more than two kinds of plastic film through adhesive. It is the most ideal soft packaging material in the market at the same time. Low density polyethylene (LDPE) and CPP have unique moisture resistance and thermal sealing. In the process of production, organic solvents such as ink, adhesives and their diluents are sandwiched in the middle layer of the composite membrane in the process of production. If the content is higher or less volatile, it may occur and migrate to the food. The residual solvent is usually a mixture of several organic solvents, mainly toluene and B While toluene is recognized as a carcinogenic substance, and its adsorbability is high, it is easy to remain residual. Therefore, this study has studied the migration of residual toluene in the common plastic composite film and the steamed plastic composite membrane with the plastic composite packaging film as the experimental material. The effect of residual toluene to pork in the membrane was studied, and the effects of cooking conditions on the membrane barrier property and mechanical properties were investigated. The migration mathematical model was established and the prediction effect was evaluated. The transfer conditions were studied by infrared absorption spectroscopy, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis and other technical means. The mechanism of toluene migration is discussed in order to provide theoretical basis for guaranteeing food safety and establishing relevant laws and regulations. The main results are as follows: (1) the higher the temperature, the higher the mobility of residual toluene in the plastic composite membrane. The longer the migration time, the higher the transfer rate of toluene, and finally to a stable value. The migration rates of toluene to different food analog liquid in the ordinary plastic composite membrane are in turn: isooctane 50% ethanol 3% acetic acid 10% ethanol. The migration rates of toluene to different food analog liquid and seasonings in the steamed plastic composite membrane are respectively: olive oil 3% acetic acid super. Pure water; 3g/100mL sodium chloride 0.1g/100mL sodium glutamate 5g/100mL sucrose; the greater the thickness of the inner film thickness, the better the barrier property, the lower the mobility of toluene to the simulated solution. In the ordinary plastic composite membrane, the size of the transfer rate of toluene through the inner membrane of different materials is as follows: LDPE30LDPE50CPP30CPP50. The mobility of toluene in the composite membrane has a certain effect. The greater the microwave power, the longer the heating time, the higher the mobility of toluene. No matter which power is used for microwave heating, when the simulation solution is heated to about 80 C, the difference of toluene mobility is not significant. (2) the optimum extraction conditions for the toluene in pork are: isooctane as an extraction solvent, oscillation. The recovery of toluene was 40 min, the recovery rate of toluene was between 80.3% and 88.7%, and the relative standard deviation (RSD) was between 3.2% and 6.1%. The higher the cooking temperature, the longer the time, the greater the mobility of toluene, but at the temperature of 121 and 135 C, the change of toluene mobility was not obvious after 20 min, the higher the fat content in the pork, the greater the toluene mobility; contact with the higher the transfer rate of toluene. The ratio of plastic surface area to pork volume (surface area volume ratio) has little effect on the migration of toluene; high temperature cooking can reduce the membrane barrier performance and the longer the cooking time, the weaker the membrane barrier performance. With the increase of cooking temperature and time, the breaking force and elongation at break of the membrane decrease, especially the elongation at break. (3) the empirical value (Dexp) and Fick law calculation value of the toluene transfer diffusion coefficient (Dexp) and Fick law are calculated by the Brandsch empirical model and the Fick law calculation model. The results show that the toluene diffusion coefficient Dexp and DFick increase with the increase of temperature. In most cases, the diffusion coefficient of toluene in the plastic composite membrane has been found. The test value is higher than the Fick law calculation value (Dexp? Dfick). Only CPP30 samples at 4 ~ 20 C migration temperature, Dexp? DFick when toluene migrated into isooctane; no matter which analog liquid is used, the empirical value of toluene diffusivity (Dexp) is the same at the same temperature, and the toluene fraction in the plastic composite membrane during the migration process is calculated by the definition formula of distribution coefficient. The smaller the distribution coefficient (KP.F), the smaller the migration of toluene to the simulated solution. The higher the temperature, the smaller the KP.F value of toluene migrated to the same analogue liquid. The KP.F value of toluene migration to different analog liquid in the ordinary plastic composite membrane is 3% acetic acid 10% ethanol and 50% ethanol isooctane. The KP.F value of the transfer is in turn: ultra pure water 3% acetic olive oil; a single layer migration mathematical model is established and simplified. Dexp and KP.F are used as important parameters in the model, and the calculated value of toluene migration is compared with the experimental value. The results show that the model can predict the change trend of toluene migration well. Except at 4 degrees C The model value of the migration of toluene to isooctane in CPP30 samples at 20 C is slightly smaller than the experimental value. Under other conditions, the model values of toluene migration in three samples of LDPE30, CPP30 and RCPP70 are both greater than or approximately equal to the experimental values. (4) ordinary plastic composite membrane (LDPE, CPP) and steamed plastic composite membrane (RCPP) are treated by migration conditions. In the infrared absorption spectrum of the three samples, some absorption peaks move to the low wavelength direction, indicating that the intermolecular force in the membrane decreases. The scanning electron microscope shows that the microstructure of the sample section after treatment is wrinkled and distorted, and the microstructure changes of the CPP film are slightly smaller than that of the LDPE film, and the isooctane and the olive oil are micro to the ordinary film and the cooking membrane. DSC analysis showed that the melting point and enthalpy of the film decreased after the treatment, indicating that the thermal stability of the membrane became worse, the crystallinity decreased, and the change amplitude of the CPP film was less than that of the LDPE film. The crystallinity of the membrane in the RCPP sample without contact fluid was reduced, but the thermal stability was small, and the TG curve showed LD after treatment. The thermal decomposition temperature of PE and CPP samples decreased and the thermal stability decreased. The thermal stability of RCPP samples changed little after high temperature cooking.

【學(xué)位授予單位】：沈陽(yáng)農(nóng)業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TS206.4

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