CN104494260A

CN104494260A - Degradable foamed co-extruded PET barrier film

Info

Publication number: CN104494260A
Application number: CN201410752407.XA
Authority: CN
Inventors: 夏嘉良; 高学文; 夏瑜; 唐敏艳; 俞晓琴
Original assignee: KUNSHAN ZHANGPU COLOR PRINTING FACTORY
Current assignee: KUNSHAN ZHANGPU COLOR PRINTING FACTORY
Priority date: 2014-12-11
Filing date: 2014-12-11
Publication date: 2015-04-08
Anticipated expiration: 2034-12-11
Also published as: JP2018500215A; WO2016090801A1; CN104494260B

Abstract

The invention relates to a degradable foamed co-extruded PET barrier film. The degradable foamed co-extruded PET barrier film is characterized in that materials of all layers in the laminated film have approximately-consistent biodegradability through introducing biological groups, and the added amount of an additive master batch in the materials of each layer is controlled to be 0.3-15% the total mass of the materials of the corresponding layer; the hydrophilic activity of hydrophilic groups in the additive master batch needs to be greater than or equal to that of the hydrophilic groups in the materials of each layer; through adding the additive master batch, the mole ratio of the hydrophilic groups and carbon atoms of the materials of each layer is approximately consistent, namely that the biological activity is approximately consistent, so that the degradation rate of the materials of all the layers in the laminated film is approximately consistent. The degradable foamed co-extruded PET barrier film has the contributions that through balancing the mole ratio of the hydrophilic groups and carbon atoms of the materials of each layer, the approximately-consistent biological activity and approximately-consistent biodegradation rate are obtained, and the appearance, functions and physical and mechanical properties of products are kept invariable.

Description

Degradable foaming coextrusion PET barrier film

Technical field

The present invention relates to multi-layer compound film technical field, particularly one biodegradable degradable foaming coextrusion PET barrier film.

Background technology

Multi-layer co-extruded laminated film refers to by multiple different polymer, adopts the film that coextrusion blow moiding method, coextrusion casting method or coextrusion drawing process are composited.This film is widely used in food, meat processing product, commodity, cosmetics, chemical products, agricultural chemicals, war products etc. as plastic package material, and can realize product sealing flexible package and meet inflation or vacuumize, the various packaging function such as thermoforming, have that high resistant is wet under circumstances, the various barrier property such as resistance oxygen, oil resistance, guarantor are fragrant.

Along with a large amount of laminated film is in the use of every field, the pollution of laminated film to environment increasingly sharpens.Because it is difficult to degraded, along with growing with each passing day of consumption, the pollution that laminated film causes has become international public hazards.Some conventional methods of current process laminated film discarded object as burned, burying, all existing defects such as recycling, and have certain limitation to bring serious load to environment, therefore exploitation reduces the biodegradable laminated film of environmental pollution is the important channel solving environmental pollution.

According to the applicant understood, at present about having the biodegradation technique of the laminated film of identical degradation rate and application technology or a blank, there is not yet relevant report at home and abroad.But the present situation increased sharply from market demand and protecting ecology balance; the multi-layer co-extruded laminated film that research has biodegradable performance is extremely urgent; wherein; the degradation rate of the layers of material in multi-layer co-extruded laminated film in biodegradation process how is made to reach unanimity; do not lose original mechanical performance and shelf life, be the important subject with realistic meaning simultaneously.

Summary of the invention

The object of the invention is to provide the foaming coextrusion PET barrier film that a kind of biodegradation rate reaches unanimity.

For achieving the above object, the first technical scheme that the present invention adopts is: a kind of degradable foaming coextrusion PET barrier film, and the structure of this laminated film is as follows:

PET(ester group)/EAA-TIE(carboxyl+acid anhydrides)/EPO(without)/PO-TIE(acid anhydrides)/PA (amide groups) formula (1)

In formula (1), the implication represented successively is from left to right:

Pet sheet shows skin, and its function is protective layer or presentation layer, and its material is polyester, and the hydrophilic radical that polyester contains is ester group;

EAA-TIE represents the first adhesive layer, and its material is the ethylene acrylic acid co polymer of maleic anhydride graft, and the hydrophilic radical that the ethylene acrylic acid co polymer of maleic anhydride graft contains is carboxyl and acid anhydrides;

EPO represents middle level, and its function is toughening layer, and its material is polypropylene or polyethylene, and polypropylene or polyethylene be not containing hydrophilic radical;

PO-TIE represents the second adhesive layer, and its material is the polyolefin copolymer of maleic anhydride graft, and the hydrophilic radical that the polyolefin copolymer of maleic anhydride graft contains is acid anhydrides;

PA represents internal layer, and its function is coating layer, and its material is polyamide, and the hydrophilic radical that polyamide contains is amide groups;

Its innovation is: the layers of material in described laminated film all obtains by introducing bio-based the biodegradability reached unanimity, described bio-based is the addition type masterbatch that a class has biological degradation activity under garbage disposal plant or composting conditions, this addition type masterbatch evenly adds in layers of material in proportion, then prepares laminated film by melting co-extrusion method;

Described addition type masterbatch is made up of carrier and activating agent, described activating agent is the polymer containing hydrophilic radical, wherein, the effective ingredient of activating agent is hydrophilic radical, and described hydrophilic radical refers at least one in carboxylate, carboxyl, hydroxyl, aldehyde radical, amide groups, acid anhydrides and ester group;

In described formula (1) layers of material and addition type masterbatch, hydrophilic radical arranges from high to low according to hydrophilic active and is followed successively by carboxylate, carboxyl, hydroxyl, aldehyde radical, amide groups, acid anhydrides, ester group;

Described carrier pin is selected by the similar principle that mixes layers of material:

For outer field polyester material, the carrier in addition type masterbatch is polyester;

For the ethylene acrylic acid co polymer material of the maleic anhydride graft of the first adhesive layer, the carrier in addition type masterbatch is ethylene acrylic acid co polymer;

For middle layer material, when central layer material is polyethylene, the carrier in addition type masterbatch is polyethylene; When central layer material is polypropylene, the carrier in addition type masterbatch is polypropylene or polyethylene;

For the polyolefin copolymer material of the maleic anhydride graft of the second adhesive layer, when central layer material is polyethylene, the second adhesive layer selects the polyethylene and ethylene copolymers of maleic anhydride graft, and the carrier in addition type masterbatch is polyethylene; When central layer material is polypropylene, the second adhesive layer selects the polypropylene copolymer of maleic anhydride graft, and the carrier in addition type masterbatch is polypropylene or polyethylene;

For the polyamide material of internal layer, the carrier in addition type masterbatch is polyamide;

The addition of described addition type masterbatch in layers of material controls the 0.3-15% scope in this layer material gross mass; In described addition type masterbatch, the hydrophilic active of hydrophilic radical should be more than or equal to the hydrophilic active of hydrophilic radical in formula (1) layers of material; By adding addition type masterbatch, the hydrophilic radical of layers of material and the mol ratio of carbon atom in formula (1) are reached unanimity, and namely biologically active reaches unanimity, thus the layers of material degradation rate of laminated film is reached unanimity.

