CN111647143A - Copolymer material for laminating film and preparation method and application thereof - Google Patents

Copolymer material for laminating film and preparation method and application thereof Download PDF

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CN111647143A
CN111647143A CN201910893564.5A CN201910893564A CN111647143A CN 111647143 A CN111647143 A CN 111647143A CN 201910893564 A CN201910893564 A CN 201910893564A CN 111647143 A CN111647143 A CN 111647143A
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copolymer material
albemarle
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CN111647143B (en
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张欣舟
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Hainan Pujing Environmental Protection Technology Co ltd
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Pujing Chemical Industry SHA Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28—Polyesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a copolymer material for laminating, a preparation method and application thereof, wherein the copolymer material comprises one or more than one C- (A)x‑By)n-a polymer of structure D; wherein A is a polyglycolide structure; the molecular structural formula of B is G-R1-W, wherein G and W are selected from-CO-NH-, -CO-R2‑CO‑OH，‑CO‑，‑(CH2)2NH‑CO‑，‑CH2‑CH(OH)‑CH2-or-NH; wherein R is1Is a copolymerization structure formed by aliphatic groups, aromatic groups or aliphatic or aromatic groups, R2Is alkyl, aryl or alkenyl; x is 1-1500, y is 1-1500, and n is 1-10000; c and D are terminal groups selected from hydroxyl, carboxyl, amino,One or more of alkyl, aryl, ether, alkylene or halogenated hydrocarbon. Compared with the prior art, the invention has the advantages of excellent mechanical properties such as mechanical strength, toughness and the like, degradability, good hydrolytic stability, high melt thermal stability and the like.

Description

Copolymer material for laminating film and preparation method and application thereof
Technical Field
The invention relates to a polyglycolic acid composite material, in particular to a copolymer material for a lamination, belonging to the technical field of high molecular compounds.
Background
In order to prevent the paper material from being impregnated with liquid and to improve durability, paper food container packages, containers, sanitary products, etc. are usually covered with a plastic film on the inner and outer surfaces to prevent water and leakage, which is called as a film coating. Polyethylene (PE) or polypropylene (PP) is generally used as a raw material for the laminated film, but because the Polyethylene (PE) and the polypropylene (PP) cannot be biodegraded, a large amount of white garbage is generated, and environmental pollution is caused.
In order to solve the pollution problem, a coated paper covered with degradable plastic is developed in the industry, and PLA (polylactic acid) is one of the coated paper. PLA can be naturally decomposed, has no toxicity, meets the requirements of environmental protection, but has the defects of brittleness, poor toughness and tensile property, poor thermal stability and the like, so that the application range of the PLA is greatly limited, and the prior PLA laminating technology has certain requirements on the thickness of a laminated film, which cannot be lower than 22g/m2Resulting in excessive cost of PLA lamination. The other biodegradable material PBS (poly butylene succinate) has low processing temperature, low viscosity and poor melt strength, so the application range of the two materials in the laminating field is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a copolymer material for a curtain coating film and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a copolymer material for laminating film is composed of one or more of C- (A)x-By)n-a polymer of structure D;
a is selected from
Figure BDA0002209541190000011
One or more of the structures;
the molecular structural formula of B is G-R1-W, wherein G and W are selected from-CO-NH-, -CO-R2-CO-OH，-CO-，-(CH2)2NH-CO-，-CH2-CH(OH)-CH2-or-NH; wherein R is1Is a copolymerization structure formed by aliphatic groups, aromatic groups or aliphatic or aromatic groups, R2Is alkyl, aryl or alkenyl;
x is 1-1500, y is 1-1500, and n is 1-10000;
c and D are end groups, and are selected from one or more of hydroxyl, carboxyl, amino, alkyl, aryl, ether, alkylene or halogenated hydrocarbon groups.
The copolymer material prepared by the invention has the weight-average molecular weight of 10000-1000000 and the ratio (Mw/Mn) of the weight-average molecular weight to the number-average molecular weight of 1-10, preferably 1.2-8, and more preferably 1.5-5.
The copolymer material has a melt index (MFR) of 0.1 to 1000g/10min, preferably 0.15 to 500g/10min, more preferably 0.2 to 100g/10 min.
