CN105837786B - Cellulose nanometer fibril composite bicomponent aqueous polyurethane and its preparation method and application - Google Patents
Cellulose nanometer fibril composite bicomponent aqueous polyurethane and its preparation method and application Download PDFInfo
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- CN105837786B CN105837786B CN201610157014.3A CN201610157014A CN105837786B CN 105837786 B CN105837786 B CN 105837786B CN 201610157014 A CN201610157014 A CN 201610157014A CN 105837786 B CN105837786 B CN 105837786B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 65
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 229920002678 cellulose Polymers 0.000 title claims abstract description 30
- 239000001913 cellulose Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 229920005862 polyol Polymers 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 230000010355 oscillation Effects 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 14
- 238000010298 pulverizing process Methods 0.000 claims abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002861 polymer material Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 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
- -1 poly- ammonia Ester polyol Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 13
- 230000000996 additive effect Effects 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 7
- 239000011527 polyurethane coating Substances 0.000 abstract description 5
- 239000013066 combination product Substances 0.000 description 14
- 229940127555 combination product Drugs 0.000 description 14
- 239000003973 paint Substances 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Reinforced Plastic Materials (AREA)
- Paints Or Removers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention discloses a kind of cellulose nanometer fibril composite bicomponent aqueous polyurethane and its preparation method and application.NFC is directly added into polyurethane polyol aqueous dispersion by cell pulverization sonic oscillation method, then is solidified with polyisocyanate cross, series NFC composite bicomponent water-based polyurethane polymer is obtained.The composition polymer is preparing the application in aqueous polyurethane coating, binder and polymer material.When NFC additive amount is the 1% of dual-component aqueous polyurethane hard resin quality, the mechanical performance of composition polymer is optimal, compared with pure dual-component aqueous polyurethane cross-linking products, stretch modulus, which improves 99.7%, tensile strength and improves 86.5%, storage modulus and improve 24.1%, loss modulus, improves 79.9%.
Description
Technical field
The present invention relates to a kind of cellulose nanometer fibril (NFC) composite bicomponent aqueous polyurethane and preparation method thereof and use
On the way.
Background technique
With the raising of global environmental consciousness and sound, the volatile organic compound in traditional solvent type coating of environmental regulation
The discharge of object (VOC) is more and more severely limited.Water paint using water as decentralized medium, have it is non-ignitable, nontoxic, do not pollute ring
The advantages that border and the saving energy.Waterborne two-component polyurethane coating is by the high-performance of two part solvent type polyurethane coating and aqueous
The low VOC content of coating combines, it has also become the hot spot of domestic rustproof lacquer research.Waterborne two-component polyurethane coating be by containing-
The aqueous polyol component of OH group is formed with the low-viscosity polyisocyanate component containing-NCO group, and two components are moisture
Shot is interparticle heterogeneous film forming when crosslinking forms a film, thus the mechanical property of film forming matter, resistant to liquid dielectric behavior relatively have
The homogeneous film forming of solvent type two-component system is poor, it is necessary to double from molecular level enhancing with composite modified method by chemistry
The comprehensive performance of component waterborne polyurethane.
The granted patent (ZL 201310410925.9) of inventor discloses a kind of Cellulose nanocrystal palpus (CNW) Composite Double
Aqueous terpenes based polyurethanes of component and its preparation method and application.The diameter range of CNW be 5~40nm, length range be 100~
600nm, it is obvious to bi-component waterborne terpenes based polyurethanes mechanical performance reinforcing effect.But the preparation method of CNW is generally strong acid
Hydrolysis, yield is lower, and high speed centrifugation (10000 revs/min or more) are needed in last handling process, is difficult to realize industrial applications.NFC
It is considered as the smallest structural unit in plant fiber, it is by bundles of high-intensitive and high Young's modulus of elasticity cellulosic molecule
Chain is made up of hydrogen bond, wherein being dispersed with the cellulose crystals and unformed cellulosic polymer of crystallization.The diameter range of NFC
For 10~50nm, length range is 50~600 μm, and draw ratio is very big, reaches 1000 or more, and cellulose nanometer fibril can be with
Reticular structure is formed in composite material, enhances the intensity of polymer.The preparation method of NFC is generally Mechanical Method, to preparation work
Skill is of less demanding, and yield is higher, and it is commercially available to have commercial prod.Therefore, compared with common non-nanofiber element, NFC has
The characteristics such as high-purity, high-crystallinity, high Young's modulus, high intensity, compared with CNW, NFC yield is high, at low cost, has again in addition
The lightweight of biomaterial, degradable, bio-compatible and the characteristics such as renewable, show it in high-performance composite materials huge
Application prospect, especially as the reinforced phase of composite material, it has shown brilliant characteristic.