For achieving the above object, the second technical scheme that the present invention adopts is: a kind of degradable foaming coextrusion PET barrier film, and the structure of this laminated film is as follows:

PET(ester group)/EAA-TIE(carboxyl+acid anhydrides)/EPO(without)/EAA-TIE(carboxyl+acid anhydrides)/PET(ester group) formula (2)

In formula (2), the implication represented successively is from left to right:

EAA-TIE represents the second adhesive layer, and its material is the ethylene acrylic acid co polymer of maleic anhydride graft, and the hydrophilic radical that the ethylene acrylic acid co polymer of maleic anhydride graft contains is carboxyl and acid anhydrides;

Pet sheet shows internal layer, and its function is coating layer, and its material is polyester, and the hydrophilic radical that polyester contains is ester group;

In described formula (2) layers of material and addition type masterbatch, hydrophilic radical arranges from high to low according to hydrophilic active and is followed successively by carboxylate, carboxyl, hydroxyl, aldehyde radical, amide groups, acid anhydrides, ester group;

For the ethylene acrylic acid co polymer material of the maleic anhydride graft of the first adhesive layer and the second adhesive layer, the carrier in addition type masterbatch is ethylene acrylic acid co polymer;

For the polyester material of internal layer, the carrier in addition type masterbatch is polyester;

The addition of described addition type masterbatch in layers of material controls the 0.3-15% scope in this layer material gross mass; In described addition type masterbatch, the hydrophilic active of hydrophilic radical should be more than or equal to the hydrophilic active of hydrophilic radical in formula (2) layers of material; By adding addition type masterbatch, the hydrophilic radical of layers of material and the mol ratio of carbon atom in formula (2) are reached unanimity, and namely biologically active reaches unanimity, thus the layers of material degradation rate of laminated film is reached unanimity.

Related content in technique scheme is explained as follows:

1, in above-mentioned first and second technical schemes, in described skin, polyester is amorphization PETG, or PETG-1,4-CHDM ester, and the density of polyester is 1.300-1.400g/cm ³.Carry out the PET polyester copolymer obtained by modification by copolymerization with dicarboxylic acids, be referred to as amorphization PETG (APET); Carry out the PET polyester copolymer obtained by modification by copolymerization with dihydroxylic alcohols, be referred to as PETG-1,4-CHDM ester (PETG); Chemical element contained by it is equally carbon, hydrogen, oxygen with paper, belongs to degradability plastics.After the packaging product made with this material is discarded, finally become water and carbon dioxide.

2, in above-mentioned first and second technical schemes, described first adhesive layer adopts the ethylene acrylic acid co polymer of maleic anhydride graft, and the density of the ethylene acrylic acid co polymer of maleic anhydride graft is 0.920-0.940g/cm ³, maleic anhydride grafting ratio is 0.3%-10% weight; In ethylene acrylate copolymer, acrylic acid molar content is 8%-28%.

3, in above-mentioned first and second technical schemes, described middle level is with polyethylene or polypropylene for raw material, and adopt at least one in physical blowing and chemical blowing means to be processed by extruded type foaming, after foaming, poly density is 0.600-0.850g/cm ³, after foaming, polyacrylic density is 0.600-0.850g/cm ³.

4, in above-mentioned first technical scheme, described second adhesive layer adopts the polyolefin copolymer of maleic anhydride graft, and when central layer material is polyethylene, the second adhesive layer selects the polyethylene and ethylene copolymers of maleic anhydride graft, and density is 0.910-0.950g/cm ³, maleic anhydride grafting ratio is 0.3%-10% weight; When central layer material is polypropylene, the second adhesive layer selects the polypropylene copolymer of maleic anhydride graft, and density is 0.880-0.910 g/cm ³, maleic anhydride grafting ratio is 0.3%-10% weight.

5, in above-mentioned second technical scheme, described second adhesive layer adopts the ethylene acrylic acid co polymer of maleic anhydride graft, and the density of the ethylene acrylic acid co polymer of maleic anhydride graft is 0.920-0.940g/cm ³, maleic anhydride grafting ratio is 0.3%-10% weight; In ethylene acrylate copolymer, acrylic acid molar content is 8%-28%.

6, in above-mentioned first technical scheme, described internal layer adopts polyamide material, and the density of polyamide is 1.12-1.14 g/cm ³, polyamide is PA6 homopolymers or PA6,66 copolymers or amorphous polyamides.

7, in above-mentioned second technical scheme, in described internal layer, polyester is amorphization PETG, or PETG-1,4-CHDM ester, and the density of polyester is 1.300-1.400g/cm ³.

8, in such scheme, described outer field function is protective layer or presentation layer, and wherein, when its function is protective layer, what play is wear-resisting, heatproof effect; When its function is presentation layer, can be used for printed representation relevant information, or transparent display pack content.

9, in such scheme, described laminated film can obtain corresponding additional function by coating, metal evaporation, compound.

10, in such scheme, the material of described skin and internal layer is polyamide, and described film can two-sided heat-sealing.

Know-why of the present invention is: the material forming laminated film is divided into water wetted material and hydrophobic material two class, and wherein, water wetted material itself, containing hydrophilic radical, namely possesses biodegradability under garbage disposal plant or composting conditions, and hydrophobic material is not containing hydrophilic radical, by adding hydrophilic radical to give its biodegradability in hydrophobic material, addition type masterbatch adds in layers of material in proportion, carrier and activating agent are fully mixed by blending method, then laminated film is prepared by melting co-extrusion method, at high temperature, under the effect of high shear, its stable combining is made by bending winding the mutually between hydrogen bond action and macromolecular chain between macromolecular chain, form stable macromolecular, with this hydrophilic radical in activating agent added and evenly spread in layers of material, in biodegradation environment, first degradable active agent is decomposed by the microorganisms and causes molecular chain rupture, and also there is molecular chain rupture with it by the carrier that hydrogen bond is connected, and then cause this macromolecular to decompose, thus reach the biodegradable object of composite plastic film.

Biodegradation process of the present invention is from distinctive expansion, bioactive compound in plastics can make the invasion and attack being more easily subject to microbial bacterial containing carbon polymer, can acidic materials be produced after microbial bacterial engulfs bioactive compound, thus carbon containing polymer substrate is expanded.When expansion contact is to heat and moisture, the molecular structure containing carbon polymer can be expanded, expand in polymer molecular structure after space for the creativity, the combination of bioactive compound and masterbatch will attract can metabolism and in the micropopulation of polymer.These micropopulations secretion acid solution cuts off the molecule long-chain of polymer further, until polymer is broken down into inert humus, carbon dioxide and methane.This biodegradation process can carry out under aerobic environment, also can carry out under anaerobic; Can carry out under the condition having illumination, heat and humidity, also can carry out under the condition of unglazed photograph, heat and humidity.The key of technical solution of the present invention is: in described addition type masterbatch, the hydrophilic active of hydrophilic radical should be more than or equal to the hydrophilic active of hydrophilic radical in laminated film layers of material; By adding addition type masterbatch, the hydrophilic radical of layers of material and the mol ratio of carbon atom in laminated film are reached unanimity, and namely biologically active reaches unanimity, thus the layers of material degradation rate of laminated film is reached unanimity.When adding bio-based, the addition type masterbatch selecting hydrophilic active to be greater than hydrophilic active in composite film material adds in the layers of material of laminated film, weaken original hydrophilic active in composite film material, by adding addition type masterbatch, the hydrophilic radical of layers of material and the mol ratio of carbon atom in laminated film are reached unanimity, namely biologically active reaches unanimity, thus the layers of material degradation rate of laminated film is reached unanimity.

Contribution of the present invention is: by the mol ratio and hydrophilic active that balance hydrophilic radical and carbon atom in layers of material, the biologically active of layers of material in complex thin film structure is reached unanimity, thus the layers of material degradation rate of laminated film is reached unanimity; When addition accounts for the 0.3-15% of this layer material gross mass, can keep film before by compost treatment, the outward appearance of its product, function and physical and mechanical properties are constant.