The invention adopts the structure regulator to regulate the skeleton of polyglycolide, the polyglycolide is a high molecular material with good biocompatibility and biodegradability, the mechanical property of the polyglycolide is regulated by adding the structure regulator into the polymer, and G-R is introduced into the polyglycolide structure of the polymer1The structure-W, and thus the higher the molecular weight, the lower the melt index, the higher the melt strength, and the higher the mechanical strength. Compared with the conventional PLA blending material in the prior art, the problem of the compatibility of the polymer and the blending phase when in use is not needed to be worried about, and the stability is improved.
The invention also provides a preparation method of the copolymer material for the laminating film, which comprises the following steps: feeding polyglycolide, a structure regulator and an additive into an extruder, and extruding and granulating to obtain the copolymer material;
wherein the structure regulator is selected from the group consisting of compounds having i-R1-j, wherein i and j are each selected from one of isocyanate group (-N ═ C ═ O), acid chloride group, oxazoline group, acid anhydride, epoxy group or amine group;
the additive is selected from one or more of an antioxidant, a metal deactivator, an end capping agent, a nucleating agent, an acid scavenger, a heat stabilizer, a UV stabilizer, a lubricating plasticizer or a crosslinking agent.
The mass fractions of the structure regulator and the additive are 0.01-5%, preferably 0.01-3%, and more preferably 0.01-1%.
The structure regulator is selected from one or more of polyisocyanates, acrylates, organic peroxides, polyols, polybasic acids and polyamine compounds;
polyisocyanates such as JQ-1, JQ-1E, JQ-2E, JQ-3E, JQ-4, JQ-5, JQ-6, emulsifiable MDI, tetraisocyanate; the acrylic esters are exemplified by 1, 4-butylene glycol diacrylate, ethylene glycol dimethacrylate, butyl acrylate, etc.; the organic peroxide is selected from dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide and the like; examples of the polyhydric alcohol, polybasic acid and polyamine compounds include hexahydrophthalic anhydride, triethylenetetramine, dimethylaminopropylamine, diethylaminopropylamine, propylenediamine, polyethylene glycol, polypropylene glycol and trimethylolpropane.
More specifically, the present invention is to provide a novel,
the antioxidant is selected from one or more of the following products: BASF Irganox 168, BASF Irganox 101, BASF Irganox 245, BASF Irganox 1024, BASF Irganox 1076, BASF Irganox1098, BASF Irganox 3114, BASF Irganox MD 1024, BASF Irganox MD 1025, ADEKA AO-60, ADEKA AO-80, STAB PEP-36, STAB8T, Albemarle AT-10, Albemarle AT-245, Albemarle AT-330, Albemarle AT-626, Albemarle AT-702, Albemarle AT-733, Albemarle AT-816, Albemarle AT-1135;
the metal passivator is selected from one or more of oxalic acid derivatives, hydrazine compounds, salicylic acid derivatives, benzotriazole compounds or guanidine compounds; preferably one or more of the following models: BASF Chem-180, Eastman OABH, Naugard XL-1, Naugard MD24, ADEKA STAB CDA-1 or ADEKA STAB CDA-16;
the blocking agent is selected from one or more of hydroxyl, carboxyl, amino, ester group, isocyanate group, silane group, acyl chloride, oxazoline group, acid anhydride or epoxy group;
the nucleating agent is selected from one or more of talc powder, calcium oxide, carbon black, calcium carbonate, mica, sodium succinate, glutarate, sodium caproate, sodium 4-methylvalerate, adipate, tert-butyl aluminum benzoate (Al-PTB-BA), aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate, carboxylic acid metal salts such as sodium beta-naphthoate and the like, and sorbierite derivatives such as dibenzylidene sorbitol (DBS), di (P-methyl benzylidene) sorbitol (P-M-DBS) or di (P-chloro substituted benzylidene) sorbitol (P-Cl-DBS) and the like; preferably one or more of the following models: surlyn 9020, Surlyn1601, Surlyn1605, Surlyn1650, Surlyn1652, Surlyn1702, Surlyn1705, Surlyn8920, Surlyn8940, Surlyn pc-350, Surlyn pc-2000;
the acid scavenger is selected from one or more of calcium stearate, calcium lactate, hydrotalcite, zinc oxide, magnesium oxide or aluminum oxide;
the heat stabilizer is selected from one or more of lead salt heat stabilizer, metal soap heat stabilizer, organic tin heat stabilizer or rare earth heat stabilizer;