Existing document report is using NFC composite acrylic resin, polylactic acid, epoxy resin etc. at present, due to NFC specific surface
Product is big, surface hydroxyl very abundant, hydrophily are strong, be difficult uniformly, be effectively dispersed in hydrophobic polymer resin matrix.Often
Mixed method has mechanical mixing method, freeze-drying casting method, infusion process etc..Chemistry is carried out using NFC surface-active hydroxyl
Graft modification increases its oleophylic/hydrophobicity, can reach uniform, stable dispersion in organic solvent and hydrophobic resin matrix
Effect.And preparing compound water-soluble or water-dispersion type high molecular material using the hydrophily of NFC is be different from the prior art one
The ideal method of kind.
The water-base resin system of the existing document report compound one-component of NFC at present, film forming procedure pertain only to physics at
Membrane process.The film forming procedure of double-component waterborne polyurethane system is directed not only to physical film deposition, while chemical crosslinking film forming also occurs,
NFC can be made to be securely fixed in resin cross-linked network system by chemical reaction.It is participated in using the activity hydroxy on the surface NFC
In the cross-linking reaction of dual-component polyurethane, enhance the interaction of NFC and resin matrix interface, it can effective reinforced polymeric material
Composite effect.
Summary of the invention
The purpose of the present invention is to provide a kind of cellulose nanometer fibril composite bicomponent aqueous polyurethane and its preparation sides
Method.This method utilize NFC hydrophily, can with dual-component aqueous polyurethane direct combination, using the surface NFC activity hydroxy with
Polyisocyanate is chemically crosslinked, and is enhanced the interaction of NFC and resin matrix interface, can be effectively improved the property of composite material
Energy.
The technical solution of the present invention is as follows: a kind of cellulose nanometer fibril composite bicomponent aqueous polyurethane, composition are as follows: composition
By mass percentage are as follows: cellulose nanometer fibril content is the 0.01~2% of dual-component aqueous polyurethane hard resin quality；
Polyisocyanate is mixed by isocyanate group with 0.8~1.6:1 of the mass ratio of the material of hydroxyl with polyurethane polyol；Cellulose is received
Rice fibril is added directly into polyurethane polyol aqueous dispersion by cell pulverization sonic oscillation method, then is handed over polyisocyanate
Connection solidification, obtains cellulose nanometer fibril composite bicomponent aqueous polyurethane.
The cellulose nanometer fibril be high length-diameter ratio fibril, 400~600 μm of fibre length, fibre diameter 10~
50nm。
The polyurethane polyol hydroxyl value be 50~150mg/g, polyurethane polyol aqueous dispersion solid content 30~
50%.
The polyisocyanate is the hexamethylene diisocyanate tripolymer of hydrophilic modifying.
The method of the preparation compound double-component waterborne polyurethane of cellulose nanometer fibril, cellulose nanometer fibril is led to
It crosses cell pulverization sonic oscillation method to be directly added into polyurethane polyol aqueous dispersion, then solidifies with polyisocyanate cross, obtain
Obtain cellulose nanometer fibril composite bicomponent water-based polyurethane polymer.
The cell pulverization sonic oscillation method, power are 1000~1800W, and the time is 10~20min.
The cellulose nanometer fibril composite bicomponent aqueous polyurethane prepare aqueous polyurethane coating, binder or
Application in polymer material.
The utility model has the advantages that
1. preparation method of the present invention is simple, NFC is modified without surface, it is polynary to be uniformly and stably dispersed in without drying
In alcohol aqueous dispersion, and NFC draw ratio is high, can form reticular structure in composite material, enhance the intensity of polymer.
