CN109504010A - A kind of preparation method of environmental protection food package film - Google Patents
A kind of preparation method of environmental protection food package film Download PDFInfo
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- CN109504010A CN109504010A CN201811268553.XA CN201811268553A CN109504010A CN 109504010 A CN109504010 A CN 109504010A CN 201811268553 A CN201811268553 A CN 201811268553A CN 109504010 A CN109504010 A CN 109504010A
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- C08J5/18—Manufacture of films or sheets
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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Abstract
The invention discloses a kind of preparation methods of environmentally friendly food package film, include the following steps: S1, mix hydroxyapatite, attapulgite modified, zinc oxide, titanium dioxide, dry, it crushes, starch, water is added in sieving, it heats and stirs, then heating continues to stir, and obtains mixture A;S2, polylactic acid-polycaprolactone co-polymer, polyvinyl alcohol, glycerol, D-sorbite, pentaerythrite are mixed, heats and stir, mixture A, methylcellulose, oleic acid, alginate, stabilizer is added, increase temperature, stirring obtains mixture B;S3, mixture B carries out to hot-melt extruded Blown Film, last qualitative winding, pack to get.Packaging film produced by the present invention, is readily biodegradable, and has good mechanical performance, antibiotic property, water resistance, and good combination property can satisfy the application in real life.
Description
Technical field
The present invention relates to packaging technical field of membrane, and in particular to a kind of preparation method of environmental protection food package film.
Background technique
Although plastic material possesses more excellent performance and wide applicability, but it from oil product and can not be dropped
Solution finds function admirable and reproducible alternative materials then becomes mesh in crisis of resource and environmental pollution more serious today
The most important thing of preceding Material Field research.Especially in field of membrane preparation, current commodity development leads to the dosage of packaging material
Acutely increase, especially membrane material is widely used as most light packaging material, while also resulting in a large amount of white
Pollution, developing has excellent properties, and degradable membrane material has very big economic and social benefit.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of preparation method of environmentally friendly food package film,
Packaging film obtained is readily biodegradable, and has good mechanical performance, antibiotic property, water resistance, good combination property.
The invention proposes a kind of preparation methods of environmentally friendly food package film, include the following steps:
S1, hydroxyapatite, attapulgite modified, zinc oxide, titanium dioxide are mixed, dry, pulverize, be sieved, is added
Starch, water are heated and are stirred, and then heating continues to stir, and obtain mixture A;
S2, polylactic acid-polycaprolactone co-polymer, polyvinyl alcohol, glycerol, D-sorbite, pentaerythrite are mixed, heating is simultaneously
Mixture A, methylcellulose, oleic acid, alginate, stabilizer is added in stirring, increases temperature, and stirring obtains mixture B;
S3, mixture B carries out to hot-melt extruded Blown Film, last qualitative winding, pack to get.
Preferably, the attapulgite modified preparation process is as follows:
S1, attapulgite dry, pulverize, is sieved, silane coupling agent is added, grinding obtains material A;
S2, ricinoleic acid, humic acid are mixed, and adjusts pH value, stirred, material A is added, increased temperature and grind, do
It is dry, it obtains attapulgite modified.
Preferably, in the attapulgite modified preparation process, attapulgite is placed at 120-140 DEG C dry 30-
50min is crushed, and crosses 200-300 mesh, and silane coupling agent is added, grinds 1-2h at 50-60 DEG C, obtains material A.
Preferably, in the attapulgite modified preparation process, ricinoleic acid, humic acid are mixed, and adjusts pH value
For 4-5,60-65 DEG C at a temperature of stir 20-30min, material A is added, temperature is increased to 75- with the rate of 2-3 DEG C/min
80 DEG C and grinding 2-4h is kept the temperature, is placed at 100-106 DEG C dry 2-4h, obtains attapulgite modified.
Preferably, in S1, by weight by 6-10 parts of hydroxyapatites, 10-16 parts of attapulgite modified, 2-4 parts of oxidations
Zinc, 1-3 parts of titanium dioxide mixing, dry, pulverize, be sieved, 70-90 parts of starch, 50-90 parts of water are added, heats and stirs, then
Heating continues to stir, and obtains mixture A.
