WO2023236267A1 - Degradable bio-based moisture-permeable waterproof film and preparation method therefor - Google Patents
Degradable bio-based moisture-permeable waterproof film and preparation method therefor Download PDFInfo
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- WO2023236267A1 WO2023236267A1 PCT/CN2022/101260 CN2022101260W WO2023236267A1 WO 2023236267 A1 WO2023236267 A1 WO 2023236267A1 CN 2022101260 W CN2022101260 W CN 2022101260W WO 2023236267 A1 WO2023236267 A1 WO 2023236267A1
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- WIPO (PCT)
- Prior art keywords
- parts
- permeable waterproof
- agent
- waterproof membrane
- based moisture
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 238000004383 yellowing Methods 0.000 claims abstract description 26
- 239000004970 Chain extender Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 19
- 239000004626 polylactic acid Substances 0.000 claims abstract description 19
- IYKFYARMMIESOX-SPJNRGJMSA-N adamantanone Chemical compound C([C@H](C1)C2)[C@H]3C[C@@H]1C(=O)[C@@H]2C3 IYKFYARMMIESOX-SPJNRGJMSA-N 0.000 claims abstract description 4
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 46
- 238000005266 casting Methods 0.000 claims description 32
- -1 polymethylethylene carbonate Polymers 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 27
- 238000001125 extrusion Methods 0.000 claims description 23
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 238000004078 waterproofing Methods 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- QVRCRSYOVMLBKS-UHFFFAOYSA-N 5-hydroperoxy-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound CC1CCC2C(C)(C)C1(OO)C2 QVRCRSYOVMLBKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 230000003487 anti-permeability effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims 2
- NOVBFCUKZQSNBX-UHFFFAOYSA-N OO.CC(C)O Chemical compound OO.CC(C)O NOVBFCUKZQSNBX-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000181 anti-adherent effect Effects 0.000 description 6
- 230000036760 body temperature Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FRQPHGSNRQEKOX-UHFFFAOYSA-N 6h-benzo[c][1,2]benzoxazine Chemical group C1=CC=C2NOC3=CC=CC=C3C2=C1 FRQPHGSNRQEKOX-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000003972 cyclic carboxylic anhydrides Chemical class 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
Definitions
- the present invention relates to the technical field of moisture-permeable waterproof membranes, and in particular to a degradable bio-based moisture-permeable waterproof membrane and a preparation method thereof.
- a breathable waterproof membrane is a membrane that allows moisture vapor to pass through, but blocks the passage of liquid water molecules.
- Water vapor is water molecules in a gaseous state. Due to their very small size, water vapor can penetrate from one side of the moisture-permeable waterproof membrane to the other side through the principle of capillary phenomenon, thereby achieving the effect of water vapor (moisture vapor) permeability.
- moisture vapor moisture vapor
- the moisture-permeable waterproof membrane can have a waterproof effect.
- breathable waterproof membrane is to be attached to clothing products.
- the body temperature is too high, the body will regulate body temperature through the perspiration mechanism of the skin.
- sweat stays on the skin surface for a long time, it can easily cause discomfort and easily introduce bacteria.
- the use of breathable waterproof membrane can accelerate the removal of sweat from the skin surface to keep the skin surface dry.
- the moisture-permeable waterproof membrane can simultaneously prevent external liquid water molecules from passing through the moisture-permeable waterproof membrane and reaching the skin, thus having a waterproof effect.
- the moisture-permeable waterproof membranes on the market are mainly polymer compounds made of tetrafluoroethylene, which have excellent chemical stability and corrosion resistance.
- PTFE is not degradable and has poor environmental performance.
- one of the purposes of the present invention is to provide a degradable bio-based moisture-permeable waterproof membrane, which has biodegradability and can improve the environmental protection of the waterproof membrane.
- the second object of the present invention is to provide a method for preparing a degradable bio-based moisture-permeable waterproof membrane.
- a degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
- the hydrophilic anti-reflection agent is one or more of phenylpolyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF or PTMEG).
- PEO phenylpolyethylene oxide
- PPO polypropylene oxide
- PTHF polytetrahydrofuran
- PTMEG polytetrahydrofuran
- the chain extender is one or more of isocyanate, cyclic carboxylic acid anhydride, phosphate ester, and bicyclic imide ester.
- the isocyanate is one or more of hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate;
- the cyclic carboxylic anhydride is pyromellitic anhydride or trimellitic anhydride;
- the phosphate ester is triphenyl phosphite;
- the bicyclic imide ester is dibenzoxazine.
- the initiator is 2,5-dimethyln-hexane-2,5-dimethylhydroxyperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, terpene hydroperoxide, peroxide
- One or more of benzoyl hydrogen oxide and 2,6,6-trimethylbicyclo[3.1.1]heptyl hydroperoxide is one or more of benzoyl hydrogen oxide and 2,6,6-trimethylbicyclo[3.1.1]heptyl hydroperoxide.
- the compatibilizer is maleic anhydride grafted polyolefin (MAH-g-poe, MAH-g-PVOH), styrene-maleic anhydride copolymer (SMA), glycidyl methacrylate grafted One or more than two types of polyolefin copolymers (GMA-g-PVOH).
- the anti-yellowing agent is a hindered phenolic ultraviolet absorber; the anti-yellowing agent destroys the molecular structure of the material by absorbing the energy of destructive ultraviolet rays in sunlight, thereby causing deterioration of the physical properties and color of the material.
- the anti-yellowing agent is light stabilizer 770, light stabilizer 622 or light stabilizer 944.
- the slippery anti-sticking agent is one or more of erucamide, stearic acid amide, oleic acid amide, palmitamide, nano-silica, nano-talc, calcined kaolin, and nano-calcium carbonate.
- the smooth anti-adhesive agent forms a protective layer on the surface of the film by forming an organic and inorganic compound system to prevent the film from adhering to the metal roller.
- the slippery anti-sticking agent is a compound of erucamide and nanosilica with a mass ratio of 1:1.
- a method for preparing a degradable bio-based moisture-permeable waterproof membrane including the following preparation steps:
- the preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
- cylinder temperature is 150°C-200°C
- machine head temperature is 150°C-180°C
- extrusion and pelletizing to form 3-5mm balls or round cake-shaped small particles, and then further dehydrated , dry at 80°C-110°C until the moisture content is ⁇ 0.2% to obtain extrusion granulated blend particles;
- S2 Casting film Add the above blend particles into the extrusion casting machine, and cast the film into a film when the screw speed of the casting machine is 100-200r/min and the cylinder temperature is 160°C-200°C.