2. cell pulverization sonic oscillation method is applied to preparation NFC composite bicomponent water-based polyurethane polymer, and it is common
Mechanical mixing method is compared, and cell pulverization sonic oscillation method significantly improves NFC dispersion efficiency and dispersion effect, to composition polymer
Mechanical performance significantly improve (experimental result of reference implementation example 2 and comparative example 2).
3. chemistry occurs with thermoset substrate resin using the activity hydroxy on the surface NFC by the present invention and physics is compound, enhancing
The interaction of NFC and resin matrix interface can effectively improve the performance of composite material.When NFC additive amount is bi-component waterborne
Urethane solid resin quality 1% when, the mechanical performance of composition polymer is optimal, with pure dual-component aqueous polyurethane be crosslinked produce
Object is compared, stretch modulus improve 99.7%, tensile strength improve 86.5%, storage modulus improve 24.1%, loss
Modulus improves 79.9%.
Detailed description of the invention
The transmission electron microscope figure of Fig. 1 NFC.NFC used be high length-diameter ratio fibril, 400~600 μm of fibre length,
10~50nm of fibre diameter.
Shadow of Fig. 2 NFC additive amount to dual-component aqueous polyurethane combination product storage modulus (G') and loss modulus (G ")
It rings.Compared with pure dual-component aqueous polyurethane cross-linking products (NFC additive amount is 0%), when temperature is less than product glass transition
When temperature, the G' and G " of combination product are significantly increased after addition NFC, show that NFC has obviously the mechanical performance of combination product
Humidification；With the increase of NFC additive amount, the equal first increases and then decreases of G' and G " of combination product shows that NFC additive amount is larger
When difficulty disperse influence combination product performance easy to reunite.
Influence of Fig. 3 NFC additive amount to dual-component aqueous polyurethane combination product tensile property.It is poly- with pure bi-component waterborne
Urethane cross-linking products (NFC additive amount is 0%) are compared, and the stretch modulus and tensile strength of combination product are obvious after addition NFC
Increase；With the increase of NFC additive amount, the equal first increases and then decreases of stretch modulus and tensile strength of combination product.When NFC is added
When amount is the 1% of dual-component aqueous polyurethane hard resin quality, the mechanical performance of composition polymer is optimal, with pure bi-component water
Property urethane crosslinks product is compared, and stretch modulus improves 99.7%, tensile strength and improves 86.5%.
Specific embodiment
NFC used in the present invention is the cellulose nanometer fibril of commercial mechanical method preparation, Japanese Daicel Co., Ltd..Institute
Polyurethane polyol aqueous dispersion is commercially available aqueous polyurethane polyhydroxy performed polymer, and Shanghai thinks to contain the limited public affairs of polymer material
Department.The polyisocyanate is the poly- diisocyanate industrial goods of commercially available hydrophilic modifying, and it is limited that Sheng polymer material is thought in Shanghai
Company.
A kind of preparation method of NFC composite bicomponent aqueous polyurethane, the NFC of Different adding amount is surpassed by cell pulverization
Sound oscillation method is directly added into polyurethane polyol aqueous dispersion, then by polyisocyanate based on hydroxyl and isocyanate group chemistry
Amount obtains NFC composite bicomponent water-based polyurethane polymer than cooperation, crosslinking curing.The composition polymer is preparing aqueous gather
Application in urethane coating, binder and polymer material.
The NFC Different adding amount range is the 0.01~2% of dual-component aqueous polyurethane hard resin quality.
The NFC be high length-diameter ratio fibril, 400~600 μm of fibre length, 10~50nm of fibre diameter.
The polyurethane polyol hydroxyl value be 50~150mg/g, polyurethane polyol aqueous dispersion solid content 30~
50%.
The cell pulverization sonic oscillation method, power are 1000~1800W, and the time is 10~20min.
The polyisocyanate is the hexamethylene diisocyanate tripolymer of hydrophilic modifying.
Described measuring by hydroxyl and isocyanate group chemistry than range is the mass ratio of the material 1: 0.8~1.6.