among them, examples of the lead salt-based heat stabilizer are tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, and basic lead carbonate; examples of the metal soap heat stabilizer include zinc stearate, calcium stearate, magnesium stearate, etc.; examples of the organotin-based heat stabilizer include sulfur-containing organotins, organotin carboxylates, and the like;
the ultraviolet stabilizer is selected from one or more of triazine, phentriazine, diphenyl acetone, salicylate and acetonitrile; specific product models are exemplified by UV944, UV770, UV783, UV622, UV531, UV326, UV327, UV292, UV123 and the like;
the lubricant is selected from one or more of saturated hydrocarbons, metal soaps, aliphatic amides, fatty acids, fatty acid esters or fatty alcohols; saturated hydrocarbon lubricants such as paraffin wax, liquid paraffin wax, microcrystalline wax, low molecular weight polyethylene, and the like; metallic soap lubricants are exemplified by zinc stearate, calcium stearate or magnesium stearate; aliphatic amides such as EBS, oleamide and the like; fatty acids such as stearic acid, hydroxystearic acid; fatty acid esters such as PETS, glyceryl monostearate, glyceryl polystearate, etc.; fatty alcohols are exemplified by stearyl alcohol, pentaerythritol, and the like;
the preparation method of the polyglycolide comprises the following steps:
(1) putting glycolide and a ring-opening catalyst into a prefabricated reactor, uniformly mixing, and carrying out prepolymerization reaction at the temperature of 80-160 ℃ for no more than 120 min;
(2) adding the material obtained in the step (1) into a plug flow reactor, and carrying out polymerization reaction at the temperature of 120-280 ℃ for 1 min-72 h;
(3) adding the material obtained in the step (2) into a devolatilization reactor, and performing polymer devolatilization under the conditions of 160-280 ℃ and absolute pressure not exceeding 5000Pa, wherein the reaction time is 1 minute-24 hours.
The ring-opening catalyst is selected from one or more of rare earth elements, rare earth element oxides, metal magnesium compounds, alkali metal chelates and organic guanidine catalysts, and the addition amount of the ring-opening catalyst is 5-0.01% of the mass of the glycolide, preferably 5-0.1%, and more preferably 3-1%.
The extruder is a double-screw extruder, and the extrusion temperature is 200-300 ℃, preferably 230-280 ℃, and more preferably 240-270 ℃.
The form of the plug flow reactor includes, but is not limited to, a static mixer, a twin-screw unit, a horizontal disc reactor, and the like.
The invention also provides a laminated product prepared from the copolymer material, which comprises base paper and a laminated layer prepared from the copolymer material; the tensile modulus of the PE-coated layer is more than 5800MPa, preferably more than 6000MPa, and more preferably more than 6500 MPa; the tensile strength of the laminated layer is 90MPa or more, preferably 100MPa or more, and more preferably 110MPa or more.
Compared with the prior art, the invention has the following advantages:
(1) the copolymer material is a novel polyglycolide material, can be quickly and completely degraded, is green and harmless, and meets the requirement of green environmental protection;
(2) the mechanical properties such as mechanical strength, toughness and the like are excellent, the tensile strength and tensile modulus are high, and the quality is reliable;
(3) the stability is good, and the polymer material has better thermal melting stability and hydrolytic stability;
(4) the polymer material has the advantages of simple preparation process, easy implementation and low production cost, and only reduces the preparation cost of the laminating paper.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention relates to a copolymer material for a laminating film, which comprises one or more than one of C- (A)x-By)n-a polymer of structure D;
(1) a is selected from
Figure BDA0002209541190000051
One or more of the structures;
(2) the molecular structural formula of B is G-R1-W, wherein G and W are selected from-CO-NH-, -CO-R2-CO-OH，-CO-，-(CH2)2NH-CO-，-CH2-CH(OH)-CH2-or-NH; wherein R is1Is a copolymerization structure formed by aliphatic groups, aromatic groups or aliphatic or aromatic groups, R2Is alkyl, aryl or alkenyl;
(3) x is 1-1500, y is 1-1500, and n is 1-10000;
(4) c and D are end groups, and are selected from one or more of hydroxyl, carboxyl, amino, alkyl, aryl, ether, alkylene or halogenated hydrocarbon groups.