- the temperature of the first section of the casting roller is 0°C-10°C, and the other rollers are at normal temperature, resulting in a degradable bio-based moisture-permeable waterproof membrane with a thickness of 0.01-0.05mm and a width of 0.4-1.5m.
- the biodegradable bio-based moisture-permeable waterproof membrane of the present invention uses degradable materials such as polymethylethylene carbonate and polylactic acid as the main base material. Diene, chain extender, initiator, compatibilizer, anti-yellowing agent and slippery anti-adhesive agent make it have good moisture permeability and waterproof performance.
- the hydrophilic anti-permeability agent enhances the waterproof performance of the system
- the diamond Alkanone and tetrahydrodipolycyclopentadiene introduce a cyclic structure into the system to enhance the moisture permeability of the system, so that the system has moisture permeability and waterproof properties on the basis of better moisture permeability and waterproofing, making it environmentally friendly Effect.
- the hydrophilic antireflection agent is polytetrahydrofuran; the chain extender is hexamethylene diisocyanate; the initiator is 2,5-dimethyln-hexane-2,5-dimethylhydroxyperoxide; the compatibilizer is Styrene-maleic anhydride copolymer; anti-yellowing agent is light stabilizer 770; smooth anti-sticking agent is a compound of erucamide and nano-silica with a mass ratio of 1:1.
- a degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
- polymethylethylene carbonate 20 parts of polylactic acid; 3 parts of hydrophilic antireflection agent; 0.1 part of adamantane; 0.1 part of tetrahydrodipolycyclopentadiene; 1 part of chain extender; 0.1 part of initiator ; 3 parts of compatibilizer; 0.5 parts of anti-yellowing agent; 1.5 parts of smooth and anti-adhesive agent.
- the preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
- a degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
- the preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
- a degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
- polymethylethylene carbonate 50 parts of polymethylethylene carbonate; 30 parts of polylactic acid; 10 parts of hydrophilic antireflection agent; 1 part of adamantane; 1 part of tetrahydrodipolycyclopentadiene; 5 parts of chain extender; 1 part of initiator ; 10 parts of compatibilizer; 5 parts of anti-yellowing agent; 10 parts of smooth and anti-adhesive agent.
- the preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
- a degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
- the preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
- mixing and granulating weigh polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, chain extender, initiator, compatibilizer, anti-yellowing agent and slippery anti-sticking agent in proportion Afterwards, stir for 3 minutes in a high-speed mixer with a speed of 60r/min, and then pass through the feeding hopper into a twin-screw underwater granulator at a speed of 100r/min, a cylinder temperature of 200°C, and a machine head temperature of 150°C. Extrusion and granulation to form 3-5mm ball or round cake-shaped small particles, and then further dehydrated, dried at 110°C until the moisture content is ⁇ 0.2%, to obtain extrusion granulated blend particles;
- a degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
- the preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
- mixing and granulation weigh the polymethylethylene carbonate, polylactic acid, compatibilizer, anti-yellowing agent and smooth anti-sticking agent in proportion, and stir for 3 minutes in a high-speed mixer with a speed of 60r/min. , and then extruded and cut into 3-5mm balls or The round cake-shaped small particles are further dehydrated and dried at 110°C until the moisture content is ⁇ 0.2% to obtain extrusion granulated blend particles;
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A degradable bio-based moisture-permeable waterproof film and a preparation method therefor. The moisture-permeable waterproof film comprises 30-50 parts of polymethyl ethylene carbonate; 20-30 parts of polylactic acid; 3-10 parts of a hydrophilic anti-reflection agent; 0.1-1 part of adamantanone; 0.1-1 part of tetrahydrodicyclopentadiene; 1-5 parts of a chain extender; 0.1-1 part of an initiator; 3-10 parts of a compatibilizer; 0.5-5 parts of an anti-yellowing agent; and 1.5-10 parts of a smooth anti-sticking agent. The degradable bio-based moisture-permeable waterproof film uses degradable materials such as the polymethyl ethylene carbonate and the polylactic acid as main base materials, the hydrophilic anti-reflection agent enhances the waterproofness properties of a system, and the adamantanone and the tetrahydrodicyclopentadiene introduce a cyclic structure into the system to enhance the moisture permeability of the system, so that the system has the moisture permeability and waterproofness properties on the basis of good moisture permeability and waterproofness, and the system has an environmentally friendly effect.
Description
本发明涉及透湿防水膜技术领域，尤其涉及一种可降解生物基透湿防水膜及其制备方法。The present invention relates to the technical field of moisture-permeable waterproof membranes, and in particular to a degradable bio-based moisture-permeable waterproof membrane and a preparation method thereof.
透湿防水膜是一种可允许水气通过，但会阻挡液体水分子通过的薄膜。水气为气体状态的水分子，由于体积非常细小，可藉由毛细现象原理，由透湿防水膜的一侧渗透至另一侧，从而达到透水气(湿气)的效果。然而，一旦水气凝结成液体水分子，在表面张力以及内聚力的共同作用下，液体水分子会倾向聚集形成一体积较大的分子团，进而无法由透湿防水膜的一侧穿过至另一侧，因此，透湿防水膜可具有防水的效果。A breathable waterproof membrane is a membrane that allows moisture vapor to pass through, but blocks the passage of liquid water molecules. Water vapor is water molecules in a gaseous state. Due to their very small size, water vapor can penetrate from one side of the moisture-permeable waterproof membrane to the other side through the principle of capillary phenomenon, thereby achieving the effect of water vapor (moisture vapor) permeability. However, once water vapor condenses into liquid water molecules, under the combined action of surface tension and cohesive force, the liquid water molecules will tend to aggregate to form a larger molecular cluster, which will then be unable to pass from one side of the breathable waterproof membrane to the other. On one side, therefore, the moisture-permeable waterproof membrane can have a waterproof effect.