Detailed description of the invention

Below in conjunction with embodiment, the invention will be further described:

Embodiment one: (example of the first technical scheme)

A kind of degradable foaming coextrusion PET barrier film, the structure of this laminated film is as follows:

PET/EAA-TIE/EPO/PO-TIE/PA formula (1)

In formula (1), the implication represented successively is from left to right:

Pet sheet shows skin, and its function is protective layer or presentation layer, and its material is polyester, and monomer whose molecular formula is [OCH ₂-CH ₂oCOC ₆h ₄cO], the hydrophilic radical that polyester contains is ester group-COO-;

EAA-TIE represents the first adhesive layer, and its material is the ethylene acrylic acid co polymer of maleic anhydride graft, and the ethylene acrylic monomer whose molecular formula of maleic anhydride graft is { [CH ₂-CH ₂] _15.5[CH ₂-CH (COOH)] ₁} _3.7[C ₄h ₂o ₃] ₁, the hydrophilic radical that the ethylene acrylic acid co polymer of maleic anhydride graft contains is carboxyl-COOH and acid anhydrides OC-O-CO;

EPO represents middle level, and its function is toughening layer, and its material is polythene PE, and monomer whose molecular formula is-[CH ₂-CH ₂] _n-, polyethylene is not containing hydrophilic radical;

PO-TIE represents the second adhesive layer, and its material is the polyethylene and ethylene copolymers PE-TIE(95%PE+5% maleic anhydride of maleic anhydride graft), be mixed to form by the polyethylene of 95% weight and the maleic anhydride of 5% weight, monomer whose molecular formula is-[CH ₂-CH ₂] _n-[C ₄h ₂o ₃] _m, the hydrophilic radical that the polyethylene and ethylene copolymers of maleic anhydride graft contains be acid anhydrides-OC-O-CO-;

PA represents internal layer, and its function is coating layer, and its material is polyamide PA6, and monomer whose molecular formula is-[NH-(CH ₂) ₅-CO] _n-, the hydrophilic radical that polyamide contains is amide groups-CONH ₂-.

Namely the concrete structure formula of formula (1) is PET/EAA-TIE/PE/PE-TIE/PA6.

In described skin, polyester is amorphization PETG, or PETG-1,4-CHDM ester, and the density of polyester is 1.300-1.400g/cm ³.

Described first adhesive layer adopts the ethylene acrylic acid co polymer of maleic anhydride graft, and the density of the ethylene acrylic acid co polymer of maleic anhydride graft is 0.920-0.940g/cm ³, the mass percentage of maleic anhydride grafting ratio is 0.3%-10%; In ethylene acrylate copolymer, acrylic acid molar content is 8%-28%.

Described middle level take polyethylene as raw material, and adopt at least one in physical blowing and chemical blowing means to be processed by extruded type foaming, after foaming, poly density is 0.600-0.850g/cm ³.

Described second adhesive layer adopts the polyolefin copolymer of maleic anhydride graft, and when central layer material is polyethylene, the second adhesive layer selects the polyethylene and ethylene copolymers of maleic anhydride graft, and density is 0.910-0.950g/cm ³, the mass percentage of maleic anhydride grafting ratio is 0.3%-10%; When central layer material is polypropylene, the second adhesive layer selects the polypropylene copolymer of maleic anhydride graft, and density is 0.880-0.910 g/cm ³, maleic anhydride grafting ratio is 0.3%-10% weight.

Described internal layer adopts polyamide material, and the density of polyamide is 1.12-1.14 g/cm ³, polyamide is PA6 homopolymers or PA6,66 copolymers or amorphous polyamides.

Layers of material in described laminated film all obtains by introducing bio-based the biodegradability reached unanimity, described bio-based is the addition type masterbatch that a class has biological degradation activity under garbage disposal plant or composting conditions, this addition type masterbatch evenly adds in layers of material in proportion, then prepares laminated film by melting co-extrusion method;

Described addition type masterbatch is made up of carrier and activating agent, and described activating agent is the polymer containing hydrophilic radical, and wherein, the effective ingredient of activating agent is hydrophilic radical, and described hydrophilic radical refers to carboxylate-COO ^-, carboxyl-COOH, hydroxyl-OH, aldehyde radical-CHO, amide groups-CONH ₂, acid anhydrides-OC-O-CO-and ester group-COOR at least one.

In described formula (1) layers of material and addition type masterbatch, hydrophilic radical arranges from high to low according to hydrophilic active and is followed successively by carboxylate-COO ^-, carboxyl-COOH, hydroxyl-OH, aldehyde radical-CHO, amide groups-CONH ₂, acid anhydrides-OC-O-CO-, ester group-COOR.

In complex thin film structure according to embodiment one, the hydrophilic active of hydrophilic radical contained by various material sorts as carboxyl > amide groups > acid anhydrides > ester group from high to low, and namely the hydrophilic active of layers of material sorts from high to low as the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft in formula (1)) the polyethylene and ethylene copolymers PE-TIE(95%PE+5% maleic anhydride of > polyamide PA6> maleic anhydride graft) > polyester PET > polythene PE.

Select hydrophilic active to be greater than EAA-TIE(carboxyl in composite film material) sodium alginate of hydrophilic active as interpolation activating agent, weaken the hydrophilic active of original hydrophilic radical in composite film material.

1, the monomer molecule formula of known sodium alginate is (C ₅h ₇o ₄cOONa) _nfrom this monomer molecule formula, the hydrophilic radical contained in sodium alginate is carboxylic acid sodium (-COONa), hydroxyl (-OH) and ester group (-COOR), wherein, the hydrophilic active of carboxylic acid sodium (-COONa) is greater than the hydrophilic active of carboxyl (-COOH), in sodium alginate, the hydrophilic active of carboxylic acid sodium (-COONa) is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft) in the hydrophilic active of carboxyl (-COOH), therefore the present embodiment selective polymer sodium alginate adds in layers of material as activating agent.

2, because the hydrophilic active of carboxylic acid sodium in sodium alginate is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of the maleic anhydride graft in composite film material with the highest hydrophilic active) in the hydrophilic active of carboxyl (-COOH), play a leading role in biodegradation process, and the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft in composite film material) in carboxyl (-COOH), amide groups (-CONH in polyamide PA6 ₂), the polyethylene and ethylene copolymers PE-TIE(95%PE+5% maleic anhydride of maleic anhydride graft) middle acid anhydrides (-OC-O-CO-), in polyester PET, the effect of the hydrophilic active of ester group (-COOR) is weakened, in order to simplify statement, EAA-TIE is supposed in following calculating, the hydrophilic radical of PA6, PE-TIE and PET and carbon atom mol ratio are 0.

3, calculate: the hydrophilic radical of sodium alginate and carbon atom mol ratio are 2/3.

4, the hydrophilic radical of EAA-TIE, PA6, PE-TIE, PET, PE and carbon atom mol ratio are 0.

5, the addition due to addition type masterbatch is less, and carrier in addition type masterbatch is same or similar with the polymer be added, and in order to simplify statement, the quality of carrier in addition type masterbatch is ignored in following calculating.

Be the mass percent that a reference value calculates sodium alginate in layers of material respectively and adds according to the sodium alginate addition of 1%, 2.2% mole below:

A.1% the sodium alginate addition of mole

If in formula (1) layers of material respectively with sodium alginate with the ratio of mole for 99:1 mixes, calculate the mol ratio that layers of material adds hydrophilic radical after sodium alginate and carbon atom:

99/100* polyester _{(n hydrophilic radical: n carbon atom)}+ 1/100* sodium alginate _{(n hydrophilic radical: n carbon atom)}=99/100*0+1/100*2/3=0.0067;

The ethylene acrylic acid co polymer of 99/100* maleic anhydride graft _{(n hydrophilic radical: n carbon atom)}+ 1/100* sodium alginate _{(n hydrophilic radical: n carbon atom)}=99/100*0+1/100*2/3=0.0067;

99/100* polyethylene _{(n hydrophilic radical: n carbon atom)}+ 1/100* sodium alginate _{(n hydrophilic radical: n carbon atom)}=99/100*0+1/100*2/3=0.0067;

99/100* maleic anhydride grafted polyethylene copolymer _{(n hydrophilic radical: n carbon atom)}+ 1/100* sodium alginate _{(n hydrophilic radical: n carbon atom)}=99/100*0+1/100*2/3=0.0067;

99/100* polyamide _{(n hydrophilic radical: n carbon atom)}+ 1/100* sodium alginate _{(n hydrophilic radical: n carbon atom)}=99/100*0+1/100*2/3=0.0067.