The copolymer material prepared by the invention has the weight-average molecular weight of 10000-1000000 and the ratio (Mw/Mn) of the weight-average molecular weight to the number-average molecular weight of 1-10, preferably 1.2-8, and more preferably 1.5-5.
The melt index (MFR) of the copolymer material is from 0.1 to 1000g/10min, preferably from 0.15 to 500g/10min, more preferably from 0.2 to 100g/10 min.
The preparation method of the copolymer material for the laminating film comprises the following steps:
(1) preparation of polyglycolide
(1-1) putting glycolide and a ring-opening catalyst into a prefabricated reactor, uniformly mixing, and carrying out prepolymerization reaction at the temperature of 80-160 ℃ for no more than 120 min; the ring-opening catalyst can be one or more of rare earth elements, rare earth element oxides, metal magnesium compounds, alkali metal chelates and organic guanidine catalysts, and the addition amount of the ring-opening catalyst is 5-0.01 percent, preferably 5-0.1 percent and more preferably 3-1 percent of the mass of the glycolide;
(1-2) adding the material obtained in the step (1-1) into a plug flow reactor, and carrying out polymerization reaction at the temperature of 120 ℃ and 280 ℃ for 1 minute to 72 hours; the form of the plug flow reactor includes, but is not limited to, a static mixer, a twin-screw unit, a horizontal disc reactor, and the like.
(1-3) adding the material obtained in the step (1-2) into a devolatilization reactor, and performing polymer devolatilization under the conditions of 160 ℃ and 280 ℃ and the absolute pressure of not more than 5000Pa, wherein the reaction time is 1 minute to 24 hours.
(2) Extrusion granulation
And (3) feeding the polyglycolide, the structure regulator and the additive prepared by the preparation method into an extruder, and extruding and granulating to obtain the copolymer material.
Wherein,
the extruder is a double-screw extruder, and the extrusion temperature is 200-300 ℃, preferably 230-280 ℃, and more preferably 240-270 ℃.
The mass fractions of the structure regulator and the additive are both 0.01-5%, preferably 0.01-3%, and more preferably 0.01-1%.
The structure regulator is selected from the group consisting of compounds having i-R1-j, wherein i and j are each selected from one of isocyanate group (-N ═ C ═ O), acid chloride group, oxazoline group, acid anhydride, epoxy group or amine group; can be selected from polyisocyanates such as JQ-1, JQ-1E, JQ-2E, JQ-3E, JQ-4, JQ-5, JQ-6, emulsifiable MDI, tetraisocyanate, etc., acrylates such as 1, 4-butanediol diacrylate, ethylene glycol dimethacrylate, butyl acrylate, etcAnd one or more of organic peroxides such as dicumyl peroxide, benzoyl peroxide and di-tert-butyl peroxide, polyhydric alcohols, polybasic acids and polyamine compounds such as hexahydrophthalic anhydride, triethylenetetramine, dimethylaminopropylamine, diethylaminopropylamine, propylenediamine, polyethylene glycol, polypropylene glycol and trimethylolpropane.
The additive is selected from one or more of an antioxidant, a metal deactivator, an end capping agent, a nucleating agent, an acid scavenger, a heat stabilizer, an ultraviolet stabilizer, a lubricating plasticizer or a crosslinking agent;
more specifically, the present invention is to provide a novel,
antioxidant agent
One or more antioxidants selected from the group consisting of commercial products such as BASF Irganox 168, BASF Irganox 101, BASF Irganox 245, BASF Irganox 1024, BASF Irganox 1076, BASF Irganox1098, BASF Irganox 3114, BASF Irganox MD 1024, BASF Irganox MD 1025, ADEKA AO-60, ADEKA AO-80, STAB PEP-36, STAB8T, Albemarle AT-10, Albemarle AT-245, Albemarle AT-330, Albemarle AT-626, Albemarle AT-702, Albemarle AT-733, Albemarle AT-816, and Albemarle AT-1135.