透湿防水膜的其中一种应用为贴附于衣物产品上。当人体温度过高时，人体会通过皮肤的排汗机制达到调节体温的效果。然而，汗水长时间停留在皮肤表面时，容易导致不适并容易衍生细菌。而透湿防水膜的使用可加速排除皮肤表面的汗水，以维持皮肤表面的干爽。并且，透湿防水膜可同步防止外界的液体水分子穿过透湿防水膜达到皮肤，而具有防水的效果。One application of breathable waterproof membrane is to be attached to clothing products. When the body temperature is too high, the body will regulate body temperature through the perspiration mechanism of the skin. However, when sweat stays on the skin surface for a long time, it can easily cause discomfort and easily introduce bacteria. The use of breathable waterproof membrane can accelerate the removal of sweat from the skin surface to keep the skin surface dry. Moreover, the moisture-permeable waterproof membrane can simultaneously prevent external liquid water molecules from passing through the moisture-permeable waterproof membrane and reaching the skin, thus having a waterproof effect.
目前，市面上的透湿防水膜主要由四氟乙烯经聚合而成的高分子化合物，具有优良的化学稳定性、耐腐蚀性，但聚四氟乙烯不具备降解性，环保性能较差。At present, the moisture-permeable waterproof membranes on the market are mainly polymer compounds made of tetrafluoroethylene, which have excellent chemical stability and corrosion resistance. However, PTFE is not degradable and has poor environmental performance.
发明内容Contents of the invention
为了克服现有技术的不足，本发明目的之一在于提供一种可降解生物基透湿防水膜，其具有生物降解性能，能够提高防水膜的环保性。In order to overcome the shortcomings of the existing technology, one of the purposes of the present invention is to provide a degradable bio-based moisture-permeable waterproof membrane, which has biodegradability and can improve the environmental protection of the waterproof membrane.
本发明目的之二在于提供一种可降解生物基透湿防水膜的制备方法。The second object of the present invention is to provide a method for preparing a degradable bio-based moisture-permeable waterproof membrane.
本发明目的之一采用如下技术方案实现：One of the objectives of the present invention is achieved by adopting the following technical solutions:
一种可降解生物基透湿防水膜，包括如下重量份的组分：A degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
聚甲基乙撑碳酸酯30份-50份；聚乳酸20份-30份；亲水增透剂3份-10份；金刚烷酮0.1份-1份；四氢二聚环戊二烯0.1份-1份；扩链剂1份-5份；引发剂0.1份-1份；相容剂3份-10份；抗黄变剂0.5份-5份；爽滑抗粘剂1.5份-10份。30 parts to 50 parts of polymethylethylene carbonate; 20 parts to 30 parts of polylactic acid; 3 parts to 10 parts of hydrophilic antireflection agent; 0.1 part to 1 part of adamantanone; 0.1 part of tetrahydrodicyclopentadiene part-1 part; chain extender 1 part-5 parts; initiator 0.1 part-1 part; compatibilizer 3 parts-10 parts; anti-yellowing agent 0.5 part-5 parts; smooth anti-sticking agent 1.5 parts-10 parts share.
进一步地，所述亲水增透剂为苯聚环氧乙烷(PEO)、聚环氧丙烷(PPO)、聚四氢呋喃(PTHF或PTMEG)中的一种或两种以上。亲水增透剂为预聚体环氧类化合物，能进一步提高材料的透气性。Further, the hydrophilic anti-reflection agent is one or more of phenylpolyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF or PTMEG). The hydrophilic anti-reflection agent is a prepolymer epoxy compound, which can further improve the breathability of the material.
优选地，所述扩链剂为异氰酸酯、环状羧酸酐、磷酸酯、双环亚胺酯中的一种或两种以上。Preferably, the chain extender is one or more of isocyanate, cyclic carboxylic acid anhydride, phosphate ester, and bicyclic imide ester.
进一步优选地，所述异氰酸酯为六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或两种以上；所述环状羧酸酐为均苯四甲酸酐或偏苯三酸酐；所述磷酸酯为亚磷酸三苯酯；所述双环亚胺酯为双苯并噁嗪。Further preferably, the isocyanate is one or more of hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate; the cyclic carboxylic anhydride is pyromellitic anhydride or trimellitic anhydride; The phosphate ester is triphenyl phosphite; the bicyclic imide ester is dibenzoxazine.
优选地，所述引发剂为2,5-二甲基正己烷-2,5-二甲羟基过氧化物、过氧化氢异丙苯、叔丁基过氧化氢、萜烷过氧化氢、过氧化氢苯甲酰、2,6,6-三甲基二环[3.1.1]庚烷基氢过氧化物中的一种或两种以上。Preferably, the initiator is 2,5-dimethyln-hexane-2,5-dimethylhydroxyperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, terpene hydroperoxide, peroxide One or more of benzoyl hydrogen oxide and 2,6,6-trimethylbicyclo[3.1.1]heptyl hydroperoxide.
进一步地，所述相容剂为马来酸酐接枝聚烯烃(MAH-g-poe、MAH-g-PVOH)、苯乙烯-马来酸酐共聚物(SMA)、甲基丙烯酸缩水甘油酯接枝聚烯烃共聚物(GMA-g-PVOH)中的一种或两种以上。Further, the compatibilizer is maleic anhydride grafted polyolefin (MAH-g-poe, MAH-g-PVOH), styrene-maleic anhydride copolymer (SMA), glycidyl methacrylate grafted One or more than two types of polyolefin copolymers (GMA-g-PVOH).
进一步地，所述抗黄变剂为受阻酚类紫外线吸收剂；抗黄变剂通过吸收阳光中的破坏性紫外光线的能量对材料分子结构的破坏从而引起材料的物性和颜色的劣化。优选地，抗黄变剂为光稳定剂770、光稳定剂622或光稳定剂944。Furthermore, the anti-yellowing agent is a hindered phenolic ultraviolet absorber; the anti-yellowing agent destroys the molecular structure of the material by absorbing the energy of destructive ultraviolet rays in sunlight, thereby causing deterioration of the physical properties and color of the material. Preferably, the anti-yellowing agent is light stabilizer 770, light stabilizer 622 or light stabilizer 944.