Preferably, in S1, hydroxyapatite, attapulgite modified, zinc oxide, titanium dioxide are mixed, at 100-110 DEG C
Lower dry 2-3h is crushed, and crosses 200-300 mesh, and starch, water is added, is heated to 60-70 DEG C and stirs 1-2h, then heat to
90-95 DEG C is continued to stir 15-30min, obtains mixture A.
Preferably, in S2, by weight by 50-60 parts of polylactic acid-polycaprolactone co-polymers, 80-100 parts of polyvinyl alcohol,
10-15 parts of glycerol, 5-10 parts of D-sorbites, 12-16 parts of pentaerythrite mixing, heat and stir, 86-120 parts of mixtures are added
A, 0.5-0.8 parts of methylcellulose, 2-4 parts of oleic acid, 2-5 parts of alginates, 0.5-1.0 parts of stabilizers increase temperature, stir,
Obtain mixture B.
Preferably, in S2, polylactic acid-polycaprolactone co-polymer, polyvinyl alcohol, glycerol, D-sorbite, pentaerythrite are mixed
It closes, is heated to 60-70 DEG C and stirs 20-40min, mixture A, methylcellulose, oleic acid, alginate, stabilizer is added, rise
High-temperature stirs 1-3h to 120-160 DEG C, with the revolving speed of 200-500r/min, obtains mixture B.
Preferably, in S3, the temperature of the hot melt is 170-180 DEG C.
In preparation method of the invention, using polylactic acid-polycaprolactone co-polymer, polyvinyl alcohol, starch as major ingredient, packet
Dress film has the characteristic being readily biodegradable, environmental protection, pollution very little, then adds hydroxyapatite, attapulgite modified, dioxy
Change the material matchings such as titanium, glycerol, D-sorbite, pentaerythrite, zinc oxide to use, the machinery of packaging film can not only be effectively improved
Performance can also significantly improve the antibiotic property, water resistance, tensile strength of packaging film, enhance the comprehensive performance of packaging film.The present invention
The attapulgite modified of addition is to be modified to obtain to attapulgite jointly using silane coupling agent, ricinoleic acid, humic acid
, attapulgite modified preparation process through the invention realizes and intercalation modifying modified to the surface of attapulgite, improves
The interlayer microenvironment of attapulgite, is conducive to the phase interaction between polylactic acid-polycaprolactone co-polymer, polyvinyl alcohol, starch
With dispersibility very well, applies in the present invention, can promote the dispersibility of other raw materials and major ingredient, further enhance packaging film
Mechanical performance, antibiotic property, water resistance;The present invention adds glycerol, D-sorbite, pentaerythrite, so that the flexibility of packaging film
Increase;The titanium dioxide and zinc oxide that the present invention adds have very strong chemical activity, and various microorganisms can be made to occur organic point
Solution, generates good antibacterial effect, and with attapulgite modified mating reaction, titanium dioxide and zinc oxide dispersibility can be improved, into
One step enhances antibacterial effect.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of environmental protection food package film, includes the following steps:
S1, by weight by 10 parts of hydroxyapatites, 10 parts attapulgite modified, 4 parts of zinc oxide, 1 part of titanium dioxide mix
It closes, dry 2h, crushes at 110 DEG C, crosses 300 meshes, 70 parts of starch, 90 parts of water are added, is heated to 60 DEG C and stirs 2h, then
It is warming up to 90 DEG C to continue to stir 30min, obtains mixture A;
S2, by weight by 50 parts of polylactic acid-polycaprolactone co-polymers, 100 parts of polyvinyl alcohol, 10 parts of glycerol, 10 parts of mountains
Pears sugar alcohol, 12 parts of pentaerythrite mixing, are heated to 70 DEG C and stir 20min, 120 parts of mixture A, 0.5 part of Methyl cellulose are added
Element, 4 parts of oleic acid, 2 parts of alginates, 1.0 parts of stabilizers increase temperature to 120 DEG C, stir 1h with the revolving speed of 500r/min, obtain
To mixture B;
S3, the at a temperature of progress hot-melt extruded Blown Film by mixture B control at 180 DEG C, last qualitative winding, packaging
To obtain the final product;
Wherein, the attapulgite modified preparation process is as follows:
S1, attapulgite is placed in at 120 DEG C dry 50min, crushed, cross 200 meshes, silane coupling agent is added, 60
1h is ground at DEG C, obtains material A;
S2, by ricinoleic acid, humic acid mix, and adjust pH value be 5,60 DEG C at a temperature of stir 30min, admixture
Expect A, temperature is increased to 80 DEG C with the rate of 3 DEG C/min and keep the temperature grinding 2h, is placed at 106 DEG C dry 2h, obtains modified bumps
Stick soil.