By calculating above: in PET/EAA-TIE/PE/PE-TIE/PA6 structure layers of material respectively with sodium alginate with the ratio of mole for 99:1 mixes, calculate mixed hydrophilic radical all identical with the mol ratio of carbon atom, namely the hydrophilic active of layers of material all reaches unanimity, and its degradation rate all reaches unanimity.The Mass Calculation that in layers of material, sodium alginate adds is as follows:

If with the addition of the PET after sodium alginate is 1 mole, the quality of PET is m _1-1, the quality of sodium alginate is m _2-1;

M _1-1the molecular weight of=PET (gram/mol) * PET content (%) * mole (mol)

=192.17*99%*1=190.25 gram;

M _2-1the molecular weight of=sodium alginate (gram/mol) * sodium alginate content (%) * mole (mol)

=198.12*1%*1=1.98 gram;

If with the addition of the EAA-TIE after sodium alginate is 1 mole, the quality of EAA-TIE is m _1-2, the quality of sodium alginate is m _2-2;

M _1-2the molecular weight of=EAA-TIE (gram/mol) * EAA-TIE content (%) * mole (mol)

=37.41 * 99%*1=39.39 gram;

M _2-2the molecular weight of=sodium alginate (gram/mol) * sodium alginate content (%) * mole (mol)

=198.12*1%*1=1.98 gram;

If with the addition of the PE after sodium alginate is 1 mole, the quality of PE is m _1-3, the quality of sodium alginate is m _2-3;

M _1-3the molecular weight of=PE (gram/mol) * PE content (%) * mole (mol)

=28.05*99%*1=27.77 gram;

M _2-3the molecular weight of=sodium alginate (gram/mol) * sodium alginate content (%) * mole (mol)

=198.12*1%*1=1.98 gram;

If with the addition of the PE-TIE after sodium alginate is 1 mole, the quality of PE-TIE is m _1-4, the quality of sodium alginate is m _2-4;

M _1-4the molecular weight of=PE-TIE (gram/mol) * PE-TIE content (%) * mole (mol)

=32.67*99%*1=32.34 gram;

M _2-4the molecular weight of=sodium alginate (gram/mol) * sodium alginate content (%) * mole (mol)

=198.12*1%*1=1.98 gram;

If with the addition of the PA6 after sodium alginate is 1 mole, the quality of PA6 is m _1-5, the quality of sodium alginate is m _2-5;

M _1-5the molecular weight of=PA6 (gram/mol) * PA6 content (%) * mole (mol)

=113.16 * 99%*1=112.03 gram;

M _2-5the molecular weight of=sodium alginate (gram/mol) * sodium alginate content (%) * mole (mol)

=198.12*1%*1=1.98 gram;

For outer PET, the percentage that the quality of the sodium alginate of interpolation accounts for PET quality is: 1.98/ (190.25+1.98) * 100%=1.03%; The calculating of the mass percent of the sodium alginate added in all the other layers of materials by that analogy;

The interpolation mass percent of PET/EAA-TIE/PE/PE-TIE/PA6 sodium alginate is from left to right:

1.03/4.79/6.66/5.77/1.74。

B.2.2% the sodium alginate addition of mole

If in formula (1) layers of material respectively with sodium alginate with the ratio of mole for 97.8:2.2 mixes, calculate the mol ratio that layers of material adds hydrophilic radical after sodium alginate and carbon atom:

97.8/100* polyester (n hydrophilic radical: n carbon atom)+2.2/100* sodium alginate (n hydrophilic radical: n carbon atom)=97.8/100*0+2.2/100*2/3=0.0147;

Ethylene acrylic acid co polymer (n hydrophilic radical: n carbon atom)+2.2/100* sodium alginate (n hydrophilic radical: n the carbon atom)=97.8/100*0+2.2/100*2/3=0.0147 of 97.8/100* maleic anhydride graft;

97.8/100* polyethylene (n hydrophilic radical: n carbon atom)+2.2/100* sodium alginate (n hydrophilic radical: n carbon atom)=97.8/100*0+2.2/100*2/3=0.0147;

97.8/100* maleic anhydride grafted polyethylene copolymer (n hydrophilic radical: n carbon atom)+2.2/100* sodium alginate (n hydrophilic radical: n carbon atom)=97.8/100*0+2.2/100*2/3=0.0147;

97.8/100* polyamide (n hydrophilic radical: n carbon atom)+2.2/100* sodium alginate (n hydrophilic radical: n carbon atom)=97.8/100*0+2.2/100*2/3=0.0147.

By calculating above: in PET/EAA-TIE/PE/PE-TIE/PA6 structure layers of material respectively with sodium alginate with the ratio of mole for 97.8:2.2 mixes, calculate mixed hydrophilic radical all identical with the mol ratio of carbon atom, namely the hydrophilic active of layers of material all reaches unanimity, and its degradation rate all reaches unanimity.The Mass Calculation that in layers of material, sodium alginate adds is as follows:

M _1-1the molecular weight of=PET (gram/mol) * PET content (%) * mole (mol)

=192.17*97.8%*1=187.94 gram;

=198.12*2.2%*1=4.36 gram;

=37.41 * 97.8%*1=36.59 gram;

=198.12*2.2%*1=4.36 gram;

M _1-3the molecular weight of=PE (gram/mol) * PE content (%) * mole (mol)

=28.05*97.8%*1=27.43 gram;

=198.12*2.2%*1=4.36 gram;

=32.67*97.8%*1=31.95 gram;

=198.12*2.2%*1=4.36 gram;

M _1-5the molecular weight of=PA6 (gram/mol) * PA6 content (%) * mole (mol)

=113.16 * 97.8%*1=110.67 gram;

=198.12*2.2%*1=4.36 gram;

For outer PET, the percentage that the quality of the sodium alginate of interpolation accounts for PET quality is: 4.36/ (187.94+4.36) * 100%=2.27%; The calculating of the mass percent of the sodium alginate added in all the other layers of materials by that analogy;

2.27/10.65/13.72/12.01/3.79。

When the addition of sodium alginate accounts in 0.3-15% scope of equivalent layer material gross mass, the mechanical performance of this layer material and barrier property are not affected.

In order to improve fitness of process and the dispersiveness of hydrophilic radical, the polymer that compatibility is very excellent can be selected to carry out copolymerization.Such as: the copolymer of polycaprolactone (PCL) and sodium alginate copolymerization, the copolymer of PLA (PLA) and sodium alginate copolymerization.

The copolymer of A, polycaprolactone (PCL) and sodium alginate copolymerization

1, the monomer molecule formula of known sodium alginate is (C ₅h ₇o ₄cOONa) _n, the monomer molecule formula of polycaprolactone is [CH2-(CH2) 4-COO] _m, percent grafting is the monomer molecule formula of the polycaprolactone co-polymer of the sodium alginate grafting of 50-80% quality is [CH2-(CH2) 4-COO] _m(C ₅h ₇o ₄cOONa) _n, from this monomer molecule formula, the hydrophilic radical contained in sodium alginate is carboxylic acid sodium (-COONa), hydroxyl (-OH) and ester group (-COOR), the hydrophilic radical contained in polycaprolactone is ester group (-COOR), wherein, the hydrophilic active of carboxylic acid sodium (-COONa) is greater than the hydrophilic active of carboxyl (-COOH), in sodium alginate, the hydrophilic active of carboxylic acid sodium (-COONa) is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft) in the hydrophilic active of carboxyl (-COOH), the present embodiment selection percent grafting is that the polycaprolactone co-polymer of the sodium alginate grafting of 60% quality adds in layers of material as activating agent.