NFC composite bicomponent aqueous polyurethane system prepared by the present invention, manufacturing method are easy.By poly- the two of hydrophilic modifying
Isocyanates, aqueous polyalcohol and NFC after mixing, add appropriate distilled water regulation system viscosity, film, at room temperature
It places 2 days, dries 1h then at 100 DEG C of baking ovens, survey paint film property.
The stretch modulus of combination product is 200~400MPa (25 DEG C), and tensile strength is 7~15MPa (25 DEG C), energy storage mould
Amount is 1500~2000MPa (10 DEG C), and loss modulus is 80~180MPa (10 DEG C).
Embodiment 1:NFC additive amount is the 0.5% of dual-component aqueous polyurethane hard resin quality
0.065g NFC is added in 20.00g polyurethane polyol aqueous dispersion (solid content 35%), it is super with cell pulverization
Sound oscillation method disperses 10min, power 1080W, adds 6.00g water-based isocyanate crosslinking agent, is uniformly mixed, addition
After the dilution of 6.00g water, the film on polyfluortetraethylene plate after placing 2 days at room temperature, dries 1h then at 100 DEG C of baking ovens, surveys
Paint film property.Combination product stretch modulus 258.9MPa (25 DEG C), tensile strength 11.7MPa (25 DEG C), storage modulus
1693.2MPa (10 DEG C), loss modulus 112.5MPa (10 DEG C).
Embodiment 2:NFC additive amount is the 1% of dual-component aqueous polyurethane hard resin quality
0.26g NFC is added in 40.00g polyurethane polyol aqueous dispersion (solid content 35%), it is super with cell pulverization
Sound oscillation method disperses 10min, power 1260W, adds 12.00g water-based isocyanate crosslinking agent, is uniformly mixed, addition
After the dilution of 12.00g water, the film on polyfluortetraethylene plate after placing 2 days at room temperature, dries 1h then at 100 DEG C of baking ovens,
Survey paint film property.Combination product stretch modulus 388.2MPa (25 DEG C), tensile strength 13.8MPa (25 DEG C), storage modulus
1895.3MPa (10 DEG C), loss modulus 161.4MPa (10 DEG C).
Embodiment 3:NFC additive amount is the 1.5% of dual-component aqueous polyurethane hard resin quality
0.195g NFC is added in 20.00g polyurethane polyol aqueous dispersion (solid content 35%), it is super with cell pulverization
Sound oscillation method disperses 15min, power 1260W, adds 6.00g water-based isocyanate crosslinking agent, is uniformly mixed, addition
After the dilution of 6.00g water, the film in polytetrafluoroethylene (PTFE) template after placing 2 days at room temperature, dries 1h then at 100 DEG C of baking ovens,
Survey paint film property.Combination product stretch modulus 326.1MPa (25 DEG C), tensile strength 12.4MPa (25 DEG C), storage modulus
1949.7MPa (10 DEG C), loss modulus 148.0MPa (10 DEG C).
Embodiment 4:NFC additive amount is the 2% of dual-component aqueous polyurethane hard resin quality
0.39g NFC is added in 30.00g polyurethane polyol aqueous dispersion (solid content 35%), it is super with cell pulverization
Sound oscillation method disperses 20min, power 1440W, adds 9.00g water-based isocyanate crosslinking agent, after mixing, addition
After the dilution of 9.00g water, the film on polyfluortetraethylene plate after placing 2 days at room temperature, dries 1h then at 100 DEG C of baking ovens, surveys
Paint film property.Combination product stretch modulus 268.6MPa (25 DEG C), tensile strength 11.5MPa (25 DEG C), storage modulus
1902.9MPa (10 DEG C), loss modulus 144.8MPa (10 DEG C).
Comparative example 1: NFC is not added
10.00g polyurethane polyol aqueous dispersion (solid content 35%) is mixed with 3.00g water-based isocyanate crosslinking agent
Uniformly, after the dilution of addition 3.00g water, the film on polyfluortetraethylene plate after placing 2 days at room temperature, is dried then at 100 DEG C
Case dries 1h, surveys paint film property.Cross-linking products stretch modulus 194.4MPa (25 DEG C), tensile strength 7.4MPa (25 DEG C), energy storage mould
Measure 1527.4MPa (10 DEG C), loss modulus 89.7MPa (10 DEG C).
