CN110254008A - A kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film - Google Patents

A kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film Download PDF

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Publication number
CN110254008A
CN110254008A CN201910479335.9A CN201910479335A CN110254008A CN 110254008 A CN110254008 A CN 110254008A CN 201910479335 A CN201910479335 A CN 201910479335A CN 110254008 A CN110254008 A CN 110254008A
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layer
additive
resin
degradation
internal
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Inventor
张建华
张博
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TIANJIN JIANNA WOTE PLASTICIZATION TECHNOLOGY Co Ltd
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TIANJIN JIANNA WOTE PLASTICIZATION TECHNOLOGY Co Ltd
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Priority to CN201910479335.9A priority Critical patent/CN110254008A/en
Publication of CN110254008A publication Critical patent/CN110254008A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention belongs to biology base degradation technique field more particularly to a kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding films, including surface layer, middle layer, internal layer；The surface layer includes surface layer resin layer, surface layer additive layer, and the surface layer resin layer is sixfold controlled degradation (LCSZ) resin, and the surface layer additive layer is environment controlled degradation (HJZJ) additive；The middle layer includes middle layer resin layer, middle layer additive layer, the middle layer additive layer is located at the lower section of middle layer resin layer, the middle layer resin layer is modified poly (propylene carbonate) (SHQ-MPC) resin, and the middle layer additive layer is oxidative biological base controlled degradation (YSZJ) additive；The internal layer includes inner layer resin layer, internal layer additive layer, the internal layer additive layer is located at the lower section of inner layer resin layer, the inner layer resin layer is modification biological base polyolefin adhesion (SHQ-MTIE) resin, and the internal layer additive layer is water-retaining property controlled degradation (BSZJ) additive.

Description

A kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film
Technical field
The invention belongs to biology base degradation technique field more particularly to a kind of multi-layer co-extruded biology bases of biology base high barrier Blown film.
Background technique
With economic rapid development, people get worse the destruction of environment, especially nondegradable plastics, by people Arbitrarily throw out without care after, due to being not easy to be deposited in soil for a long time by soil microbial degradation, caused to ecological environment serious Pollution.Disposable tableware, Phthalates and agricultural mulching etc. are difficult to be recycled, traditional processing method with Based on burning and burying.Burning can generate a large amount of pernicious gas, pollute environment；It buries in the then polymer short time therein not It can be decomposed by the microorganisms, also pollute environment.The plastic foil of residual abandoning is present in soil, hinders the development of crop root system and to water Divide, the absorption of nutrient, reduces the gas permeability of soil, lead to crop production reduction；After movement eats the plastic foil of residual abandoning, it will cause intestines Obstruction and it is dead；The synthetic netting and fishline being lost in ocean or discard in ocean cause phase to marine organisms When harm, therefore advocate green consumption with reinforcement environmental protection it is imperative.
In order to reduce white pollution, preserving the ecological environment, people start to study degredation plastic, and the of research Generation degradative plastics is degradation plastic, and this degradation plastic is added to dropping for sub-fraction on the basis of original raw material It solves masterbatch or starch-based initial material, major part is not can be carried out degradation, be also unfavorable for the recycling and reconstruction of plastics；The of research Two generation degradative plastics are biology base controllable full-degradable plastics, and using resourceful, reproducible biomass as raw material, degradation process is green Color, cleaning also help the benign cycle in building soil and environmental system, are to alleviate oil crisis, eliminate having for white pollution Effect approach.
Currently, the object base high-separation multi-layer co-extrusion bio-based blow moulding film of practical application, not thorough enough, implementation result of degrading It is bad.
Summary of the invention
The present invention provides a kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film, to solve in above-mentioned background technique The structure of proposition is simple, not thorough enough problem of degrading.