2, because the hydrophilic active of carboxylic acid sodium in copolymer is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of the maleic anhydride graft in composite film material with the highest hydrophilic active) in the hydrophilic active of carboxyl (-COOH), play a leading role in biodegradation process, and the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft in composite film material) in carboxyl (-COOH), amide groups (-CONH in polyamide PA6 ₂), the polyethylene and ethylene copolymers PE-TIE(95%PE+5% maleic anhydride of maleic anhydride graft) middle acid anhydrides (-OC-O-CO-), in polyester PET, the effect of the hydrophilic active of ester group (-COOR) is weakened, in order to simplify statement, EAA-TIE is supposed in following calculating, the hydrophilic radical of PA6, PE-TIE and PET and carbon atom mol ratio are 0.

In the polycaprolactone co-polymer of 3, sodium alginate grafting, the hydrophilic radical of sodium alginate and carbon atom mol ratio are 2/3; Hydrophilic radical and the carbon atom mol ratio of polycaprolactone are 1/7, calculate: the hydrophilic radical of the polycaprolactone co-polymer of sodium alginate grafting and carbon atom mol ratio=2/3*60%+1/7*40%=0.4571.

Below according to the polycaprolactone co-polymer addition of the sodium alginate grafting of 2% mole be a reference value calculate respectively sodium alginate grafting in layers of material polycaprolactone co-polymer add mass percent:

If in formula (1) layers of material respectively with the polycaprolactone co-polymer of sodium alginate grafting with the ratio of mole for 98:2 mixes, calculate the mol ratio that layers of material adds hydrophilic radical after the polycaprolactone co-polymer of sodium alginate grafting and carbon atom:

98/100* polyester _{(n hydrophilic radical: n carbon atom)}the polycaprolactone co-polymer of+2/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98/100*0+2/100*45.71/100=0.0091;

The ethylene acrylic acid co polymer of 98/100* maleic anhydride graft _{(n hydrophilic radical: n carbon atom)}the polycaprolactone co-polymer of+2/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98/100*0+2/100*45.71/100=0.0091;

98/100* polyethylene _{(n hydrophilic radical: n carbon atom)}the polycaprolactone co-polymer of+2/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98/100*0+2/100*45.71/100=0.0091;

98/100* maleic anhydride grafted polyethylene copolymer _{(n hydrophilic radical: n carbon atom)}the polycaprolactone co-polymer of+2/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98/100*0+2/100*45.71/100=0.0091;

98/100* polyamide _{(n hydrophilic radical: n carbon atom)}the polycaprolactone co-polymer of+2/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98/100*0+2/100*45.71/100=0.0091;

By calculating above: in PET/EAA-TIE/PE/PE-TIE/PA6 structure layers of material respectively with the polycaprolactone co-polymer of sodium alginate grafting with the ratio of mole for 98:2 mixes, calculate mixed hydrophilic radical all identical with the mol ratio of carbon atom, namely the hydrophilic active of layers of material all reaches unanimity, and its degradation rate all reaches unanimity.The Mass Calculation that the polycaprolactone co-polymer of sodium alginate grafting in layers of material adds is as follows:

If with the addition of the PET after the polycaprolactone co-polymer of sodium alginate grafting is 1 mole, the quality of PET is m _1-1, the quality of the polycaprolactone co-polymer of sodium alginate grafting is m _2-1;

M _1-1the molecular weight of=PET (gram/mol) * PET content (%) * mole (mol)

=192.17*98%*1=188.33 gram;

M _2-1polycaprolactone co-polymer content (%) * mole (mol) of the molecular weight of the polycaprolactone co-polymer of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=164.52*2%*1=3.29 gram;

If with the addition of the EAA-TIE after the polycaprolactone co-polymer of sodium alginate grafting is 1 mole, the quality of EAA-TIE is m _1-2, the quality of the polycaprolactone co-polymer of sodium alginate grafting is m _2-2;

=37.41 * 98%*1=36.66 gram;

M _2-2polycaprolactone co-polymer content (%) * mole (mol) of the molecular weight of the polycaprolactone co-polymer of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=164.52*2%*1=3.29 gram;

If with the addition of the PE after the polycaprolactone co-polymer of sodium alginate grafting is 1 mole, the quality of PE is m _1-3, the quality of the polycaprolactone co-polymer of sodium alginate grafting is m _2-3;

M _1-3the molecular weight of=PE (gram/mol) * PE content (%) * mole (mol)

=28.05*98%*1=27.49 gram;

M _2-3polycaprolactone co-polymer content (%) * mole (mol) of the molecular weight of the polycaprolactone co-polymer of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=164.52*2%*1=3.29 gram;

If with the addition of the PE-TIE after the polycaprolactone co-polymer of sodium alginate grafting is 1 mole, the quality of PE-TIE is m _1-4, the quality of the polycaprolactone co-polymer of sodium alginate grafting is m _2-4;

=32.67*98%*1=32.02 gram;

M _2-4polycaprolactone co-polymer content (%) * mole (mol) of the molecular weight of the polycaprolactone co-polymer of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=164.52*2%*1=3.29 gram;

If with the addition of the PA6 after the polycaprolactone co-polymer of sodium alginate grafting is 1 mole, the quality of PA6 is m _1-5, the quality of the polycaprolactone co-polymer of sodium alginate grafting is m _2-5;

M _1-5the molecular weight of=PA6 (gram/mol) * PA6 content (%) * mole (mol)

=113.16 * 98%*1=110.90 gram;

M _2-5polycaprolactone co-polymer content (%) * mole (mol) of the molecular weight of the polycaprolactone co-polymer of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=164.52*2%*1=3.29 gram;

For outer PET, the percentage that the quality of polycaprolactone co-polymer of the sodium alginate grafting added accounts for PET quality is: 3.29/ (188.33+3.29) * 100%=1.72%, and the calculating of the mass percent of the polycaprolactone co-polymer of the sodium alginate grafting added in all the other layers of materials by that analogy;

The interpolation mass percent of the polycaprolactone co-polymer of PET/EAA-TIE/PE/PE-TIE/PA6 sodium alginate grafting is from left to right:

1.72/8.24/10.69/9.32/2.88。

When the addition of the polycaprolactone co-polymer of the polycaprolactone co-polymer of sodium alginate grafting accounts in 0.3-15% scope of equivalent layer material gross mass, the mechanical performance of this layer material and barrier property are not affected.

The copolymer of B, PLA (PLA) and sodium alginate copolymerization

1, the monomer molecule formula of known sodium alginate is (C ₅h ₇o ₄cOONa) _n, the monomer molecule formula of PLA is [H-(OCH (CH3) CO) ₂-OH] _m, percent grafting is the monomer molecule formula of the copolymer of poly lactic acid of the sodium alginate grafting of 5-20% quality is [H-(OCH (CH ₃) CO) ₂-OH] _m[C ₅h ₇o ₄cOONa] _nfrom this monomer molecule formula, the hydrophilic radical contained in sodium alginate is carboxylic acid sodium (-COONa), hydroxyl (-OH) and ester group (-COOR), the hydrophilic radical contained in PLA is carboxyl (-COOH), hydroxyl (-OH) and ester group (-COOR), wherein, the hydrophilic active of carboxylic acid sodium (-COONa) is greater than the hydrophilic active of carboxyl (-COOH), in sodium alginate, the hydrophilic active of carboxylic acid sodium (-COONa) is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft) in the hydrophilic active of carboxyl (-COOH), in PLA, the content of carboxyl (-COOH) is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft) in the content of carboxyl (-COOH), in PLA, the hydrophilic active of carboxyl (-COOH) is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft) in the hydrophilic active of acid anhydrides (-OC-O-CO-), the present embodiment selection percent grafting is that the copolymer of poly lactic acid of the sodium alginate grafting of 10% quality adds in layers of material as activating agent.