进一步地，所述爽滑抗粘剂为芥酸酰胺、硬脂酸酰胺、油酸酰胺、棕榈酰胺、纳米二氧化硅、纳米滑石粉、煅烧高岭土、纳米碳酸钙中的一种或两种以上；爽滑抗粘剂通过组成有机和无机复配体系在薄膜的表层形成保护层，防止薄膜与金属辊轮的粘合。优选地，爽滑抗粘剂是质量比为1:1的芥酸酰胺和纳米二氧化硅的复配物。Further, the slippery anti-sticking agent is one or more of erucamide, stearic acid amide, oleic acid amide, palmitamide, nano-silica, nano-talc, calcined kaolin, and nano-calcium carbonate. ; The smooth anti-adhesive agent forms a protective layer on the surface of the film by forming an organic and inorganic compound system to prevent the film from adhering to the metal roller. Preferably, the slippery anti-sticking agent is a compound of erucamide and nanosilica with a mass ratio of 1:1.
本发明目的之二采用如下技术方案实现：The second object of the present invention is achieved by adopting the following technical solutions:
一种可降解生物基透湿防水膜的制备方法，包括如下制备步骤：A method for preparing a degradable bio-based moisture-permeable waterproof membrane, including the following preparation steps:
S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、亲水增透剂、金刚烷酮、四氢二聚环戊二烯、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在高速搅拌机中搅拌均匀，然后经过喂料斗在双螺杆水下的造粒机中，挤出切粒，形成圆球或圆饼状的小颗粒，再进一步地脱水后，烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulating: polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, adamantane, tetrahydrodipolycyclopentadiene, chain extender, initiator, compatibilizer, anti- After the yellowing agent and smooth anti-sticking agent are weighed in proportion, mix them evenly in a high-speed mixer, and then pass through the feeding hopper into a twin-screw underwater granulator, extrusion and granulation to form a ball or round cake. The small particles are further dehydrated and dried to a moisture content of ≤0.2% to obtain extrusion granulated blend particles;
S2，流延成膜：将上述共混物颗粒加入挤出流延机中，流延成膜，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting film formation: Add the above blend particles into an extrusion casting machine and cast them into a film to obtain a degradable bio-based moisture-permeable waterproofing film with a thickness of 0.01-0.05mm and a width of 0.4-1.5m.
优选地，该可降解生物基透湿防水膜的制备方法，包括如下制备步骤：Preferably, the preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、亲水增透剂、金刚烷酮、四氢二聚环戊二烯、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在转速60-80r/min的高速搅拌机中搅拌3-5min，然后经过喂料斗在双螺杆水下的造粒机中，在转速为100-300r/min、筒体温度为150℃-200℃、机头温度为150℃-180℃下挤出切粒，形成3-5mm的圆球或圆饼状的小颗粒，再进一步地脱水后，在80℃-110℃下烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulating: polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, adamantane, tetrahydrodipolycyclopentadiene, chain extender, initiator, compatibilizer, anti- After the yellowing agent and slippery anti-sticking agent are weighed in proportion, they are stirred for 3-5 minutes in a high-speed mixer with a speed of 60-80r/min, and then passed through the feeding hopper into a twin-screw underwater granulator. -300r/min, cylinder temperature is 150℃-200℃, machine head temperature is 150℃-180℃, extrusion and pelletizing to form 3-5mm balls or round cake-shaped small particles, and then further dehydrated , dry at 80°C-110°C until the moisture content is ≤0.2% to obtain extrusion granulated blend particles;
S2，流延成膜：将上述共混物颗粒加入挤出流延机中，在流延机螺杆转速 为100-200r/min、筒体温度为160℃-200℃下，流延成膜，其中，流延滚筒第一节温度为0℃-10℃，其它滚筒为常温，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting film: Add the above blend particles into the extrusion casting machine, and cast the film into a film when the screw speed of the casting machine is 100-200r/min and the cylinder temperature is 160℃-200℃. Among them, the temperature of the first section of the casting roller is 0℃-10℃, and the other rollers are at normal temperature, resulting in a degradable bio-based moisture-permeable waterproof membrane with a thickness of 0.01-0.05mm and a width of 0.4-1.5m.
相比现有技术，本发明的有益效果在于：Compared with the existing technology, the beneficial effects of the present invention are:
本发明的可降解生物基透湿防水膜采用聚甲基乙撑碳酸酯与聚乳酸等可降解的物料作为主基材，通过添加亲水增透剂、金刚烷酮、四氢二聚环戊二烯、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂，使其具有较好的透湿防水性能，其中，亲水增透剂增强体系的防水性能，金刚烷酮和四氢二聚环戊二烯在体系中引入环状结构，以增强体系的透湿性能，使体系在较好的透湿防水的基础上，具有透湿防水性能，使其具有环保效果。The biodegradable bio-based moisture-permeable waterproof membrane of the present invention uses degradable materials such as polymethylethylene carbonate and polylactic acid as the main base material. Diene, chain extender, initiator, compatibilizer, anti-yellowing agent and slippery anti-adhesive agent make it have good moisture permeability and waterproof performance. Among them, the hydrophilic anti-permeability agent enhances the waterproof performance of the system, and the diamond Alkanone and tetrahydrodipolycyclopentadiene introduce a cyclic structure into the system to enhance the moisture permeability of the system, so that the system has moisture permeability and waterproof properties on the basis of better moisture permeability and waterproofing, making it environmentally friendly Effect.
下面，结合具体实施方式，对本发明做进一步描述，需要说明的是，在不相冲突的前提下，以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。以下是本发明具体的实施例，在下述实施例中所采用的原材料、设备等除特殊限定外均可以通过购买方式获得。其中，亲水增透剂为聚四氢呋喃；扩链剂为六亚甲基二异氰酸酯；引发剂为2,5-二甲基正己烷-2,5-二甲羟基过氧化物；相容剂为苯乙烯-马来酸酐共聚物；抗黄变剂为光稳定剂770；爽滑抗粘剂是质量比为1:1的芥酸酰胺和纳米二氧化硅的复配物。Below, the present invention will be further described with reference to specific implementation modes. It should be noted that, on the premise of no conflict, the embodiments or technical features described below can be arbitrarily combined to form new embodiments. The following are specific embodiments of the present invention. The raw materials, equipment, etc. used in the following embodiments can be obtained through purchase unless otherwise specified. Among them, the hydrophilic antireflection agent is polytetrahydrofuran; the chain extender is hexamethylene diisocyanate; the initiator is 2,5-dimethyln-hexane-2,5-dimethylhydroxyperoxide; the compatibilizer is Styrene-maleic anhydride copolymer; anti-yellowing agent is light stabilizer 770; smooth anti-sticking agent is a compound of erucamide and nano-silica with a mass ratio of 1:1.