Embodiment 2
A kind of preparation method of environmental protection food package film, includes the following steps:
S1, by weight by 6 parts of hydroxyapatites, 16 parts attapulgite modified, 2 parts of zinc oxide, 3 parts of titanium dioxide mix
It closes, dry 3h, crushes at 100 DEG C, crosses 200 meshes, 90 parts of starch, 50 parts of water are added, is heated to 70 DEG C and stirs 1h, then
It is warming up to 95 DEG C to continue to stir 15min, obtains mixture A;
S2, by weight by 60 parts of polylactic acid-polycaprolactone co-polymers, 80 parts of polyvinyl alcohol, 15 parts of glycerol, 5 portions of sorbs
Sugar alcohol, 16 parts of pentaerythrite mixing, are heated to 60 DEG C and stir 40min, 86 parts of mixture A, 0.8 part of methylcellulose, 2 are added
Part oleic acid, 5 parts of alginates, 0.5 part of stabilizer increase temperature to 160 DEG C, stir 3h with the revolving speed of 200r/min, mixed
Close material B;
S3, the at a temperature of progress hot-melt extruded Blown Film by mixture B control at 170 DEG C, last qualitative winding, packaging
To obtain the final product;
Wherein, the attapulgite modified preparation process is as follows:
S1, attapulgite is placed in at 140 DEG C dry 30min, crushed, cross 300 meshes, silane coupling agent is added, 50
2h is ground at DEG C, obtains material A;
S2, by ricinoleic acid, humic acid mix, and adjust pH value be 4,65 DEG C at a temperature of stir 20min, admixture
Expect A, temperature is increased to 75 DEG C with the rate of 2 DEG C/min and keep the temperature grinding 4h, is placed at 100 DEG C dry 4h, obtains modified bumps
Stick soil.
Embodiment 3
A kind of preparation method of environmental protection food package film, includes the following steps:
S1, by weight by 8 parts of hydroxyapatites, 13 parts attapulgite modified, 3 parts of zinc oxide, 2 parts of titanium dioxide mix
It closing, dry 2.5h, crushes at 105 DEG C, and 220 meshes are crossed, 80 parts of starch, 75 parts of water are added, is heated to 65 DEG C and stirs 1.5h,
It then heats to 92 DEG C to continue to stir 20min, obtains mixture A;
S2, by weight by 56 parts of polylactic acid-polycaprolactone co-polymers, 90 parts of polyvinyl alcohol, 13 parts of glycerol, 8 portions of sorbs
Sugar alcohol, the mixing of 14 parts of pentaerythrites, are heated to 66 DEG C and stir 30min, be added 108 parts of mixture A, 0.6 part of methylcellulose,
3 parts of oleic acid, 3 parts of alginates, 0.7 part of stabilizer increase temperature to 140 DEG C, stir 2h with the revolving speed of 300r/min, mixed
Close material B;
S3, the at a temperature of progress hot-melt extruded Blown Film by mixture B control at 175 DEG C, last qualitative winding, packaging
To obtain the final product;
Wherein, the attapulgite modified preparation process is as follows:
S1, attapulgite is placed in at 130 DEG C dry 40min, crushed, cross 250 meshes, silane coupling agent is added, 55
1.5h is ground at DEG C, obtains material A;
S2, by ricinoleic acid, humic acid mix, and adjust pH value be 4.5,63 DEG C at a temperature of stir 25min, be added
Material A increases temperature to 78 DEG C with the rate of 3 DEG C/min and keeps the temperature grinding 3h, is placed at 103 DEG C dry 3h, obtains being modified recessed
Convex stick soil.
Test example 1
The inspection of mechanical performance and anti-microbial property is carried out to environmental protection food package film made from 1-3 of the embodiment of the present invention respectively
It surveys, test result is as shown in table 1.