Technical problem solved by the invention is realized using following technical scheme:
A kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film, including surface layer, middle layer, internal layer；
The surface layer includes surface layer resin layer, surface layer additive layer, and the surface layer additive layer is located at the lower section of surface layer resin layer, The surface layer resin layer is sixfold controlled degradation (LCSZ) resin, and the surface layer additive layer is that environment controlled degradation (HJZJ) adds Add agent；
The middle layer includes middle layer resin layer, middle layer additive layer, and the middle layer additive layer is located at the lower section of middle layer resin layer, The middle layer resin layer is modified poly (propylene carbonate) (SHQ-MPC) resin, and the middle layer additive layer is that oxidative biological base can Control degradation (YSZJ) additive；
The internal layer includes inner layer resin layer, internal layer additive layer, and the internal layer additive layer is located at the lower section of inner layer resin layer, The inner layer resin layer is modification biological base polyolefin adhesion (SHQ-MTIE) resin, and the internal layer additive layer is that water-retaining property can Control degradation (BSZJ) additive.
The percentage thickness on the surface layer is 15%, and the percentage thickness in the middle layer is 70%, the thickness hundred of the internal layer Divide than being 15%.
The percentage thickness of the surface layer resin layer is 85%, the percentage thickness of surface layer additive layer is 15%.
The percentage thickness of the middle layer resin layer is 90%, the percentage thickness of middle layer additive layer is 10%.
The percentage thickness of the inner layer resin layer is 95%, the percentage thickness of internal layer additive layer is 5%.
Environment controlled degradation (HJZJ) additive, oxidative biological base controlled degradation (YSZJ) additive, water-retaining property controllably drop It is equal to solve (BSZJ) additive are as follows: aminodithioformic acid nickel.
The invention has the benefit that
The blown film made of the technical program, can be realized degradable, and implementation result is ideal,
Its specific ingredient effect is as follows:
1 sixfold controlled degradation (LCSZ) resin: degradation modification resin is added in degradative plastics process of producing product, makes all kinds of non- Degradative plastics product becomes controllable degradable plastic products, has used the degradative plastics product of degradation modification resin when exposure When in sunlight, high temperature or external force, it will degradation, and degradation time and speed are controllable.Triple controlled degradation resins exist It is total using special process by the degradative resin of opposed polarity using multi-layer co-extruded moulding process in degradative plastics production process Working chamber is squeezed, is effectively combined together Compost Biodegradation and oxidative biodegradation, really realizes controlled degradation and complete All biodegradability.Triple controlled degradation non-toxics, comestible contact, processability is strong, can be controllable to drop with most of material compatible Xie Xing controls degradation time according to necessary requirement, and 100% environmental degradability is fully converted to water, carbon dioxide and organic matter, Will not be harmful to environment or soil, cost performance is high, and compared with other degradation techniques, cost is relatively low.Triple controlled degradation resins It is mainly used for refuse disposal system, packing business, agricultural, compost and plastics manufacturing industry, is suitable for making all kinds of degradative plastics products, Such as farm-oriented mulch, drip irrigation zone, shopping bag, plastic bag, refuse bag, courier bag, mess-tin.
2 modified poly (propylene carbonate) (SHQ-MPC) resins: polypropylene carbonate resin is with carbon dioxide and propylene oxide For raw material, a kind of environment-friendly type plastic of Wholly-degradable of synthesis, there have to be poor with other degradative resin material compatibilities, higher cost The shortcomings that, it is modified, it solves the compatibility with other resin materials, reduces costs.Modified polypropylene carbonate resin tool There are full Biodegradable and good barrier properties for gases, not will cause any destroying infection to environment, avoid white pollution Phenomenon belongs to environmentally friendly material, is modified polypropylene carbonate resin compared with EVOH, PVDC, PA petroleum base barrier material, Modified polypropylene carbonate resin barrier material barrier property is excellent, and cost performance is excellent, is a kind of environment-friendly type degradation barrier material. Modified polypropylene carbonate resin is a kind of barrier degradable material of controllability, according to the storage period of article, controllable barrier degradation Time is mainly used for making the degradative membranes such as various food packagings, medical packaging, household electrical appliances packaging.
