CN110452509A - One kind is fresh-keeping to use film - Google Patents
One kind is fresh-keeping to use film Download PDFInfo
- Publication number
- CN110452509A CN110452509A CN201910707201.8A CN201910707201A CN110452509A CN 110452509 A CN110452509 A CN 110452509A CN 201910707201 A CN201910707201 A CN 201910707201A CN 110452509 A CN110452509 A CN 110452509A
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- China
- Prior art keywords
- acid
- preservative
- adr
- hydroxymethyl cellulose
- grafting
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
Abstract
The present invention provides a kind of fresh-keeping films, and the carboxylic acids preservative of hydroxyl or amino is grafted containing hydroxymethyl cellulose, can be effectively reduced the total plate count of meat during storing, the speed that meat loss of weight and hardness reduction can be effectively reduced, extend the shelf time.In addition, antistaling agent and preservative film of the invention, raw material is easy to get, abundance, nontoxic, at low cost, biodegradable and renewable, will not generation environment burden, be widely used.Hydroxymethyl cellulose has big specific surface area and high surface can, more N- sodium hydroxy methyl glycinates, gluconic acid, fumaric acid, malic acid, adipic acid can be carried by medium, and be completely embedded it is not easily to fall off, make the polylactic acid membrane containing nano-cellulose have better fresh-keeping effect and foodsafety.
Description
Technical field
The invention belongs to field of food preservation, are related to a kind of plastic film, contain cellulose graft N- with one kind is related to
The plastics that can be used for food fresh keeping of one of sodium hydroxy methyl glycinate, gluconic acid, fumaric acid, malic acid, adipic acid
Film.
Background technique
Currently, the preservative film primary raw material of food is polyethylene (PE), although can pass through some degradable additions
Agent, such as starch, modified starch or other celluloses, photosensitizer, biodegradation agent, decline the stability of plastic packing article,
It is easier to degrade in the natural environment.But this degradation is only the labile ingredient of degradation a part biology, wherein more stable
Polyethylene then become clast and exist in the environment, in some instances it may even be possible to will cause the pollution of " micro- plastics ".
Cellulose membrane is using renewable plant resources in nature as raw material, the packing timber with fast degradation characteristic
Material has been widely used in doing because of many advantages, such as its production cost is low, production process pollution is small, waste is few, materials facilitate
The packaging of food processed.Because cellulose does not have the problems such as antibiotic property, transparency difference, so that in agricultural productions such as fresh fruit of vegetables, fresh meats
Rarely has application in product packaging.
Polylactic acid (PLA) is using lactic acid as straight-chain aliphatic polyester made of polymerizable raw material, is a kind of nontoxic, nonirritant
Synthesis high molecular material, fermentation of the raw material from starch etc., or using cellulose, rubbish from cooking as raw material obtain.Poly- cream
Acid has good biodegradability, and discarded poly-lactic acid products can be the effects of nature passes through microorganism, when shorter
It is interior to be converted into carbon dioxide and water；Can also directly compost or burning, and generated without pernicious gas.Except this, polylactic acid is removed
Outside biodegradability, also there is biocompatibility and absorbability.Polylactic acid in human body can through peracid or enzyme hydrolysis at
Lactic acid.A kind of metabolite of the lactic acid as cell can be further metabolized by the intracorporal enzyme of machine, non-toxic to humans, because
This, the preservative film fresh-keeping foodstuff made of polylactic acid is safe.Based on the above reasons, polylactic acid is a kind of good polyethylene
Substitute products, the transparency, printing and heat sealability are good.However, when polylactic acid is used for food fresh keeping, not due to barrier property
Such as conventional polyethylene film, is not suitable for storing for a long time, be easy to cause loss of moist, cause more serious food weightless.
Currently, the antistaling agent for food fresh keeping, corrosion-resistant to can be used in plastic products has the guarantor for being mostly sprayed at surface
Fresh dose or bacteriostatic agent, with the extension of preservation time, fungistatic effect is gradually decreased.N- sodium hydroxy methyl glycinate, prolongs gluconic acid
Fumarate, malic acid, adipic acid etc. are all most widely used new food preservatives in the world, have many advantages, such as efficiently, wide spectrum, energy
Effectively inhibit bacterium, mould, the microorganisms growth such as saccharomycete, be widely used in cosmetics industry, food industry, coatings industry,
The fields such as paper industry and medical industry.But N- sodium hydroxy methyl glycinate, gluconic acid, fumaric acid, malic acid, oneself two
Unstable, easy to change, easy precipitating when using such as acid, influences its application in food fresh keeping film.