实施例1Example 1
一种可降解生物基透湿防水膜，包括如下重量份的组分：A degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
聚甲基乙撑碳酸酯30份；聚乳酸20份；亲水增透剂3份；金刚烷酮0.1份；四氢二聚环戊二烯0.1份；扩链剂1份；引发剂0.1份；相容剂3份；抗黄变剂0.5份；爽滑抗粘剂1.5份。30 parts of polymethylethylene carbonate; 20 parts of polylactic acid; 3 parts of hydrophilic antireflection agent; 0.1 part of adamantane; 0.1 part of tetrahydrodipolycyclopentadiene; 1 part of chain extender; 0.1 part of initiator ; 3 parts of compatibilizer; 0.5 parts of anti-yellowing agent; 1.5 parts of smooth and anti-adhesive agent.
该可降解生物基透湿防水膜的制备方法，包括如下制备步骤：The preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、亲水增透剂、金刚烷酮、四氢二聚环戊二烯、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在转速60r/min的高速搅拌机中搅拌3min，然后经过喂料斗在双螺杆水下的造粒机中，在转速为100r/min、筒体温度为200℃、机头温度为150℃下挤出切粒，形成3-5mm的圆球或圆饼状的小颗粒，再进一步地脱水后，在110℃下烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulating: polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, adamantane, tetrahydrodipolycyclopentadiene, chain extender, initiator, compatibilizer, anti- After the yellowing agent and smooth anti-sticking agent are weighed in proportion, stir for 3 minutes in a high-speed mixer with a speed of 60r/min, and then pass through the feeding hopper into a twin-screw underwater granulator. The body temperature is 200℃ and the machine head temperature is 150℃. It is extruded and pelletized to form 3-5mm balls or round cake-shaped small particles. After further dehydration, it is dried at 110℃ until the moisture content is ≤0.2 % to obtain extrusion granulated blend particles;
S2，流延成膜：将上述共混物颗粒加入挤出流延机中，在流延机螺杆转速为200r/min、筒体温度为200℃下，流延成膜，其中，流延滚筒第一节温度为5℃，其它滚筒为常温，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting to form a film: Add the above blend particles into the extrusion casting machine, and cast the film into a film when the screw speed of the casting machine is 200r/min and the cylinder temperature is 200°C. The casting roller The temperature of the first section is 5°C, and the other rollers are at normal temperature. A degradable bio-based moisture-permeable waterproof membrane with a thickness of 0.01-0.05mm and a width of 0.4-1.5m is obtained.
实施例2Example 2
一种可降解生物基透湿防水膜，包括如下重量份的组分：A degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
聚甲基乙撑碳酸酯40份；聚乳酸25份；亲水增透剂8份；金刚烷酮0.5份；四氢二聚环戊二烯0.6份；扩链剂3份；引发剂0.3份；相容剂5份；抗黄变剂3份；爽滑抗粘剂6份。40 parts of polymethylethylene carbonate; 25 parts of polylactic acid; 8 parts of hydrophilic antireflection agent; 0.5 parts of adamantane; 0.6 parts of tetrahydrodipolycyclopentadiene; 3 parts of chain extender; 0.3 parts of initiator ; 5 parts compatibilizer; 3 parts anti-yellowing agent; 6 parts smooth anti-adhesive agent.
该可降解生物基透湿防水膜的制备方法，包括如下制备步骤：The preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、亲水增透剂、金刚烷酮、四氢二聚环戊二烯、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在转速60r/min的高速搅拌机中搅拌3min，然后经过喂料斗在双螺杆水下的造粒机中，在转速为100r/min、筒体温度为200℃、机头温度为150℃下挤出切粒，形成3-5mm的圆球或圆饼状的小颗粒，再进一步地脱水后，在110℃下烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulating: polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, adamantane, tetrahydrodipolycyclopentadiene, chain extender, initiator, compatibilizer, anti- After the yellowing agent and smooth anti-sticking agent are weighed in proportion, stir for 3 minutes in a high-speed mixer with a speed of 60r/min, and then pass through the feeding hopper into a twin-screw underwater granulator. The body temperature is 200℃ and the machine head temperature is 150℃. It is extruded and pelletized to form 3-5mm balls or round cake-shaped small particles. After further dehydration, it is dried at 110℃ until the moisture content is ≤0.2 % to obtain extrusion granulated blend particles;
S2，流延成膜：将上述共混物颗粒加入挤出流延机中，在流延机螺杆转速为200r/min、筒体温度为200℃下，流延成膜，其中，流延滚筒第一节温度为5℃，其它滚筒为常温，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting to form a film: Add the above blend particles into the extrusion casting machine, and cast the film into a film when the screw speed of the casting machine is 200r/min and the cylinder temperature is 200°C. The casting roller The temperature of the first section is 5°C, and the other rollers are at normal temperature. A degradable bio-based moisture-permeable waterproof membrane with a thickness of 0.01-0.05mm and a width of 0.4-1.5m is obtained.
实施例3Example 3
一种可降解生物基透湿防水膜，包括如下重量份的组分：A degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
聚甲基乙撑碳酸酯50份；聚乳酸30份；亲水增透剂10份；金刚烷酮1份；四氢二聚环戊二烯1份；扩链剂5份；引发剂1份；相容剂10份；抗黄变剂5份；爽滑抗粘剂10份。50 parts of polymethylethylene carbonate; 30 parts of polylactic acid; 10 parts of hydrophilic antireflection agent; 1 part of adamantane; 1 part of tetrahydrodipolycyclopentadiene; 5 parts of chain extender; 1 part of initiator ; 10 parts of compatibilizer; 5 parts of anti-yellowing agent; 10 parts of smooth and anti-adhesive agent.