Metal passivator
Can be selected from one or more of oxalic acid derivatives such as BASF Chem-180, Eastman OABH, Naugard XL-1, Naugard MD24, ADEKASTAB CDA-1, and ADEKA STAB CDA-16, hydrazine compounds, salicylic acid derivatives, benzotriazole compounds, guanidine compounds, etc.
End-capping agents
May be selected from one or more of monofunctional hydroxyl, carboxyl, amino, ester, isocyanate, silane, acid chloride, oxazoline, anhydride, epoxy, and the like.
Nucleating agent
One or more selected from talc, calcium oxide, carbon black, calcium carbonate, mica, sodium succinate, glutarate, sodium caproate, sodium 4-methylpentanoate, adipate, aluminum tert-butylbenzoate (Al-PTB-BA), aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate, sodium β -naphthoate and other metal carboxylates, dibenzylidene sorbitol (DBS), bis (P-methylbenzylidene) sorbitol (P-M-DBS), bis (P-chloro substituted benzylidene) sorbitol (P-Cl-DBS) and other sorbitol benzylidene derivatives, Surlyn 9020, Surlyn1601, Surlyn1605, Surlyn1650, Surlyn1652, Surlyn1702, Surlyn1705, Surlyn8920, Surlyn8940, Surlyn PC-350, Surlyn PC-2000 and the like.
Acid scavenger
Can be selected from one or more of metal stearate or lactate such as calcium stearate and calcium lactate, hydrotalcite, zinc oxide magnesium oxide, and aluminum oxide.
Heat stabilizer
Can be selected from lead salt heat stabilizer (tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, basic lead carbonate, etc.); metal soap heat stabilizers (zinc stearate, calcium stearate, magnesium stearate, etc.); organotin heat stabilizers (sulfur-containing organotin compounds, organotin carboxylates, etc.); rare earth heat stabilizer, etc.
Ultraviolet stabilizer
Can be selected from one or more of triazine, benzotriazine, diphenyl acetone, salicylate and acetonitrile such as UV944, UV770, UV783, UV622, UV531, UV326, UV327, UV292 and UV 123.
Lubricant agent
It may be selected from one or more of saturated hydrocarbons (paraffin wax, liquid paraffin, microcrystalline wax, low molecular weight polyethylene, etc.), metal soaps (zinc stearate, calcium stearate, magnesium stearate, etc.), fatty acid amides (EBS, oleamide, etc.), fatty acids (stearic acid, hydroxystearic acid), fatty acid esters (PETS, glyceryl monostearate, glyceryl polystearate, etc.), and fatty alcohols (stearyl alcohol, pentaerythritol, etc.).
(3) Injection molded into test bars and tested
Drying the particles obtained by granulation of the extruder for 4 hours at 120 ℃, putting the particles into an injection molding machine, and performing performance test by injection molding into sample strips at the conditions of the injection molding temperature of 250 ℃ and the mold temperature of 100 ℃.
The test contents comprise a tensile modulus and strength test, a melt index test and a degradation performance test.
Tensile modulus and Strength test
The test is carried out according to the test standard of GB/T10401-2006, and the stretching speed is 50 mm/min.
Melt index test
The melt index was measured according to GB/T3682 at 230 ℃ and a weight of 2.16 kg.
Test for degradation Properties
Taking 5g of polymer, and degrading the polymer in 250ml of deionized water by shaking at 65 ℃ (60 r/min); after 7 days, samples were taken, dried at 30 ℃ under vacuum to constant weight, and the residual mass was determined.
The laminated product prepared by the copolymer material comprises base paper and a laminated layer prepared by the copolymer material; the tensile modulus of the laminated film layer is more than 5800MPa, preferably more than 6000MPa, and more preferably more than 6500 MPa; the tensile strength of the laminated film layer is 90MPa or more, preferably 100MPa or more, and more preferably 110MPa or more.
The following is a specific embodiment of the present invention.
Comparative example 1
Feeding polylactic acid (PLA), an antioxidant STAB PEP-36 with the mass fraction of 0.03% and a metal deactivator Chem-180 with the mass fraction of 0.06% into an extruder, extruding and granulating to obtain the laminating material of the comparative example 1, and performing performance tests, wherein the results are listed in Table 1.