3 modification biological base polyolefin adhesion (SHQ-MTIE) resins: biology base polyolefin bonding resin have hydrophilic group and Two kinds of functional groups of hydrophobic group, by modification, Graft Polyolefin maleic anhydride is acidified it, lowers crystallinity, with other drops Solution resin has affinity and adhesive force.Modification biological base polyolefin bonding resin is a kind of high molecular polymer, and appearance is white Or yellowish graininess or pulverulent solids, it is nontoxic, tasteless, pollution-free, it is a kind of water-soluble resin, there is preferable chemistry Stability has many characteristics, such as caking property.Modification biological base polyolefin bonding resin has two kinds of groups of hydrophilic group and hydrophobic group, makes It can bond with petroleum base resin and bond with bio-based resin, and compatibility is good.Modification biological Ji Juxitingnianheshu Rouge is mainly used for the bonding of bio-based resin polyolefins or the bonding of petroleum base resin polyolefin.
4 are added degradant additive by proportion in material modification production process, and various modified resins is made to become controllably dropping The modified resin raw material of solution, is added degradant additive in degradation products production process, becomes all kinds of non-degradable plastic products Controllable completely degradable plastic product；Degradant additive is added in resin in plastic product production process, and without changing life Equipment and program are produced, the degradative plastics product of degradant additive is added to, when being exposed in sunlight, high temperature or external force, It will degrade, and degradation time and speed are controllable；Degradant additive is non-toxic, and comestible contact, processability is strong, can be with big portion Point material compatible, controlled degradation control degradation time according to necessary requirement, 100% environmental degradability, be fully converted to water, Carbon dioxide and organic matter, will not be harmful to environment or soil, and cost performance is high, and compared with other degradation techniques, cost is relatively low； Degradant additive is mainly used for refuse disposal system, packing business, agricultural, compost and plastics manufacturing industry, is suitable for making all kinds of drops Solve plastic products, such as farm-oriented mulch, drip irrigation zone, shopping bag, plastic bag, refuse bag, courier bag, mess-tin.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention；
In figure: the surface layer 1-, the middle layer 2-, 3- internal layer, the surface layer 4- resin layer, the surface layer 5- additive layer, the middle layer 6- resin layer, the middle layer 7- Additive layer, 8- inner layer resin layer, 9- internal layer additive layer.
Specific embodiment
A kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film, including surface layer 1, middle layer 2, internal layer 3；
Surface layer 1 includes surface layer resin layer 4, surface layer additive layer 5, and surface layer additive layer 5 is located at the lower section of surface layer resin layer 4, table Layer resin layer 4 is sixfold controlled degradation (LCSZ) resin, and surface layer additive layer 5 is environment controlled degradation (HJZJ) additive；
Middle layer 2 includes middle layer resin layer 6, middle layer additive layer 7, and middle layer additive layer 7 is located at the lower section of middle layer resin layer 6, in Layer resin layer 6 is modified poly (propylene carbonate) (SHQ-MPC) resin, and middle layer additive layer 7 is oxidative biological base controlled degradation (YSZJ) additive；
Internal layer 3 includes inner layer resin layer 8, internal layer additive layer 9, and internal layer additive layer 9 is located at the lower section of inner layer resin layer 8, interior Layer resin layer 8 is modification biological base polyolefin adhesion (SHQ-MTIE) resin, and internal layer additive layer 9 is water-retaining property controlled degradation (BSZJ) additive.
The percentage thickness on surface layer 1 is 15%, and the percentage thickness in middle layer 2 is 70%, and the percentage thickness of internal layer 3 is 15%.
The percentage thickness of surface layer resin layer 4 is 85%, the percentage thickness of surface layer additive layer 5 is 15%.