该可降解生物基透湿防水膜的制备方法，包括如下制备步骤：The preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、亲水增透剂、金刚烷酮、四氢二聚环戊二烯、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在转速60r/min的高速搅拌机中搅拌3min，然后经过喂料斗在双螺杆水下的造粒机中，在转速为100r/min、筒体温度为200℃、机头温度为150℃下挤出切粒，形成3-5mm的圆球或圆饼状的小颗粒，再进一步地脱水后，在110℃下烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulating: polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, adamantane, tetrahydrodipolycyclopentadiene, chain extender, initiator, compatibilizer, anti- After the yellowing agent and smooth anti-sticking agent are weighed in proportion, stir for 3 minutes in a high-speed mixer with a speed of 60r/min, and then pass through the feeding hopper into a twin-screw underwater granulator. The body temperature is 200℃ and the machine head temperature is 150℃. It is extruded and pelletized to form 3-5mm balls or round cake-shaped small particles. After further dehydration, it is dried at 110℃ until the moisture content is ≤0.2 % to obtain extrusion granulated blend particles;
S2，流延成膜：将上述共混物颗粒加入挤出流延机中，在流延机螺杆转速为200r/min、筒体温度为200℃下，流延成膜，其中，流延滚筒第一节温度为5℃，其它滚筒为常温，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting to form a film: Add the above blend particles into the extrusion casting machine, and cast the film into a film when the screw speed of the casting machine is 200r/min and the cylinder temperature is 200°C. The casting roller The temperature of the first section is 5°C, and the other rollers are at normal temperature. A degradable bio-based moisture-permeable waterproof membrane with a thickness of 0.01-0.05mm and a width of 0.4-1.5m is obtained.
对比例1Comparative example 1
一种可降解生物基透湿防水膜，包括如下重量份的组分：A degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
聚甲基乙撑碳酸酯30份；聚乳酸20份；亲水增透剂3份；扩链剂1份； 引发剂0.1份；相容剂3份；抗黄变剂0.5份；爽滑抗粘剂1.5份。30 parts of polymethylethylene carbonate; 20 parts of polylactic acid; 3 parts of hydrophilic anti-reflection agent; 1 part of chain extender; 0.1 part of initiator; 3 parts of compatibilizer; 0.5 part of anti-yellowing agent; smooth and anti- 1.5 parts of adhesive.
该可降解生物基透湿防水膜的制备方法，包括如下制备步骤：The preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、亲水增透剂、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在转速60r/min的高速搅拌机中搅拌3min，然后经过喂料斗在双螺杆水下的造粒机中，在转速为100r/min、筒体温度为200℃、机头温度为150℃下挤出切粒，形成3-5mm的圆球或圆饼状的小颗粒，再进一步地脱水后，在110℃下烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulating: weigh polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, chain extender, initiator, compatibilizer, anti-yellowing agent and slippery anti-sticking agent in proportion Afterwards, stir for 3 minutes in a high-speed mixer with a speed of 60r/min, and then pass through the feeding hopper into a twin-screw underwater granulator at a speed of 100r/min, a cylinder temperature of 200°C, and a machine head temperature of 150°C. Extrusion and granulation to form 3-5mm ball or round cake-shaped small particles, and then further dehydrated, dried at 110°C until the moisture content is ≤0.2%, to obtain extrusion granulated blend particles;
S2，流延成膜：将上述共混物颗粒加入挤出流延机中，在流延机螺杆转速为200r/min、筒体温度为200℃下，流延成膜，其中，流延滚筒第一节温度为5℃，其它滚筒为常温，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting to form a film: Add the above blend particles into the extrusion casting machine, and cast the film into a film when the screw speed of the casting machine is 200r/min and the cylinder temperature is 200°C. The casting roller The temperature of the first section is 5°C, and the other rollers are at normal temperature. A degradable bio-based moisture-permeable waterproof membrane with a thickness of 0.01-0.05mm and a width of 0.4-1.5m is obtained.
对比例2Comparative example 2
一种可降解生物基透湿防水膜，包括如下重量份的组分：A degradable bio-based moisture-permeable waterproof membrane includes the following components by weight:
聚甲基乙撑碳酸酯60份；聚乳酸40份；相容剂3份；抗黄变剂0.5份；爽滑抗粘剂1.5份。60 parts of polymethylethylene carbonate; 40 parts of polylactic acid; 3 parts of compatibilizer; 0.5 parts of anti-yellowing agent; 1.5 parts of smooth and anti-adhesive agent.
该可降解生物基透湿防水膜的制备方法，包括如下制备步骤：The preparation method of the degradable bio-based breathable waterproof membrane includes the following preparation steps:
S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在转速60r/min的高速搅拌机中搅拌3min，然后经过喂料斗在双螺杆水下的造粒机中，在转速为100r/min、筒体温度为200℃、机头温度为150℃下挤出切粒，形成3-5mm的圆球或圆饼状的小颗粒，再进一步地脱水后，在110℃下烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulation: weigh the polymethylethylene carbonate, polylactic acid, compatibilizer, anti-yellowing agent and smooth anti-sticking agent in proportion, and stir for 3 minutes in a high-speed mixer with a speed of 60r/min. , and then extruded and cut into 3-5mm balls or The round cake-shaped small particles are further dehydrated and dried at 110°C until the moisture content is ≤0.2% to obtain extrusion granulated blend particles;
S2，流延成膜：将上述共混物颗粒加入挤出流延机中，在流延机螺杆转速 为200r/min、筒体温度为200℃下，流延成膜，其中，流延滚筒第一节温度为5℃，其它滚筒为常温，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting to form a film: Add the above blend particles into the extrusion casting machine, and cast the film into a film when the screw speed of the casting machine is 200r/min and the cylinder temperature is 200°C. The casting roller The temperature of the first section is 5°C, and the other rollers are at normal temperature. A degradable bio-based moisture-permeable waterproof membrane with a thickness of 0.01-0.05mm and a width of 0.4-1.5m is obtained.
测试方法：Test Methods:
按照《GB/T 20991-2007个体防护装备鞋的测试方法》6.6水蒸气渗透性的测定和6.10鞋帮耐水解的测定测试薄膜的透湿率、抗水解性；按照《GB/T 1038-2000塑料薄膜和薄片气体透过量试验方法——压差法》测试薄膜的透气性；按照《GB/T 4744-2013纺织品防水性能的检测和评价静水压法》测试薄膜的耐水压效果；按照《GB/T 39935-2021塑料制品薄膜和片材抗粘连性的测定》评估薄膜的抗黏连特性；耐黄变按照ASTM D1148-2013橡胶耐黄变测试方法进行。According to "GB/T 20991-2007 Test Methods for Personal Protective Equipment Shoes" 6.6 Determination of water vapor permeability and 6.10 Determination of upper hydrolysis resistance, test the moisture permeability and hydrolysis resistance of the film; in accordance with "GB/T 1038-2000 Plastics" Test method for gas permeability of films and sheets - differential pressure method" to test the air permeability of the film; test the water pressure resistance of the film according to "GB/T 4744-2013 Detection and Evaluation of Waterproof Performance of Textiles Hydrostatic Pressure Method"; test the water pressure resistance of the film according to "GB/T 4744-2013 Testing and Evaluation of Waterproof Performance of Textiles" /T 39935-2021 Determination of anti-adhesion properties of films and sheets of plastic products" to evaluate the anti-adhesion properties of films; yellowing resistance is carried out in accordance with ASTM D1148-2013 Rubber Yellowing Resistance Test Method.