Table 1
As can be seen from Table 1, the environmentally friendly food package film that the present invention obtains has good mechanical performance and antibacterial effect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of environmental protection food package film, which comprises the steps of:
S1, hydroxyapatite, attapulgite modified, zinc oxide, titanium dioxide are mixed, dry, pulverize, is sieved, addition starch,
Water is heated and is stirred, and then heating continues to stir, and obtains mixture A;
S2, polylactic acid-polycaprolactone co-polymer, polyvinyl alcohol, glycerol, D-sorbite, pentaerythrite are mixed, heats and stirs
It mixes, mixture A, methylcellulose, oleic acid, alginate, stabilizer is added, increase temperature, stirring obtains mixture B;
S3, mixture B carries out to hot-melt extruded Blown Film, last qualitative winding, pack to get.
2. the preparation method of environmentally friendly food package film according to claim 1, which is characterized in that described attapulgite modified
Preparation process is as follows:
S1, attapulgite dry, pulverize, is sieved, silane coupling agent is added, grinding obtains material A;
S2, ricinoleic acid, humic acid are mixed, and adjusts pH value, stirred, material A is added, increased temperature and grind, it is dry, it obtains
To attapulgite modified.
3. the preparation method of environmentally friendly food package film according to claim 2, which is characterized in that described attapulgite modified
In preparation process, attapulgite is placed at 120-140 DEG C dry 30-50min, crushes, crosses 200-300 mesh, silane is added
Coupling agent grinds 1-2h at 50-60 DEG C, obtains material A.
4. the preparation method of environmentally friendly food package film according to claim 2, which is characterized in that described attapulgite modified
In preparation process, by ricinoleic acid, humic acid mix, and adjust pH value be 4-5,60-65 DEG C at a temperature of stir 20-
Material A is added in 30min, increases temperature to 75-80 DEG C with the rate of 2-3 DEG C/min and keeps the temperature grinding 2-4h, is placed in 100-106
Dry 2-4h, obtains attapulgite modified at DEG C.
5. the preparation method of environmentally friendly food package film according to claim 1, which is characterized in that in S1, by weight by 6-
10 parts of hydroxyapatites, 10-16 parts of attapulgite modified, 2-4 parts of zinc oxide, 1-3 parts of titanium dioxide mixing, dry, pulverize, mistake
Sieve is added 70-90 parts of starch, 50-90 parts of water, heats and stir, and then heating continues to stir, and obtains mixture A.
6. the preparation method of environmentally friendly food package film according to claim 1, which is characterized in that in S1, by hydroxyapatite,
Attapulgite modified, zinc oxide, titanium dioxide mixing, dry 2-3h, crushes at 100-110 DEG C, crosses 200-300 mesh, adds
Enter starch, water, be heated to 60-70 DEG C and stir 1-2h, then heats to 90-95 DEG C and continue to stir 15-30min, mixed
Expect A.
7. the preparation method of environmentally friendly food package film according to claim 1, which is characterized in that in S2, by weight by 50-
60 parts of polylactic acid-polycaprolactone co-polymers, 80-100 parts of polyvinyl alcohol, 10-15 parts of glycerol, 5-10 parts of D-sorbites, 12-16 parts
Pentaerythrite mixing, heats and stirs, and A, 0.5-0.8 parts of methylcellulose of 86-120 parts of mixtures, 2-4 parts of oleic acid, 2-5 are added
Part alginate, 0.5-1.0 parts of stabilizers, increase temperature, and stirring obtains mixture B.
8. the preparation method of environmentally friendly food package film according to claim 1, which is characterized in that in S2, polylactic acid-is gathered oneself
Lactone copolymers, polyvinyl alcohol, glycerol, D-sorbite, pentaerythrite mixing, are heated to 60-70 DEG C and stir 20-40min, add
Enter mixture A, methylcellulose, oleic acid, alginate, stabilizer, increases temperature to 120-160 DEG C, with 200-500r/min
Revolving speed stir 1-3h, obtain mixture B.
9. the preparation method of environmentally friendly food package film according to claim 1, which is characterized in that in S3, the temperature of the hot melt
Degree is 170-180 DEG C.
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