Comparative example 2
And (3) feeding polybutylene succinate (PBS), an antioxidant STAB PEP-36 with the mass fraction of 0.03% and a metal passivator Chem-180 with the mass fraction of 0.06% into an extruder, extruding and granulating to obtain the laminating material of the comparative example 1, and performing performance tests, wherein the results are listed in Table 1.
Example 1
This example is the preparation of polyglycolide, the steps of the preparation method are:
(1) uniformly mixing glycolide, a ring-opening polymerization catalyst with the addition amount of 0.01 part of the mass of the added glycolide, dihydrate and tin dichloride in a prefabricated kettle type reactor at 120 ℃, and carrying out prepolymerization reaction for 60 min;
(2) feeding the materials of the prefabricated kettle type reaction kettle into a polymerization reactor, and reacting for 300min at 200 ℃ under the absolute pressure condition of 0.1MPa, wherein the polymerization reactor is a plug flow reactor, in particular a static mixer;
(3) and (3) putting the materials in the polymerization reactor into a devolatilization reactor, and reacting at 220 ℃, at a mixing speed of 200RPM, an absolute pressure of 50Pa and a reaction time of 30min to obtain the polyglycolide.
Example 2
This example is to further prepare polyglycolic acid composite for laminating products, i.e. copolymer material in the present invention, by using polyglycolide prepared in example 1.
The preparation method comprises the following specific steps:
putting the polyglycolide polymer obtained in the example 1, an antioxidant STAB PEP-36 with the mass fraction of 0.03%, a metal passivator Chel-180 with the mass fraction of 0.06% and a structure regulator ECN1299 (cresol formaldehyde epoxy resin) with the mass fraction of 0.5% into a double-screw extruder for granulation, wherein the extrusion temperature is 250 ℃; the pellets were dried at 120 ℃ for 4 hours, placed in an injection molding machine, injection-molded at 250 ℃ and a mold temperature of 100 ℃ and injection-molded into sample bars for testing, and the results are shown in Table 1.
Example 3
This example is to further prepare polyglycolic acid composite for laminating products, i.e. copolymer material in the present invention, by using polyglycolide prepared in example 1.
The procedure of this example was different from the procedure of example 2 in that the structural regulator was 1% by mass and the structural regulator was EPOCROS RPS1005 (oxazoline compound), and the test results of the polymer obtained in this example are shown in Table 1.
TABLE 1 Performance test data for examples 2-3 and comparative examples 1-2
Figure BDA0002209541190000101
The MFR after extrusion pelletization reflects the melt thermal stability of the polymer, the higher the MFR after pelletization, the worse the melt thermal stability, as can be seen from Table 1, the lower the MFR values of examples 2 and 3, the higher the melt thermal stability, compared to PLA and PBS; as can be seen from relevant tensile test data, the tensile strength and the tensile modulus of the invention are much higher than those of PLA and PBS, which shows that the mechanical properties such as mechanical strength, toughness and the like are excellent; as can be seen from degradation experiments, degradation data also show that the hydrolysis stability of the invention is better, and the coating film of the invention has degradability and meets the requirements of environmental protection.
Example 4
This example is the preparation of polyglycolide, the steps of the preparation method are:
(1) uniformly mixing glycolide, a ring-opening polymerization catalyst with the addition amount of 5% of the mass of the added glycolide, dihydrate and tin dichloride in a prefabricated kettle type reactor at 80 ℃, and carrying out prepolymerization reaction for 120 min;
(2) feeding the materials of the prefabricated kettle type reaction kettle into a polymerization reactor, and reacting for 72 hours at 120 ℃ under the absolute pressure condition of 0.1MPa, wherein the polymerization reactor is a plug flow reactor, in particular to a horizontal disc reactor;
(3) and (3) putting the materials in the polymerization reactor into a devolatilization reactor, and reacting for 24 hours at 160 ℃, at the mixing speed of 200RPM and the absolute pressure of 5000Pa to obtain the polyglycolide.