2, because in the copolymer of poly lactic acid of sodium alginate grafting, the hydrophilic active of carboxylic acid sodium is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of the maleic anhydride graft in composite film material with the highest hydrophilic active) in the hydrophilic active of carboxyl (-COOH), in the copolymer of poly lactic acid of sodium alginate grafting, the content of carboxyl is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft) in the content of carboxyl (-COOH), play a leading role in biodegradation process, and the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft in composite film material) in carboxyl (-COOH), amide groups (-CONH in polyamide PA6 ₂), the polyethylene and ethylene copolymers PE-TIE(95%PE+5% maleic anhydride of maleic anhydride graft) middle acid anhydrides (-OC-O-CO-), in polyester PET, the effect of the hydrophilic active of ester group (-COOR) is weakened, in order to simplify statement, EAA-TIE is supposed in following calculating, the hydrophilic radical of PA6, PE-TIE and PET and carbon atom mol ratio are 0.

In the copolymer of poly lactic acid of 3, sodium alginate grafting, the hydrophilic radical of sodium alginate and carbon atom mol ratio are 2/3; Hydrophilic radical and the carbon atom mol ratio of PLA are 2/3, calculate: the hydrophilic radical of the copolymer of poly lactic acid of sodium alginate grafting and carbon atom mol ratio=2/3*10%+2/3*90%=2/3.

Below according to the copolymer of poly lactic acid addition of the sodium alginate grafting of 1.5% mole be a reference value calculate respectively sodium alginate grafting in layers of material copolymer of poly lactic acid add mass percent:

If in formula (1) layers of material respectively with the copolymer of poly lactic acid of sodium alginate grafting with the ratio of mole for 98.5:1.5 mixes, calculate the mol ratio that layers of material adds hydrophilic radical after the copolymer of poly lactic acid of sodium alginate grafting and carbon atom:

98.5/100* polyester _{(n hydrophilic radical: n carbon atom)}the copolymer of poly lactic acid of+1.5/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98.5/100*0+1.5/100*2/3=0.0010;

The ethylene acrylic acid co polymer of 98.5/100* maleic anhydride graft _{(n hydrophilic radical: n carbon atom)}the copolymer of poly lactic acid of+1.5/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98.5/100*0+1.5/100*2/3=0.0010;

98.5/100* polyethylene _{(n hydrophilic radical: n carbon atom)}the copolymer of poly lactic acid of+1.5/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98.5/100*0+1.5/100*2/3=0.0010;

98.5/100* maleic anhydride grafted polyethylene copolymer _{(n hydrophilic radical: n carbon atom)}the copolymer of poly lactic acid of+1.5/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98.5/100*0+1.5/100*2/3=0.0010;

98.5/100* polyamide _{(n hydrophilic radical: n carbon atom)}the copolymer of poly lactic acid of+1.5/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98.5/100*0+1.5/100*2/3=0.0010;

By calculating above: in PET/EAA-TIE/PE/PE-TIE/PA6 structure layers of material respectively with the copolymer of poly lactic acid of sodium alginate grafting with the ratio of mole for 98.5:1.5 mixes, calculate mixed hydrophilic radical all identical with the mol ratio of carbon atom, namely the hydrophilic active of layers of material all reaches unanimity, and its degradation rate all reaches unanimity.The Mass Calculation that the polycaprolactone co-polymer of sodium alginate grafting in layers of material adds is as follows:

If with the addition of the PET after the copolymer of poly lactic acid of sodium alginate grafting is 1 mole, the quality of PET is m _1-1, the quality of the copolymer of poly lactic acid of sodium alginate grafting is m _2-1;

M _1-1the molecular weight of=PET (gram/mol) * PET content (%) * mole (mol)

=192.17*98.5%*1=189.29 gram;

M _2-1copolymer of poly lactic acid content (%) * mole (mol) of the molecular weight of the copolymer of poly lactic acid of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=165.74*1.5%*1=2.49 gram;

If with the addition of the EAA-TIE after the copolymer of poly lactic acid of sodium alginate grafting is 1 mole, the quality of EAA-TIE is m _1-2, the quality of the copolymer of poly lactic acid of sodium alginate grafting is m _2-2;

=37.41 * 98.5%*1=36.85 gram;

M _2-2copolymer of poly lactic acid content (%) * mole (mol) of the molecular weight of the copolymer of poly lactic acid of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=165.74*1.5%*1=2.49 gram;

If with the addition of the PE after the copolymer of poly lactic acid of sodium alginate grafting is 1 mole, the quality of PE is m _1-3, the quality of the copolymer of poly lactic acid of sodium alginate grafting is m _2-3;

M _1-3the molecular weight of=PE (gram/mol) * PE content (%) * mole (mol)

=28.05*98.5%*1=27.63 gram;

M _2-3copolymer of poly lactic acid content (%) * mole (mol) of the molecular weight of the copolymer of poly lactic acid of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=165.74*1.5%*1=2.49 gram;

If with the addition of the PE-TIE after the copolymer of poly lactic acid of sodium alginate grafting is 1 mole, the quality of PE-TIE is m _1-4, the quality of the copolymer of poly lactic acid of sodium alginate grafting is m _2-4;

=32.67*98.5%*1=32.18 gram;

M _2-4copolymer of poly lactic acid content (%) * mole (mol) of the molecular weight of the copolymer of poly lactic acid of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=165.74*1.5%*1=2.49 gram;

If with the addition of the PA6 after the copolymer of poly lactic acid of sodium alginate grafting is 1 mole, the quality of PA6 is m _1-5, the quality of the copolymer of poly lactic acid of sodium alginate grafting is m _2-5;

M _1-5the molecular weight of=PA6 (gram/mol) * PA6 content (%) * mole (mol)

=113.16 * 98.5%*1=111.46 gram;

M _2-5copolymer of poly lactic acid content (%) * mole (mol) of the molecular weight of the copolymer of poly lactic acid of=sodium alginate grafting (gram/mol) * sodium alginate grafting

=165.74*1.5%*1=2.49 gram;

For outer PET, the percentage that the quality of the copolymer of poly lactic acid of sodium alginate grafting accounts for PET quality is: 2.49/ (189.29+2.49) * 100%=1.30%, and the calculating of the mass percent of the copolymer of poly lactic acid of the sodium alginate grafting added in all the other layers of materials by that analogy;

The interpolation mass percent of the copolymer of poly lactic acid of PET/EAA-TIE/PE/PE-TIE/PA6 sodium alginate grafting is from left to right:

1.30/6.33/8.27/7.18/2.19。

When the addition of the copolymer of poly lactic acid of sodium alginate grafting accounts in 0.3-15% scope of equivalent layer material gross mass, the mechanical performance of this layer material and barrier property are not affected.