Comparative example 2: disperse NFC using standard machinery paddling process
0.26g NFC is added in 40.00g polyurethane polyol aqueous dispersion (solid content 35%), with mechanical mixing method
Disperse 2h, add 12.00g water-based isocyanate crosslinking agent, be uniformly mixed, after addition 12.00g water dilution, in polytetrafluoroethyl-ne
Film on alkene plate after placing 2 days at room temperature, dries 1h then at 100 DEG C of baking ovens, surveys paint film property.Combination product stretching die
Measure 173.1MPa (25 DEG C), tensile strength 6.6MPa (25 DEG C), storage modulus 1595.1MPa (10 DEG C), loss modulus 75.2MPa
(10℃)。
Claims (6)
1. a kind of cellulose nanometer fibril composite bicomponent aqueous polyurethane, which is characterized in that composition is by mass percentage are as follows:
Cellulose nanometer fibril content is the 0.01~2% of dual-component aqueous polyurethane hard resin quality；Polyisocyanate and poly- ammonia
Ester polyol is mixed by isocyanate group with the mass ratio of the material 0.8~1.6: 1 of hydroxyl；Cellulose nanometer fibril is passed through thin
Born of the same parents crush sonic oscillation method and are added directly into polyurethane polyol aqueous dispersion, then solidify with polyisocyanate cross, obtain
Cellulose nanometer fibril composite bicomponent aqueous polyurethane；The cellulose nanometer fibril is high length-diameter ratio fibril, and fiber is long
400~600 μm of degree, 10~50 nm of fibre diameter.
2. cellulose nanometer fibril composite bicomponent aqueous polyurethane as described in claim 1, which is characterized in that described is poly-
Urethane polyalcohol hydroxyl value is 50~150 mg/g, 30~50 % of polyurethane polyol aqueous dispersion solid content.
3. cellulose nanometer fibril composite bicomponent aqueous polyurethane as described in claim 1, which is characterized in that described is poly-
Isocyanates is the hexamethylene diisocyanate tripolymer of hydrophilic modifying.
4. the method for preparing any compound double-component waterborne polyurethane of cellulose nanometer fibril of claim 1 ~ 3, special
Sign is, cellulose nanometer fibril is directly added into polyurethane polyol aqueous dispersion by cell pulverization sonic oscillation method,
Solidify again with polyisocyanate cross, obtains cellulose nanometer fibril composite bicomponent water-based polyurethane polymer.
5. the method for preparation cellulose nanometer fibril composite bicomponent aqueous polyurethane, feature exist as claimed in claim 4
In the cell pulverization sonic oscillation method, power is 1000~1800 W, and the time is 10~20 min.
6. any cellulose nanometer fibril composite bicomponent aqueous polyurethane of claim 1 ~ 3 is preparing aqueous polyurethane
Application in coating, binder polymer material.
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| CN106543946A (en) * | 2016-10-28 | 2017-03-29 | 无锡市永兴金属软管有限公司 | A kind of wavy metal pipe binder based on modifying nanometer cellulose and preparation method thereof |
| CN106393297B (en) * | 2016-11-01 | 2019-08-06 | 南京林业大学 | Manufacturing method of the abrasion resistant polyurethane dipping decorative paper veneer without aldehyde glue wood-based plate |
| CN109081900B (en) * | 2018-07-06 | 2021-01-26 | 山东圣泉新材料股份有限公司 | Modified polyol and preparation method thereof, modified polyurethane material and preparation method and application thereof |
| CN110105531A (en) * | 2019-05-16 | 2019-08-09 | 浙江恒川新材料有限公司 | A kind of preparation method of paper antimicrobial coating |
| CN112480650B (en) * | 2020-12-09 | 2023-01-03 | 浙江理工大学 | Cellulose nanocrystal and cellulose nanofiber reinforced and toughened aqueous polyurethane composite material and preparation method thereof |
| CN115612390A (en) * | 2022-09-29 | 2023-01-17 | 深圳陆城装饰设计工程有限公司 | High emulsification polyurethane mortar terrace coating structure |
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