CN114106392B - 一种超强超韧自愈合纤维素-聚氨酯杂化材料及制备方法 - Google Patents
一种超强超韧自愈合纤维素-聚氨酯杂化材料及制备方法 Download PDFInfo
- Publication number
- CN114106392B CN114106392B CN202111466799.XA CN202111466799A CN114106392B CN 114106392 B CN114106392 B CN 114106392B CN 202111466799 A CN202111466799 A CN 202111466799A CN 114106392 B CN114106392 B CN 114106392B
- Authority
- CN
- China
- Prior art keywords
- film
- parts
- aqueous polyurethane
- polyurethane emulsion
- oxidized cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 104
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 229920002201 Oxidized cellulose Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229940107304 oxidized cellulose Drugs 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 229920006264 polyurethane film Polymers 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000000017 hydrogel Substances 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 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
- 239000002184 metal Substances 0.000 claims 4
- 125000005442 diisocyanate group Chemical group 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 2
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 abstract description 5
- 150000002513 isocyanates Chemical class 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 18
- 238000012512 characterization method Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 229920001046 Nanocellulose Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229920006306 polyurethane fiber Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000008113 selfheal Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Images
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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- 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
- C08G2280/00—Compositions for creating shape memory
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及一种超强超韧自愈合纤维素‑聚氨酯杂化材料及制备方法,对水性聚氨酯中初始异氰酸酯与多元醇比例以及亲水基团扩链剂含量进行设计调控,能够与Tempo氧化纤维素有着最好相容性,保证Tempo氧化纤维素‑水性聚氨酯杂化膜有着最优的湿牵伸倍率以保证杂化材料的内部取向。本发明利用其优良的自愈合以及形状记忆性能可以实现从二维膜材料到板材,管材,棒材、圆球、锥形等各种复杂三维体材料的转化,整个操作过程绿色简单有效,不需要任何其他助剂,并且最终得到的体材料具有极好的力学性能。
Description
技术领域
本发明涉及一种超强超韧自愈合纤维素-聚氨酯杂化材料及制备方法,属于高性能生物基材料的改性技术领域。
背景技术
随着经济的发展,世界各国对可挥发性有机物(VOC)的排放逐渐加强了管理,聚氨酯由于其易于水性化而受到人们的重视,目前已被广泛应用于涂料、胶黏剂、皮革饰品等。聚氨酯可以通过外乳化法或者内乳化法以水作为分散介质代替有机溶剂而成为水性聚氨酯。
水性聚氨酯具有一系列显著的优点,主要可以分为以下三个方面:
(1)水性聚氨酯以水作为分散介质,在使用时可以做到完全无VOC排放,是一种对人体和环境友好无危害的绿色材料。
(2)水性聚氨酯由于软硬段不相容性而存在一定程度的微相分离,导致其具有优异的机械性能与低温柔顺性,同时耐磨损性能、耐化学品腐蚀性能也较为突出。
(3)异氰酸酯基团可以与含活泼氢的单体进行反应,如羟基、氨基、羧基、巯基等,因此水性聚氨酯结构可设计性极强,极易对其从分子结构层次进行改性。
但是,目前对于水性聚氨酯的力学强力的显著提升的改性方法却几乎没有,可见对于水性聚氨酯力学强力提升的意义重大。在已有的关于聚氨酯力学增强的报道中,主要有有机硅交联剂、环氧树脂交联改性、无机纳米粒子的引入改性等等,但都由于引入组份与水性聚氨酯组份之间相容性不够好,从而使得其之间产生的作用力并没有达到理想效果,因此对其力学强力没有显著的提升。
纤维素是地球上几乎无穷之不尽的聚合物资源,有望满足对可持续发展不断增长的需求。而纤维素纳米纤维(CNFs)由于其非凡的力学性能,是一种新兴的天然衍生纳米材料。例如,由于其高的结晶度(≈88%),CNFs的强度达到≈1.6-7.7GPa,刚度为≈150GPa。对于CNFs的材料,近年来各个研究小组通过控制CNFs的纤维素纳米纤维的取向对齐程度和界面相容性以获得优良的机械性能。虽然这些人造纤维素材料已经取得了巨大的成就,但由于CNFs的刚性性质,其韧性仍难以提高。原因在于纤维素材料独特的刚性特质使得想要对纯纤维素材料进行定向牵伸以获得内部规整的取向较为困难,最终的使得其韧性并不高。
水性聚氨酯以及纳米纤维素作为传统溶剂型高分子材料的新一代绿色水性产物,其独有的绿色无溶剂性成为了其最具优势的特点,随着可持续发展战略的不断深化,未来这些水性环保的生物基材料一定会更加具有发展前景。因此,对于其力学强度以及韧性,耐磨性以及耐水性的提升意义重大,将大大扩展这类材料未来的应用范围。
发明内容
为了克服水性聚氨酯的以上性能缺陷,本发明提供了一种超强超韧自愈合纤维素-聚氨酯杂化材料及制备方法,在力学强度以及韧性上,有着极大的提升。此外,该材料还展现出了极好的自愈合性能以及形状记忆性能,因此也能够对材料进行各种高强韧形状材料以及三维体材料设计,使得材料能够得到更广泛的应用。整个工艺过程都处于绿色环保的体系之中,并且生产效率高,生产成本低。
本发明的发明构思是:
对水性聚氨酯中初始异氰酸酯与多元醇比例以及亲水基团扩链剂含量进行设计调控,能够与Tempo氧化纤维素有着最好相容性,保证Tempo氧化纤维素-水性聚氨酯杂化膜有着最优的湿牵伸倍率以保证杂化材料的内部取向。
本发明的技术方案是:
将制得的最优的异氰酸酯与多元醇比例以及亲水基团扩链剂含量的水性聚氨酯乳液与Tempo氧化纤维素按照一定的比例进行物理共混,待充分混合均匀铺于成膜板上进行成膜,然后将干燥后的薄膜浸泡于离子(Zn2+、Cu2+、Ca2+、Fe3+、Mg2+、Al3+)溶液一定时间取出后进行湿牵伸干燥后得到高强度高韧性的离子交联以及内部取向Tempo纤维素-水性聚氨酯膜;对于Tempo纤维素-水性聚氨酯纤维,将未牵伸的Tempo纤维素-水性聚氨酯膜切成细条浸泡于离子(Zn2+、Cu2+、Ca2+、Fe3+、Mg2+、Al3+)溶液一定时间取出后进行湿牵伸并且多根加捻,干燥后得到高强度高韧性的离子交联以及内部取向Tempo纤维素-水性聚氨酯纤维材料。
原始的Tempo纤维素-水性聚氨酯膜能够在湿状态下自愈合,我们利用将膜浸湿后进行牵伸并层层叠加待其干燥后得到高强度高韧性以及高弯曲刚度的三维立体板材;利用其这一性能我们还将湿态的膜进行在棒状、锥形等模具上缠绕得到高强高韧的管材等各种能够进行设计的形状;该膜还展现出了极好的形状记忆能力,我们将此膜进行类似于折纸的方式折成各种形状,然后将其浸湿再干燥后其折痕便会消失,与原始膜没有区别,此过程可重复至少一百次以上。