Embodiment two: (example of the first technical scheme)

In formula (2), the implication represented successively is from left to right:

EAA-TIE represents the second adhesive layer, and its material is the ethylene acrylic acid co polymer of maleic anhydride graft, and the ethylene acrylic monomer whose molecular formula of maleic anhydride graft is { [CH ₂-CH ₂] _15.5[CH ₂-CH (COOH)] ₁} _3.7[C ₄h ₂o ₃] ₁, the hydrophilic radical that the ethylene acrylic acid co polymer of maleic anhydride graft contains is carboxyl-COOH and acid anhydrides OC-O-CO;

Pet sheet shows internal layer, and its function is coating layer, and its material is polyester, and monomer whose molecular formula is [OCH ₂-CH ₂oCOC ₆h ₄cO], the hydrophilic radical that polyester contains is ester group-COO-.

Namely the concrete structure formula of formula (2) is PET/EAA-TIE/PE/EAA-TIE/PET.

Described second adhesive layer adopts the ethylene acrylic acid co polymer of maleic anhydride graft, and the density of the ethylene acrylic acid co polymer of maleic anhydride graft is 0.920-0.940g/cm ³, the mass percentage of maleic anhydride grafting ratio is 0.3%-10%; In ethylene acrylate copolymer, acrylic acid molar content is 8%-28%.

In described internal layer, polyester is amorphization PETG, or PETG-1,4-CHDM ester, and the density of polyester is 1.300-1.400g/cm ³.

The addition of described addition type masterbatch in layers of material controls the 0.3-15% scope in this layer material gross mass; In described addition type masterbatch, the hydrophilic active of hydrophilic radical should be more than or equal to the hydrophilic active of hydrophilic radical in formula (2) layers of material; By adding addition type masterbatch, the hydrophilic radical of layers of material and the mol ratio of carbon atom in formula (2) are reached unanimity, and namely biologically active reaches unanimity, thus the layers of material degradation rate of laminated film is reached unanimity.In complex thin film structure according to embodiment two, the hydrophilic active of hydrophilic radical contained by various material sorts as carboxyl > acid anhydrides > ester group from high to low, and namely in formula (2), the hydrophilic active of layers of material sorts from high to low as the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft) > polyester PET > polythene PE.

2, because the hydrophilic active of carboxylic acid sodium in sodium alginate is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of the maleic anhydride graft in composite film material with the highest hydrophilic active) in the hydrophilic active of carboxyl (-COOH), play a leading role in biodegradation process, and the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft in composite film material) in carboxyl (-COOH), in polyester PET, the effect of the hydrophilic active of ester group (-COOR) is weakened, in order to simplify statement, in following calculating, suppose EAA-TIE and PET hydrophilic radical and carbon atom mol ratio are 0.

4, the hydrophilic radical of EAA-TIE, PET, PE and carbon atom mol ratio are 0.

A.1% the sodium alginate addition of mole

If in formula (2) layers of material respectively with sodium alginate with the ratio of mole for 99:1 mixes, calculate the mol ratio that layers of material adds hydrophilic radical after sodium alginate and carbon atom:

99/100* polyethylene _{(n hydrophilic radical: n carbon atom)}+ 1/100* sodium alginate _{(n hydrophilic radical: n carbon atom)}=99/100*0+1/100*2/3=0.0067.

By calculating above: in PET/EAA-TIE/PE/EAA-TIE/PET structure layers of material respectively with sodium alginate with the ratio of mole for 99:1 mixes, calculate mixed hydrophilic radical all identical with the mol ratio of carbon atom, namely the hydrophilic active of layers of material all reaches unanimity, and its degradation rate all reaches unanimity.The Mass Calculation that in layers of material, sodium alginate adds is as follows:

M _1-1the molecular weight of=PET (gram/mol) * PET content (%) * mole (mol)

=192.17*99%*1=190.25 gram;

=198.12*1%*1=1.98 gram;

=37.41 * 99%*1=39.39 gram;

=198.12*1%*1=1.98 gram;

M _1-3the molecular weight of=PE (gram/mol) * PE content (%) * mole (mol)

=28.05*99%*1=27.77 gram;

=198.12*1%*1=1.98 gram;

The interpolation mass percent of PET/EAA-TIE/PE/EAA-TIE/PET sodium alginate is from left to right:

1.03/4.79/6.66/4.79/1.03。

B.2.2% the sodium alginate addition of mole

If in formula (2) layers of material respectively with sodium alginate with the ratio of mole for 97.8:2.2 mixes, calculate the mol ratio that layers of material adds hydrophilic radical after sodium alginate and carbon atom:

97.8/100* polyethylene (n hydrophilic radical: n carbon atom)+2.2/100* sodium alginate (n hydrophilic radical: n carbon atom)=97.8/100*0+2.2/100*2/3=0.0147.

By calculating above: in PET/EAA-TIE/PE/EAA-TIE/PET structure layers of material respectively with sodium alginate with the ratio of mole for 97.8:2.2 mixes, calculate mixed hydrophilic radical all identical with the mol ratio of carbon atom, namely the hydrophilic active of layers of material all reaches unanimity, and its degradation rate all reaches unanimity.The Mass Calculation that in layers of material, sodium alginate adds is as follows:

M _1-1the molecular weight of=PET (gram/mol) * PET content (%) * mole (mol)

=192.17*97.8%*1=187.94 gram;

=198.12*2.2%*1=4.36 gram;

=37.41 * 97.8%*1=36.59 gram;

=198.12*2.2%*1=4.36 gram;

M _1-3the molecular weight of=PE (gram/mol) * PE content (%) * mole (mol)

=28.05*97.8%*1=27.43 gram;

=198.12*2.2%*1=4.36 gram.

2.27/10.65/13.72/10.65/2.27。

The copolymer of A, polycaprolactone (PCL) and sodium alginate copolymerization

2, because the hydrophilic active of carboxylic acid sodium in copolymer is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of the maleic anhydride graft in composite film material with the highest hydrophilic active) in the hydrophilic active of carboxyl (-COOH), play a leading role in biodegradation process, and the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft in composite film material) in carboxyl (-COOH), in polyester PET, the effect of the hydrophilic active of ester group (-COOR) is weakened, in order to simplify statement, in following calculating, suppose EAA-TIE and PET hydrophilic radical and carbon atom mol ratio are 0.

4, the hydrophilic radical of EAA-TIE, PET, PE and carbon atom mol ratio are 0.

If in formula (2) layers of material respectively with the polycaprolactone co-polymer of sodium alginate grafting with the ratio of mole for 98:2 mixes, calculate the mol ratio that layers of material adds hydrophilic radical after the polycaprolactone co-polymer of sodium alginate grafting and carbon atom:

98/100* polyethylene _{(n hydrophilic radical: n carbon atom)}the polycaprolactone co-polymer of+2/100* sodium alginate grafting _{(n hydrophilic radical: n carbon atom)}=98/100*0+2/100*45.71/100=0.0091.

By calculating above: in PET/EAA-TIE/PE/EAA-TIE/PET structure layers of material respectively with the polycaprolactone co-polymer of sodium alginate grafting with the ratio of mole for 98:2 mixes, calculate mixed hydrophilic radical all identical with the mol ratio of carbon atom, namely the hydrophilic active of layers of material all reaches unanimity, and its degradation rate all reaches unanimity.The Mass Calculation that the polycaprolactone co-polymer of sodium alginate grafting in layers of material adds is as follows:

M _1-1the molecular weight of=PET (gram/mol) * PET content (%) * mole (mol)

=192.17*98%*1=188.33 gram;

=164.52*2%*1=3.29 gram;

=37.41 * 98%*1=36.66 gram;

=164.52*2%*1=3.29 gram;

M _1-3the molecular weight of=PE (gram/mol) * PE content (%) * mole (mol)

=28.05*98%*1=27.49 gram;

=164.52*2%*1=3.29 gram.