The percentage thickness of middle layer resin layer 6 is 90%, the percentage thickness of middle layer additive layer 7 is 10%.
The percentage thickness of inner layer resin layer 8 is 95%, the percentage thickness of internal layer additive layer 9 is 5%.
Environment controlled degradation (HJZJ) additive, oxidative biological base controlled degradation (YSZJ) additive, water-retaining property controllably drop It is equal to solve (BSZJ) additive are as follows: aminodithioformic acid nickel.
The technical program uses binary process forming technique, refers on the basis of unitary technological forming (Recipe), Increase moulding process, unitary Recipe can only occupy 50% technology content in process of producing product, in addition binary at Type technique could improve the basic fundamental guarantee of product, be mainly reflected in the thinned of product and thicken, and enhancing is thinned, effectively drops Low cost improves occupation rate of market.
Binary process forming technique includes: unitary Recipe, binary moulding process.
Unitary Recipe includes:
1 oxygen-containing polyolefin controlled degradation material prescription technique；
2 oxidative biological controlled degradation material prescription techniques；
3PVA biology base controlled degradation material prescription technique；
4PBAT biology base controlled degradation material prescription technique；
5 triple controlled degradation technical formula techniques；
6 quadruple controlled degradation technical formula techniques；
7 five heavy controlled degradation technical formula techniques；
8 sixfold controlled degradation technical formula techniques；
9 three layers of water-retaining type controlled degradation technical formula technique.
Binary moulding process includes:
1 vacuum sizing moulding process；
2 intelligent weighing system moulding process；
3 interlayer material controlling intelligent control moulding process；
4 intelligent control thickness moulding process；
5 intelligent control width moulding process；
6 intelligence correction moulding process；
7 liang of bubble method moulding process；
8 three bubble method moulding process；
9 four bubble method moulding process；
10 puma manipulator automatic winding moulding process.
Principle:
Biology base controllable full-degradable plastics can be divided into starch, polyesters and other classes according to raw material point；
Starch is abundance, cheap natural macromolecular material, and native starch is small for having crystalline texture with inside Existing for granular state, molecular structure has straight chain and two kinds of branch.For different plant varieties, the form of starch granules, Size and the ratio of amylose and amylopectin content are all different.The partial size of starch granules is mostly at 15-100 μm. The chain compound that the glucose of amylose is combined with α-D-1,4 glycosidic bonds, relative molecular mass are (20-200) x104.Branch The connection type of each glucose unit removes α-D-1 in chain starch, and outside 4 glycosidic bonds, there is also α-D-1,6 glycosidic bonds, average moleculars Quality is (100-400) x106.The property of starch and relative molecular mass, branch lengths and the amylose and branch of starch The ratio of chain starch is related.The starch of high amylose content has preferable mechanical performance more suitable for preparing plastics, resulting product. Native starch is intermolecular, and there are hydrogen bonds, and dissolubility is very poor, hydrophilic but not soluble easily in water, it has highly polar crystallographic property. Since there are strong hydrogen bonding effects between the macromolecule of native starch, it is difficult to direct machine-shaping.To improve its process industrial art performance, one As be by open starch interchain hydrogen bond, make starch lose crystallization method realize.There are two types of its operating methods, and one is add Hot water content is greater than 90% starch solution, and starch granules is 60~70oStart to be swollen between C, reaches 90 in temperatureoStarch after C Particle starts to burst apart, and macromolecule interchain hydrogen bond is opened, and generates gelation；Another kind is heated under air-tight state, is plasticated crowded Starch of the water content less than 28% out.
Polylactic acid (PLA) is also referred to as polylactide, belongs to polyester family, and structural formula is (- O-CHCH3-CO-) n.