测试结果如下表1所示：The test results are shown in Table 1 below:
表1Table 1
| 测试项目Test items | 对比例1Comparative example 1 | 对比例2Comparative example 2 | 实施例1Example 1 | 实施例2Example 2 | 实施例3Example 3 |
| 氧气透气量(cm 3/cm 3.s) Oxygen permeability (cm 3 /cm 3 .s) | 0.620.62 | 0.450.45 | 0.790.79 | 0.760.76 | 0.820.82 |
| 透湿量(MVP)(g/cm 2.h) Moisture permeability (MVP) (g/cm 2 .h) | 5.55.5 | 5.05.0 | 7.27.2 | 7.37.3 | 6.96.9 |
| 黄变等级Yellowing grade | 4.54.5 | 4.54.5 | 4.54.5 | 4.54.5 | 4.54.5 |
| 静态耐水压(m水柱)Static water pressure resistance (m water column) | 5.65.6 | 4.84.8 | 6.26.2 | 6.56.5 | 6.36.3 |
| 抗粘连效果剥离拉力值(N)Anti-adhesion effect peeling tension value (N) | 4.34.3 | 6.56.5 | 0.30.3 | 0.50.5 | 0.60.6 |
上述实施方式仅为本发明的优选实施方式，不能以此来限定本发明保护的范围，本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。The above-mentioned embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantive changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of the present invention. Scope of protection claimed.
Claims (10)
- 一种可降解生物基透湿防水膜，其特征在于，包括如下重量份的组分：A degradable bio-based moisture-permeable waterproof membrane is characterized in that it includes the following components by weight:聚甲基乙撑碳酸酯30份-50份；聚乳酸20份-30份；亲水增透剂3份-10份；金刚烷酮0.1份-1份；四氢二聚环戊二烯0.1份-1份；扩链剂1份-5份；引发剂0.1份-1份；相容剂3份-10份；抗黄变剂0.5份-5份；爽滑抗粘剂1.5份-10份。30 parts to 50 parts of polymethylethylene carbonate; 20 parts to 30 parts of polylactic acid; 3 parts to 10 parts of hydrophilic antireflection agent; 0.1 part to 1 part of adamantanone; 0.1 part of tetrahydrodicyclopentadiene part-1 part; chain extender 1 part-5 parts; initiator 0.1 part-1 part; compatibilizer 3 parts-10 parts; anti-yellowing agent 0.5 part-5 parts; smooth anti-sticking agent 1.5 parts-10 parts share.
- 根据权利要求1所述的可降解生物基透湿防水膜，其特征在于，所述亲水增透剂为苯聚环氧乙烷、聚环氧丙烷、聚四氢呋喃中的一种或两种以上。The degradable bio-based moisture-permeable waterproof membrane according to claim 1, wherein the hydrophilic anti-permeability agent is one or more of benzene polyethylene oxide, polypropylene oxide, and polytetrahydrofuran. .
- 根据权利要求1所述的可降解生物基透湿防水膜，其特征在于，所述扩链剂为异氰酸酯、环状羧酸酐、磷酸酯、双环亚胺酯中的一种或两种以上。The degradable bio-based moisture-permeable waterproof membrane according to claim 1, wherein the chain extender is one or more of isocyanate, cyclic carboxylic acid anhydride, phosphate ester, and bicyclic imide ester.
- 根据权利要求3所述的可降解生物基透湿防水膜，其特征在于，所述异氰酸酯为六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或两种以上；所述环状羧酸酐为均苯四甲酸酐或偏苯三酸酐；所述磷酸酯为亚磷酸三苯酯；所述双环亚胺酯为双苯并噁嗪。The degradable bio-based moisture-permeable waterproof membrane according to claim 3, wherein the isocyanate is one or more of hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate; The cyclic carboxylic acid anhydride is pyromellitic anhydride or trimellitic anhydride; the phosphate ester is triphenyl phosphite; and the bicyclic imine ester is bisbenzoxazine.
- 根据权利要求1所述的可降解生物基透湿防水膜，其特征在于，所述引发剂为2,5-二甲基正己烷-2,5-二甲羟基过氧化物、过氧化氢异丙苯、叔丁基过氧化氢、萜烷过氧化氢、过氧化氢苯甲酰、2,6,6-三甲基二环[3.1.1]庚烷基氢过氧化物中的一种或两种以上。The degradable bio-based moisture-permeable waterproof membrane according to claim 1, wherein the initiator is 2,5-dimethyln-hexane-2,5-dimethylhydroxyperoxide, hydrogen peroxide isopropoxide One of propylbenzene, tert-butyl hydroperoxide, terpene hydroperoxide, benzoyl hydroperoxide, and 2,6,6-trimethylbicyclo[3.1.1]heptyl hydroperoxide Or two or more.
- 根据权利要求1所述的可降解生物基透湿防水膜，其特征在于，所述相容剂为马来酸酐接枝聚烯烃、苯乙烯-马来酸酐共聚物、甲基丙烯酸缩水甘油酯接枝聚烯烃共聚物中的一种或两种以上。The degradable bio-based moisture-permeable waterproof membrane according to claim 1, characterized in that the compatibilizer is maleic anhydride grafted polyolefin, styrene-maleic anhydride copolymer, glycidyl methacrylate grafted One or more than two kinds of branched polyolefin copolymers.
- 根据权利要求1所述的可降解生物基透湿防水膜，其特征在于，所述抗黄变剂为受阻酚类紫外线吸收剂。The degradable bio-based moisture-permeable waterproof membrane according to claim 1, wherein the anti-yellowing agent is a hindered phenolic ultraviolet absorber.