The interpolation mass percent of the polycaprolactone co-polymer of PET/EAA-TIE/PE/EAA-TIE/PET sodium alginate grafting is from left to right:

1.72/8.24/10.69/8.24/1.72。

The copolymer of B, PLA (PLA) and sodium alginate copolymerization

2, because in the copolymer of poly lactic acid of sodium alginate grafting, the hydrophilic active of carboxylic acid sodium is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of the maleic anhydride graft in composite film material with the highest hydrophilic active) in the hydrophilic active of carboxyl (-COOH), in the copolymer of poly lactic acid of sodium alginate grafting, the content of carboxyl is greater than the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft) in the content of carboxyl (-COOH), play a leading role in biodegradation process, and the ethylene acrylic acid co polymer EAA-TIE(95%EAA+5% maleic anhydride of maleic anhydride graft in composite film material) in carboxyl (-COOH), in polyester PET, the effect of the hydrophilic active of ester group (-COOR) is weakened, in order to simplify statement, in following calculating, suppose EAA-TIE and PET hydrophilic radical and carbon atom mol ratio are 0.

4, the hydrophilic radical of EAA-TIE, PET, PE and carbon atom mol ratio are 0.

If in formula (2) layers of material respectively with the copolymer of poly lactic acid of sodium alginate grafting with the ratio of mole for 98.5:1.5 mixes, calculate the mol ratio that layers of material adds hydrophilic radical after the copolymer of poly lactic acid of sodium alginate grafting and carbon atom:

By calculating above: in PET/EAA-TIE/PE/EAA-TIE/PET structure layers of material respectively with the copolymer of poly lactic acid of sodium alginate grafting with the ratio of mole for 98.5:1.5 mixes, calculate mixed hydrophilic radical all identical with the mol ratio of carbon atom, namely the hydrophilic active of layers of material all reaches unanimity, and its degradation rate all reaches unanimity.The Mass Calculation that the polycaprolactone co-polymer of sodium alginate grafting in layers of material adds is as follows:

M _1-1the molecular weight of=PET (gram/mol) * PET content (%) * mole (mol)

=192.17*98.5%*1=189.29 gram;

=165.74*1.5%*1=2.49 gram;

=37.41 * 98.5%*1=36.85 gram;

=165.74*1.5%*1=2.49 gram;

M _1-3the molecular weight of=PE (gram/mol) * PE content (%) * mole (mol)

=28.05*98.5%*1=27.63 gram;

=165.74*1.5%*1=2.49 gram;

The interpolation mass percent of the copolymer of poly lactic acid of PET/EAA-TIE/PE/EAA-TIE/PET sodium alginate grafting is from left to right:

1.30/6.33/8.27/6.33/1.30。

In the above-described embodiments, activating agent have selected the copolymer of sodium alginate and sodium alginate grafting, these are directly supported by above-described embodiment, but, in the present invention, except the above-mentioned activating agent pointed out, other can also be selected to contain hydrophilic radical carboxylate, carboxyl, hydroxyl, aldehyde radical, amide groups, the polymer of acid anhydrides and ester group, as: polycaprolactone, polycaprolactone polyol, polysaccharide polymer, algae based polyalcohol etc., those skilled in the art are under the inspiration of the embodiment of the present invention, can understand and predict the concrete polymer containing these groups, so addition type masterbatch of the present invention is not limited to these polymer that embodiment provides.

In the embodiment above, about the addition of addition type masterbatch numerically only gives some examples, those skilled in the art, under the inspiration of this example, easily expect that addition type masterbatch all can realize the object of the invention and effect within the scope of 0.3-15%.

In the embodiment above; for the ease of implementing (being suitable for melt extruding); a scope is each defined to the density of layers of material, copolymerization ratios, blending ratio, expansion ratio; and illustrate in instances; but these require for purposes of the invention not necessarily; can not as the foundation limiting scope, in other words, the above-mentioned various index that being suitable for outside above-mentioned scope melt extrudes all can realize the present invention and obtain corresponding technique effect.

In the present invention, although give the structural formula of laminated film, but the same material being positioned at same position in structural formula can be combined to form by one or more layers, such as, in PET/EAA-TIE/PE/EAA-TIE/PET structural formula, what this structural formula was expressed outwardly is 5 Rotating fields, but the material on optional position all can be combined to form more than two-layer or two-layer, such as PE can be combined to form by two-layer, with this, this laminated film is combined to form by 6 layers, by that analogy.Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.Those skilled in the art can on the basis of the various embodiments described above; in each number range interval, value is combined; all same effect can be reached; here the value of percentage by weight shared by the no longer exhaustive value of each density of material, the value of maleic anhydride grafting ratio and each material; all equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims

1. a degradable foaming coextrusion PET barrier film, the structure of this laminated film is as follows:

In formula (1), the implication represented successively is from left to right:

It is characterized in that: the layers of material in described laminated film all obtains by introducing bio-based the biodegradability reached unanimity, described bio-based is the addition type masterbatch that a class has biological degradation activity under garbage disposal plant or composting conditions, this addition type masterbatch evenly adds in layers of material in proportion, then prepares laminated film by melting co-extrusion method;

2. a degradable foaming coextrusion PET barrier film, the structure of this laminated film is as follows:

In formula (2), the implication represented successively is from left to right:

3. degradable foaming coextrusion barrier film according to claim 1 and 2, it is characterized in that: in described skin, polyester is amorphization PETG, or PETG-1,4-cyclohexanedimethanoester ester, the density of polyester is 1.300-1.400g/cm ³.

4. degradable foaming coextrusion barrier film according to claim 1 and 2, it is characterized in that: described first adhesive layer adopts the ethylene acrylic acid co polymer of maleic anhydride graft, and the density of the ethylene acrylic acid co polymer of maleic anhydride graft is 0.920-0.940g/cm ³, the mass percentage of maleic anhydride grafting ratio is 0.3%-10%; In ethylene acrylate copolymer, acrylic acid molar content is 8%-28%.

5. degradable foaming coextrusion barrier film according to claim 1 and 2, it is characterized in that: described middle level with polyethylene or polypropylene for raw material, adopt at least one in physical blowing and chemical blowing means to be processed by extruded type foaming, after foaming, poly density is 0.600-0.850g/cm ³, after foaming, polyacrylic density is 0.600-0.850g/cm ³.

6. degradable foaming coextrusion barrier film according to claim 1, it is characterized in that: described second adhesive layer adopts the polyolefin copolymer of maleic anhydride graft, when central layer material is polyethylene, second adhesive layer selects the polyethylene and ethylene copolymers of maleic anhydride graft, and density is 0.910-0.950g/cm ³, the mass percentage of maleic anhydride grafting ratio is 0.3%-10%; When central layer material is polypropylene, the second adhesive layer selects the polypropylene copolymer of maleic anhydride graft, and density is 0.880-0.910 g/cm ³, maleic anhydride grafting ratio is 0.3%-10% weight.

7. degradable foaming coextrusion barrier film according to claim 2, it is characterized in that: described second adhesive layer adopts the ethylene acrylic acid co polymer of maleic anhydride graft, and the density of the ethylene acrylic acid co polymer of maleic anhydride graft is 0.920-0.940g/cm ³, the mass percentage of maleic anhydride grafting ratio is 0.3%-10%; In ethylene acrylate copolymer, acrylic acid molar content is 8%-28%.

8. degradable foaming coextrusion barrier film according to claim 1, is characterized in that: described internal layer adopts polyamide material, and the density of polyamide is 1.12-1.14 g/cm ³, polyamide is PA6 homopolymers or PA6,66 copolymers or amorphous polyamides.

9. degradable foaming coextrusion barrier film according to claim 2, it is characterized in that: in described internal layer, polyester is amorphization PETG, or PETG-1,4-cyclohexanedimethanoester ester, the density of polyester is 1.300-1.400g/cm ³.