The most important two kinds of polymerizations of polylactic acid are direct polymerization method and ring-opening polymerisation method.Direct polymerization method is typical Polycondensation reaction.Using the activity of lactic acid, by heating, dehydration condensation occurs between lactic acid molecules, obtains polylactic acid.It is directly poly- Legal simple production process, production cost is low, is not required to the intermediate of reaction to be separated.But the molecular weight of polylactic acid is lower, molecule Measure distributed more widely, performance is poor.Lactide ring-opening polymerisation method produces polylactic acid using two-step method.It is cyclized and is made by acid by dehydrating lactic first Then polylactic acid is made by refined lactide ring-opening polymerisation again in lactide.Polylactic acid physical force made from ring-opening polymerisation method Better performances are learned, the production cost of the method is higher than direct polymerization method.
The degradation of polylactic acid is divided into simple hydrolysis (acid-base catalysis) and enzymatic hydrolysis degradation.The principal degradation side of polylactic acid Formula is bulk erosion.Hydrophobic polymer becomes low relative molecular weight, water by the hydrolysis of labile bond on main chain (C-O key) Then soluble molecule and monomer are further degraded to water and carbon dioxide under the action of enzyme.The degradation of polylactic acid right and wrong first The hydrolysis of crystalline region, followed by crystalline region.Hydrolysis can because carboxyl there are due to accelerate.There are autocatalysis inside polylactic acid, Inside degradation speed specific surface it is fast.When degrading beginning, the hydrolysis of ester bond is isotropic in matrix.In degradation process In, carboxyl end group is to having hydrolyzed catalytic action.With the progress of degradation, carboxyl end group amount increases, and degradation rate is accelerated.
The embodiments of the present invention have been described in detail above, but content is only the preferred embodiment of the present invention, It should not be considered as limiting the scope of the invention, any changes and modifications in accordance with the scope of the present application, It should still be within the scope of the patent of the present invention.

Claims (6)

1. a kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film, it is characterised in that:
Including surface layer, middle layer, internal layer；
The surface layer includes surface layer resin layer, surface layer additive layer, and the surface layer additive layer is located at the lower section of surface layer resin layer, The surface layer resin layer is sixfold controlled degradation (LCSZ) resin, and the surface layer additive layer is that environment controlled degradation (HJZJ) adds Add agent；
The middle layer includes middle layer resin layer, middle layer additive layer, and the middle layer additive layer is located at the lower section of middle layer resin layer, The middle layer resin layer is modified poly (propylene carbonate) (SHQ-MPC) resin, and the middle layer additive layer is that oxidative biological base can Control degradation (YSZJ) additive；
The internal layer includes inner layer resin layer, internal layer additive layer, and the internal layer additive layer is located at the lower section of inner layer resin layer, The inner layer resin layer is modification biological base polyolefin adhesion (SHQ-MTIE) resin, and the internal layer additive layer is that water-retaining property can Control degradation (BSZJ) additive.
2. a kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film according to claim 1, it is characterised in that: institute The percentage thickness for stating surface layer is 15%, and the percentage thickness in the middle layer is 70%, and the percentage thickness of the internal layer is 15%.
3. a kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film according to claim 1, it is characterised in that: institute The percentage thickness for stating surface layer resin layer is 85%, the percentage thickness of surface layer additive layer is 15%.
4. a kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film according to claim 1, it is characterised in that: institute The percentage thickness for stating middle layer resin layer is 90%, the percentage thickness of middle layer additive layer is 10%.
5. a kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film according to claim 1, it is characterised in that: institute The percentage thickness for stating inner layer resin layer is 95%, the percentage thickness of internal layer additive layer is 5%.
6. a kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film according to claim 1, it is characterised in that: institute State environment controlled degradation (HJZJ) additive, oxidative biological base controlled degradation (YSZJ) additive, water-retaining property controlled degradation (BSZJ) additive is equal are as follows: aminodithioformic acid nickel.
CN201910479335.9A 2019-06-04 2019-06-04 A kind of biology base high-separation multi-layer co-extrusion bio-based blow moulding film Withdrawn CN110254008A (en)

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Application publication date: 20190920