Therefore, it is necessary to develop the packaging films with antibiotic property can be used for the agricultural product packagings such as fresh fruit of vegetables, fresh meat
Market expands its use scope.
Summary of the invention
Aiming at the problem that lacking antibacterial degradable plastic film at present, the present invention provides a kind of film antistaling agent, uses
The carboxylic acids preservative of cellulose graft hydroxyl or amino maintains the bacteriostatic activity of preservative, and with cellulose
Property can be used in plastic film.
It is a further object of the present invention to provide a kind of polylactic acid films containing above-mentioned film antistaling agent, can be used for meat
It is fresh-keeping, it can be effectively reduced meat loss of weight, suppress growth of microorganism.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of hydroxymethyl cellulose of the carboxylic acids preservative of hydroxyl or amino grafting.The carboxymethyl cellulose with contain
The material quality ratio of the carboxylic acids preservative of hydroxyl or amino is 10:1.The preservative is selected from N- sodium hydroxy methyl glycinate, Portugal
It is grape saccharic acid, fumaric acid, malic acid, any in adipic acid.
A kind of preparation method of above-mentioned grafting hydroxymethyl cellulose, comprising the following steps:
(1) sodium metaperiodate is added in cmc soln, adjusts pH value to 3-4, normal-temperature reaction；After completion of the reaction, it is added
Excessive ethylene glycol；Then it is precipitated using ethyl alcohol, then is dialysed with pure water；
(2) solution after dialysis is added to the carboxylic acids preservative of hydroxyl or amino, pH to 7-8 is adjusted, is reacting at room temperature, instead
Film antistaling agent is obtained after answering liquid dry.
In step (1), the carboxymethyl cellulose, ethyl alcohol, sodium metaperiodate mass ratio be 1:4:1.
In step (2), the carboxylic acids preservative of the hydroxyl or amino and the mass ratio of carboxymethyl cellulose are 10:1.
In step (1), the aperture of dialysis membrane is 5 μm.
A kind of application of above-mentioned grafting hydroxymethyl cellulose as plastic products additive, function are antiseptic and inhibiting bacteria function or guarantor
It is fresh.
A kind of application of above-mentioned grafting hydroxymethyl cellulose in preservative film, food pack, food package box.
A kind of plastic products comprising above-mentioned grafting hydroxymethyl cellulose.The plastic products include preservative film, food packet
Pack, food package box and the plastic grain for preparing the said goods.
The raw material of the plastic products includes polylactic acid or polyethylene, antistaling agent, antioxidant, chain extender.
The antioxidant is selected from antioxidant 626, BHT, T501,264,245；Preferably antioxidant 245.
The chain extender selects ADR-4370F, ADR-4380, ADR-4368, ADR-4468, ADR-4300；Preferably chain extension
Agent ADR-4300.
Further, antistaling agent, antioxidant, chain extender additive amount are respectively 3-5wt%, 2-3 of polylactic acid or polyethylene
wt %、1-2 wt %。
The invention has the following advantages that
The fresh-keeping carboxylic acids preservative for containing hydroxymethyl cellulose grafting hydroxyl or amino with film of the invention, can be effective
The speed for reducing the total plate count of meat during storing, meat loss of weight and hardness reduction can be effectively reduced, extends the shelf time.
In addition, antistaling agent and preservative film of the invention, raw material is easy to get, abundance, nontoxic, at low cost, biodegradable and can
Regeneration, will not generation environment burden, be widely used.Hydroxymethyl cellulose has big specific surface area and high surface energy, passes through
Medium can carry more N- sodium hydroxy methyl glycinates, gluconic acid, fumaric acid, malic acid, adipic acid, and be completely embedded not
It is easy to fall off, make the polylactic acid membrane containing nano-cellulose that there is better fresh-keeping effect and foodsafety.
Detailed description of the invention
Fig. 1 is the influence packed to the variation of mutton weight-loss ratio；
Fig. 2 is the influence packed to mutton firmness change.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be further described, but the present invention is not by the limit of following embodiments
System.
The preparation of 1 carboxymethyl cellulose graft N of embodiment-sodium hydroxy methyl glycinate
(1) by 2 g carboxymethyl celluloses, 100 mL deionized water dissolvings, 12 h is stirred at 35 DEG C, prepare carboxymethyl cellulose
2 g sodium metaperiodates are added into cmc soln for solution；1 %H is added dropwise2SO4The pH value of solution is adjusted to 3-4 by solution,
React 6 h；After reaction, excessive ethylene glycol is added and removes unreacted sodium metaperiodate；It is precipitated using 8 mL ethyl alcohol,
Then with 5 μm of dialysis membranes with 24 h of pure water dialysis；
(2) 0.4 g N- sodium hydroxy methyl glycinate is added in the solution after dialysis, 1 molL is added dropwise-1H2SO4Solution adjusts pH
For 7-8,12 h are stirred at room temperature, 37 DEG C are dried under vacuum to constant weight and obtain the powder of cellulose graft N- sodium hydroxy methyl glycinate.