Example 5
This example is the preparation of polyglycolide, the steps of the preparation method are:
(1) uniformly mixing glycolide, a ring-opening polymerization catalyst with the addition amount of 1% of the mass of the added glycolide, dihydrate and tin dichloride in a prefabricated kettle type reactor at 160 ℃, and carrying out prepolymerization reaction for 60 min;
(2) feeding the materials of the prefabricated kettle type reaction kettle into a polymerization reactor, and reacting for 1 minute at 280 ℃ under the absolute pressure condition of 0.1MPa, wherein the polymerization reactor is a plug flow reactor, in particular a double-screw unit;
(3) and (3) putting the materials in the polymerization reactor into a devolatilization reactor, and reacting for 1min at the temperature of 280 ℃, at the mixing speed of 200RPM and the absolute pressure of 5000Pa to obtain the polyglycolide.
Example 6
This example is to further prepare polyglycolic acid composite for laminating products, i.e. copolymer material in the present invention, by using polyglycolide prepared in example 1.
The preparation method comprises the following specific steps:
putting the polyglycolide polymer obtained in the example 1, an antioxidant STAB PEP-36 with the mass fraction of 0.03%, a metal passivator Chel-180 with the mass fraction of 0.06%, a capping agent with the mass fraction of 0.1%, a nucleating agent with the mass fraction of 0.11%, an acid scavenger with the mass fraction of 0.1%, a heat stabilizer with the mass fraction of 0.1% and an organic peroxide structure regulator with the mass fraction of 5% into a double-screw extruder for granulation, and extruding at the temperature of 300 ℃ to obtain a copolymer material.
Example 7
This example is to further prepare polyglycolic acid composite for laminating products, i.e. copolymer material in the present invention, by using polyglycolide prepared in example 1.
The preparation method comprises the following specific steps:
and (2) putting the polyglycolide polymer obtained in the example 1, an antioxidant STAB PEP-36 with the mass fraction of 0.005%, a metal passivator Chel-180 with the mass fraction of 0.05% and a polybasic acid type structure regulator with the mass fraction of 0.01% into a double-screw extruder for granulation, wherein the extrusion temperature is 200 ℃, and thus obtaining the copolymer material.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (10)

1. A copolymer material for laminating film is composed of one or more of C- (A)x-By)n-a polymer of structure D;
it is characterized in that the preparation method is characterized in that,
a is selected from
Figure FDA0002209541180000011
One or more of the structures;
the molecular structural formula of B is G-R1-W, wherein G and W are selected from-CO-NH-, -CO-R2-CO-OH，-CO-，-(CH2)2NH-CO-，-CH2-CH(OH)-CH2-or-NH; wherein R is1Is a copolymerization structure formed by aliphatic groups, aromatic groups or aliphatic or aromatic groups, R2Is alkyl, aryl or alkenyl;
x is 1-1500, y is 1-1500, and n is 1-10000;
c and D are end groups, and are selected from one or more of hydroxyl, carboxyl, amino, alkyl, aryl, ether, alkylene or halogenated hydrocarbon groups.
2. The copolymer material for curtain coating as claimed in claim 1, wherein the weight average molecular weight of the copolymer material is 10000-1000000, and the ratio of the weight average molecular weight to the number average molecular weight is 1-10, preferably 1.2-8, and more preferably 1.5-5.
3. The copolymer material for the curtain coating film as claimed in claim 1, wherein the melt index of the copolymer material is 0.1-1000g/10min, preferably 0.15-500g/10min, and more preferably 0.2-100g/10 min.
4. A method for preparing the copolymer material for the curtain coating as claimed in claim 1, comprising the steps of: feeding polyglycolide, a structure regulator and an additive into an extruder, and extruding and granulating to obtain the copolymer material; wherein the structure regulator is selected from the group consisting of compounds having i-R1One or more substances with a structure of j, wherein i and j are selected from one of isocyanate group, acyl chloride group, oxazoline group, acid anhydride, epoxy group or amine group; the additive is selected from antioxidant, metal deactivator, end capping agent, nucleating agent, acid scavenger, heat stabilizer, ultraviolet stabilizerOne or more of an agent, a lubricating plasticizer or a crosslinking agent.
5. The preparation method of the copolymer material for the curtain coating as claimed in claim 4, wherein the mass fractions of the structure regulator and the additive are 0.01-5%, preferably 0.01-3%, and more preferably 0.01-1%.