- 根据权利要求1所述的可降解生物基透湿防水膜，其特征在于，所述爽滑抗粘剂为芥酸酰胺、硬脂酸酰胺、油酸酰胺、棕榈酰胺、纳米二氧化硅、纳 米滑石粉、煅烧高岭土、纳米碳酸钙中的一种或两种以上。The degradable bio-based moisture-permeable waterproof membrane according to claim 1, wherein the slippery anti-sticking agent is erucamide, stearic acid amide, oleic acid amide, palmitamide, nano-silica, nano-silica, etc. One or more of talcum powder, calcined kaolin, and nano-calcium carbonate.
- 一种如权利要求1-8任一项所述的可降解生物基透湿防水膜的制备方法，其特征在于，包括如下制备步骤：A method for preparing the degradable bio-based moisture-permeable waterproof membrane according to any one of claims 1 to 8, characterized in that it includes the following preparation steps:S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、亲水增透剂、金刚烷酮、四氢二聚环戊二烯、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在高速搅拌机中搅拌均匀，然后经过喂料斗在双螺杆水下的造粒机中，挤出切粒，形成圆球或圆饼状的小颗粒，再进一步地脱水后，烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulating: polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, adamantane, tetrahydrodipolycyclopentadiene, chain extender, initiator, compatibilizer, anti- After the yellowing agent and smooth anti-sticking agent are weighed in proportion, mix them evenly in a high-speed mixer, and then pass through the feeding hopper into a twin-screw underwater granulator, extrusion and granulation to form a ball or round cake. The small particles are further dehydrated and dried to a moisture content of ≤0.2% to obtain extrusion granulated blend particles;S2，流延成膜：将上述共混物颗粒加入挤出流延机中，流延成膜，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting film formation: Add the above blend particles into an extrusion casting machine and cast them into a film to obtain a degradable bio-based moisture-permeable waterproofing film with a thickness of 0.01-0.05mm and a width of 0.4-1.5m.
- 根据权利要求1所述的可降解生物基透湿防水膜的制备方法，其特征在于，包括如下制备步骤：The preparation method of degradable bio-based moisture-permeable waterproof membrane according to claim 1, characterized in that it includes the following preparation steps:S1，混配造粒：将聚甲基乙撑碳酸酯、聚乳酸、亲水增透剂、金刚烷酮、四氢二聚环戊二烯、扩链剂、引发剂、相容剂、抗黄变剂和爽滑抗粘剂按比例称取后，在转速60-80r/min的高速搅拌机中搅拌3-5min，然后经过喂料斗在双螺杆水下的造粒机中，在转速为100-300r/min、筒体温度为150℃-200℃、机头温度为150℃-180℃下挤出切粒，形成3-5mm的圆球或圆饼状的小颗粒，再进一步地脱水后，在80℃-110℃下烘干至水分含量≤0.2％，得到挤出造粒的共混物颗粒；S1, mixing and granulating: polymethylethylene carbonate, polylactic acid, hydrophilic anti-reflection agent, adamantane, tetrahydrodipolycyclopentadiene, chain extender, initiator, compatibilizer, anti- After the yellowing agent and slippery anti-sticking agent are weighed in proportion, they are stirred for 3-5 minutes in a high-speed mixer with a speed of 60-80r/min, and then passed through the feeding hopper into a twin-screw underwater granulator. -300r/min, cylinder temperature is 150℃-200℃, machine head temperature is 150℃-180℃, extrusion and pelletizing to form 3-5mm balls or round cake-shaped small particles, and then further dehydrated , dry at 80°C-110°C until the moisture content is ≤0.2% to obtain extrusion granulated blend particles;S2，流延成膜：将上述共混物颗粒加入挤出流延机中，在流延机螺杆转速为100-200r/min、筒体温度为160℃-200℃下，流延成膜，其中，流延滚筒第一节温度为0℃-10℃，其它滚筒为常温，得到厚度0.01-0.05mm、宽幅0.4-1.5m的可降解生物基透湿防水膜。S2, Casting film: Add the above blend particles into the extrusion casting machine, and cast the film into a film when the screw speed of the casting machine is 100-200r/min and the cylinder temperature is 160℃-200℃. Among them, the temperature of the first section of the casting roller is 0℃-10℃, and the other rollers are at normal temperature, resulting in a degradable bio-based moisture-permeable waterproof membrane with a thickness of 0.01-0.05mm and a width of 0.4-1.5m.
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| CN112210197A (en) * | 2020-10-10 | 2021-01-12 | 莱涤新材料(宁波)有限公司 | Biodegradable polylactic acid film and preparation method thereof |
| CN113943478A (en) * | 2021-05-08 | 2022-01-18 | 天津科技大学 | Flexible transparent degradable packaging film |
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| CN105017738A (en) * | 2014-11-26 | 2015-11-04 | 江苏天仁生物材料有限公司 | Fully biodegradable material taking polylactic acid/polymethyl ethylene carbonic ester as basic material and preparation method of fully biodegradable material |
| KR101558171B1 (en) * | 2015-05-08 | 2015-10-07 | 주식회사 영우티피 | Moisture-permeable waterproof film laminate including breathable hot-melt adhesive layer and manufacturing mehtod thereof |
| CN113150511A (en) * | 2021-05-08 | 2021-07-23 | 吉林省中亿医药包装有限公司 | Biodegradable preservative film with air conditioning function and preparation method thereof |
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- 2022-06-06 CN CN202210630752.0A patent/CN115044182A/en active Pending
- 2022-06-24 WO PCT/CN2022/101260 patent/WO2023236267A1/en unknown
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| US20090234042A1 (en) * | 2006-04-27 | 2009-09-17 | Basf Se | Transparent blends of polypropylene carbonate |
| CN106046725A (en) * | 2016-07-01 | 2016-10-26 | 吉林中粮生化有限公司 | High-barrier-property biodegradable mulching film and preparation method thereof |
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| CN110834451A (en) * | 2019-10-24 | 2020-02-25 | 上海若祎新材料科技有限公司 | Polyethylene film composition, polyethylene film and composite film and application thereof |
| CN111978691A (en) * | 2020-09-11 | 2020-11-24 | 中国科学院长春应用化学研究所 | Biodegradable mulching film and preparation method thereof |
| CN112210197A (en) * | 2020-10-10 | 2021-01-12 | 莱涤新材料(宁波)有限公司 | Biodegradable polylactic acid film and preparation method thereof |
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| CN115044182A (en) | 2022-09-13 |
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