The preparation of 2 carboxymethyl cellulose of embodiment grafting gluconic acid, fumaric acid, malic acid, adipic acid
(1) by 2 g carboxymethyl celluloses, 100 mL deionized water dissolvings, 12 h is stirred at 35 DEG C, prepare carboxymethyl cellulose
2 g sodium metaperiodates are added into cmc soln for solution；1 %H is added dropwise2SO4The pH value of solution is adjusted to 3, instead by solution
Answer 6 h；After reaction, excessive ethylene glycol is added and removes unreacted sodium metaperiodate；It is precipitated using 8 mL ethyl alcohol, then
With 5 μm of dialysis membranes with 24 h of pure water dialysis；
(2) 0.4 g gluconic acid, fumaric acid, malic acid or adipic acid is added in the solution after dialysis, adjustment pH is 7.0, In
Be stirred at room temperature 12 h, 37 DEG C be dried under vacuum to constant weight obtain cellulose graft gluconic acid, fumaric acid, malic acid or oneself two
Sour powder.
The preparation of 3 preservative film of embodiment
(1) polylactic acid dried to 2 h are spare in 60 DEG C of baking ovens, the expansion of the antioxidant 245,1 % of 3 % of polylactic acid quality is added
Chain agent -4300,5 % embodiment 1 in the film antistaling agent for preparing, be granulated after blender mixing using pelletizer,
Revolving speed is that 60 r/min, seven area's temperature are respectively 160/165/170/180/175/175/175 DEG C, obtains fresh-keeping film master batch；
(2) the fresh-keeping film master batch of preparation is used and is cast by the charging of single screw rod casting machine, each area's temperature of single screw extrusion machine
Spending machined parameters is respectively 160/170/175/185/180/180/180 DEG C, and setting single screw rod revolving speed is 45 r/min, is obtained
Antimicrobial preservative film, number 1.
Using identical method, different film antistaling agents prepared by embodiment 2 are added respectively, obtains and uses containing different films
The preservative film of antistaling agent.The preservative film that containing cellulose is grafted gluconic acid, fumaric acid, malic acid or adipic acid is numbered respectively is
2-5。
Using identical method, preparation is free of the polylactic acid preservative film of antistaling agent, number 6.
4 preservative film of embodiment measures mutton fresh keeping property
1. the inhibition that pair total plate count increases
Mutton is packed with antimicrobial preservative film No. 1 and No. 3, will be saved under the conditions of 4 DEG C, measures mutton micro organism quantity with storage
The variation of number of days.Other compositions mass conservation is kept, the blank polylactic acid membrane 6 of active constituent is not added as control, experimental group
Setting and experimental result are as shown in table 1:
Mutton total plate count [lg (CFU/g)] measures in 1 packaging bag of table
From table 1 it follows that the mutton of No. 1 and No. 3 preservative film containing antibacterial agent contains in bacterium colony in entire cold storage procedure
It is considerably less than the total plate count of No. 6 preservative films in amount, illustrates that antimicrobial preservative film has bacteria resistance function, can effectively slow down bacterium colony growth
Speed, to reach fresh-keeping effect.It is fresh-keeping to mutton progress containing antimicrobial preservative film, it can be by shelf life extension 5 days of mutton
Left and right.
To the inhibiting effect of meat weightlessness
Mutton is packed with No. 2 antimicrobial preservative films, will be saved under the conditions of 4 DEG C, measurement mutton weight is with the variation for storing number of days.It protects
Other compositions mass conservation is held, using No. 6 preservative films as blank control, parallel laboratory test group, experimental group setting and experimental result are set
No. 2 nano-antimicrobial preservative films have apparent inhibiting effect to the weightlessness of mutton as shown in Figure 1:, compared to nano-antibacterial is not added
The mutton weight-loss ratio of the control group of agent, nanometer mutton antimicrobial preservative film packaging is decreased obviously, and illustrates a nanometer mutton antimicrobial preservative film
Packaging can effectively extend the preservation time of mutton, and can keep mutton freshness for more time.