6. The preparation method of the copolymer material for the curtain coating as claimed in claim 4,
the antioxidant is selected from one or more of the following products: BASF Irganox 168, BASF Irganox 101, BASF Irganox 245, BASF Irganox 1024, BASF Irganox 1076, BASF Irganox1098, BASF Irganox 3114, BASF Irganox MD 1024, BASF Irganox MD 1025, ADEKA AO-60, ADEKA AO-80, STAB PEP-36, STAB8T, Albemarle AT-10, Albemarle AT-245, Albemarle AT-330, Albemarle AT-626, Albemarle AT-702, Albemarle AT-733, Albemarle AT-816, Albemarle AT-1135;
the metal passivator is selected from one or more of oxalic acid derivatives, hydrazine compounds, salicylic acid derivatives, benzotriazole compounds or guanidine compounds; preferably one or more of the following models: BASF Chem-180, Eastman OABH, Naugard XL-1, Naugard MD24, ADEKA STAB CDA-1 or ADEKA STAB CDA-16;
the blocking agent is selected from one or more of hydroxyl, carboxyl, amino, ester group, isocyanate group, silane group, acyl chloride, oxazoline group, acid anhydride or epoxy group;
the nucleating agent is selected from one or more of talcum powder, calcium oxide, carbon black, calcium carbonate, mica, sodium succinate, glutarate, sodium caproate, sodium 4-methylvalerate, adipate, tert-butyl aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate, sodium beta-sodium naphthalate and other metal carboxylates, dibenzylidene sorbitol, di (p-methyl benzylidene) sorbitol or di (p-chloro substituted benzylidene) sorbitol and other sorbierite derivatives; preferably one or more of the following models: surlyn 9020, Surlyn1601, Surlyn1605, Surlyn1650, Surlyn1652, Surlyn1702, Surlyn1705, Surlyn8920, Surlyn8940, Surlyn pc-350, Surlyn pc-2000;
the acid scavenger is selected from one or more of calcium stearate, calcium lactate, hydrotalcite, zinc oxide, magnesium oxide or aluminum oxide;
the heat stabilizer is selected from one or more of lead salt heat stabilizer, metal soap heat stabilizer, organic tin heat stabilizer or rare earth heat stabilizer;
the ultraviolet stabilizer is selected from one or more of triazine, phentriazine, diphenyl acetone, salicylate and acetonitrile;
the lubricant is selected from one or more of saturated hydrocarbons, metal soaps, aliphatic amides, fatty acids, fatty acid esters or fatty alcohols;
the structure regulator is selected from one or more of polyisocyanates, acrylates, organic peroxides, polyols, polybasic acids and polyamine compounds.
7. The method for preparing the copolymer material for the laminating film as claimed in claim 4, wherein the method for preparing the polyglycolide comprises:
(1) putting glycolide and a ring-opening catalyst into a prefabricated reactor, uniformly mixing, and carrying out prepolymerization reaction at the temperature of 80-160 ℃ for no more than 120 min;
(2) adding the material obtained in the step (1) into a plug flow reactor, and carrying out polymerization reaction at the temperature of 120-280 ℃ for 1 min-72 h;
(3) and (3) adding the material obtained in the step (2) into a devolatilization reactor, and performing polymer devolatilization at 160-280 ℃ under the absolute pressure of not more than 5000Pa, wherein the reaction time is 1 minute-24 hours.
8. The preparation method of the copolymer material for curtain coating as claimed in claim 7, wherein the ring-opening catalyst is selected from one or more of rare earth elements, rare earth element oxides, metal magnesium compounds, alkali metal chelates and organic guanidine catalysts, and the addition amount of the ring-opening catalyst is 5-0.01% by mass of glycolide, preferably 5-0.1%, and more preferably 3-1%.
9. The preparation method of the copolymer material for the lamination according to claim 4, wherein the extruder is a twin-screw extruder, and the extrusion temperature is 200-300 ℃, preferably 230-280 ℃, and more preferably 240-270 ℃.
10. A laminated article prepared from the copolymer material of claim 1, comprising a base paper and a laminated layer prepared from the copolymer material; the tensile modulus of the PE-coated layer is more than 5800MPa, preferably more than 6000MPa, and more preferably more than 6500 MPa; the tensile strength of the laminated layer is 90MPa or more, preferably 100MPa or more, and more preferably 110MPa or more.
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