Influence to meat hardness packs mutton with No. 4 antimicrobial preservative films, will save under the conditions of 4 DEG C, and measurement mutton is hard
Degree is with the variation for storing number of days.Other compositions mass conservation is kept, No. 6 preservative films of active constituent not to be added as blank control,
Parallel laboratory test group is set, and experimental group setting and experimental result are as shown in Figure 2.As shown in Figure 2, it is packed by No. 4 antimicrobial preservative films
Mutton hardness is much higher than the blank preservative film that active constituent is not added, thus further illustrates prepared by the present invention containing guarantor
Fresh agent carboxymethyl cellulose graft malic acid preservative film is able to maintain meat hardness, to reach fresh-keeping effect.
Claims (10)
1. a kind of hydroxymethyl cellulose of the carboxylic acids preservative of hydroxyl or amino grafting.
2. the hydroxymethyl cellulose of grafting according to claim 1, which is characterized in that carboxymethyl cellulose and hydroxyl or
The material quality ratio of the carboxylic acids preservative of amino is 10:1.
3. the hydroxymethyl cellulose of grafting according to claim 1, which is characterized in that the preservative is selected from N- methylol
It is Sodium Glycinate, gluconic acid, fumaric acid, malic acid, any in adipic acid.
4. a kind of preparation method of any grafting hydroxymethyl cellulose of such as claim 1-3, which is characterized in that including following step
It is rapid:
(1) sodium metaperiodate is added in cmc soln, adjusts pH value to 3-4, normal-temperature reaction；After completion of the reaction, it is added
Excessive ethylene glycol；Then it is precipitated using ethyl alcohol, then is dialysed with pure water；
(2) solution after dialysis is added to the carboxylic acids preservative of hydroxyl or amino, pH to 7-8 is adjusted, is reacting at room temperature, instead
Film antistaling agent is obtained after answering liquid dry.
5. the preparation method according to claim 4, which is characterized in that in step (1), the carboxymethyl cellulose, ethyl alcohol,
The mass ratio of sodium metaperiodate is 1:4:1；
In step (2), the carboxylic acids preservative of the hydroxyl or amino and the mass ratio of carboxymethyl cellulose are 10:1.
6. the preparation method according to claim 4, which is characterized in that in step (1), the aperture of dialysis membrane is 5 μm.
7. a kind of application such as any grafting hydroxymethyl cellulose of claim 1-3 as plastic products additive, feature exist
In function is antiseptic and inhibiting bacteria function or fresh-keeping.
8. a kind of plastic products comprising any grafting hydroxymethyl cellulose of such as claim 1-3.
9. plastic products according to claim 8, which is characterized in that the plastic products include preservative film, food packaging
Bag, food package box and the plastic grain for preparing the said goods.
10. plastic products according to claim 8, which is characterized in that the raw material of the plastic products include polylactic acid or
Polyethylene, antistaling agent, antioxidant, chain extender；
The antioxidant is selected from antioxidant 626, BHT, T501,264,245；Preferably antioxidant 245；
The chain extender selects ADR-4370F, ADR-4380, ADR-4368, ADR-4468, ADR-4300；Preferably chain extender
ADR-4300；
Further, antistaling agent, antioxidant, chain extender additive amount are respectively 3-5wt%, 2-3 wt of polylactic acid or polyethylene
%、1-2 wt %。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910707201.8A CN110452509B (en) | 2019-08-01 | 2019-08-01 | Fresh-keeping film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910707201.8A CN110452509B (en) | 2019-08-01 | 2019-08-01 | Fresh-keeping film |
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| CN110452509A true CN110452509A (en) | 2019-11-15 |
| CN110452509B CN110452509B (en) | 2021-09-07 |
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| CN201910707201.8A Active CN110452509B (en) | 2019-08-01 | 2019-08-01 | Fresh-keeping film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115772322A (en) * | 2021-09-06 | 2023-03-10 | 大禾科技发展(南京)有限公司 | Preparation method of degradable preservative film |
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| CN109897233A (en) * | 2019-03-15 | 2019-06-18 | 安徽民祯活性包装材料有限公司 | Chilled meat plastic film and preparation method thereof |
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2019
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| CN104448144A (en) * | 2013-09-15 | 2015-03-25 | 赵宝瀛 | Preparation method for carboxymethyl cellulose grafted copolymer |
| CN103724437A (en) * | 2014-01-09 | 2014-04-16 | 福建农林大学 | Multifunctional guanidine salt grafted carboxymethyl cellulose paper-making additive and preparation method thereof |
| WO2018212945A1 (en) * | 2017-05-19 | 2018-11-22 | Isp Investments Llc | Hydroxyethylpyrrolidone methacrylate/glycidyl methacrylate copolymers |
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| CN115772322A (en) * | 2021-09-06 | 2023-03-10 | 大禾科技发展(南京)有限公司 | Preparation method of degradable preservative film |
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