具体的,包含如下步骤:
水性聚氨酯乳液的制备:向反应釜内加入200份聚四氢呋喃醚二醇和100份异佛尔酮二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入24份二羟甲基丙酸,7份1,4丁二醇,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水(35%固含量)1000r/min搅拌40min后得到水性聚氨酯乳液。
Tempo氧化纤维素-水性聚氨酯乳液的制备:向反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液一定份数,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液。
Tempo氧化纤维素-水性聚氨酯乳液成膜:取Tempo氧化纤维素-水性聚氨酯乳液1份于100cm×100cm的聚四氟成膜板中室温干燥成膜,成膜厚度约为50μm,最后对其力学以及其他性能进行测试表征(测试前在RH=50%湿度下平衡24h)。
Tempo氧化纤维素-水性聚氨酯高强高韧薄膜的制备:将脱模后的薄膜分别浸泡入浓度为0.1mol/L的ZnCl2,CuCl2,CaCl2溶液中约5min,取出后进行定向牵伸约700%,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧薄膜。最后对薄膜进行力学及其他性能的测试表征(测试前在RH=50%湿度下平衡24h)。
Tempo氧化纤维素-水性聚氨酯高强高韧纤维的制备:将脱模后的薄膜切成一定宽度(100μm±20μm)的长条状分别浸泡入浓度为0.1mol/L的ZnCl2,CuCl2,CaCl2溶液中约5min,从各个离子液中取出若干根(2~8根)进行定向湿牵伸约700%同时进行加捻,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧纤维。最后对纤维进行力学及其他性能的测试表征(测试前在RH=50%湿度下平衡24h)。
Tempo氧化纤维素-水性聚氨酯高强高韧板材、管材等的制备:将成膜后的Tempo氧化纤维素-水性聚氨酯薄膜浸水后进行湿牵伸的同时进行层层叠加,由于薄膜自身好的水汽诱导下的自愈合能力,再加上牵伸后的材料取向,最终得到的板材结构完整均匀,并且有着极高的牵伸强度,韧性以及弯曲强度。将成膜后的Tempo氧化纤维素-水性聚氨酯薄膜浸水后进行湿牵伸的同时进行在聚四氟棒进行层层缠绕,在干燥后得到高强高韧的管材。
Tempo氧化纤维素-水性聚氨酯形状记忆膜:将成膜后的Tempo氧化纤维素-水性聚氨酯薄膜折成飞机等形状,在折叠的地方出现折叠线,再将折成的飞机等形状材料浸湿后,其又恢复原始膜形状,在干燥后与原始膜没有任何区别。
本发明所选用的异佛尔酮二异氰酸酯是使用较为广泛的一种制备聚氨酯的异氰酸酯,其他的异氰酸酯例如:二苯基甲烷二异氰酸酯,甲苯二异氰酸酯,六亚甲基二异氰酸酯等等也同样适用于该体系;所选的多元醇为聚四氢呋喃醚二醇,其他的多元醇例如:聚碳酸酯二醇,聚丙二醇等等均适用于本体系;所选的扩链剂为二羟甲基丙酸以及1,4丁二醇,其他的扩链剂例如丙三醇,乙二胺,三羟甲基丙烷等等均适用于本体系;
本发明所制备的改性水性聚氨酯乳液的固含量可根据需要控制在25%-40%之间。
本发明所设计的薄膜牵伸以及自加捻牵伸成纤维的工艺可对膜或纤维的牵伸长度进行控制从而得到不同强度不同弹性的膜或纤维。
本发明所制备的Tempo氧化纤维素-水性聚氨酯乳液可根据需要利用蒸馏水对其固含量进行调控。
本发明所用的聚氨酯为水性聚氨酯,但不局限与水性聚氨酯,也可以是各种溶剂型聚氨酯;氧化纤维素也不局限于Tempo氧化纤维素。
本发明所用的不同离子液由于离子在材料内部产生的离子交联结构均对于最终材料的强度提升起到了显著作用。对于水溶液对于材料的强度提升也是十分显著的。
本发明的有益效果如下:
1、本发明工艺过程简单,可控性较强,并且是绿色环保的水性体系。
2、本发明所制备纤维以及膜的力学性能优异。
3、本发明所制备膜或纤维可通过不同的牵伸倍率实现强度与弹性之间的快速转换,从而扩大了其应用范围。
4、本发明所制备的高结晶性纤维显著提升了水性聚氨酯以及纤维素材料的耐水性耐磨性等,扩大了其使用范围。
5、本发明所制备的高强高韧高性能膜或纤维具有极好的被染色性,这扩大了其在各个方面上的使用范围。
6、本发明的薄膜成纤维技术简单快捷,具有大规模,连续性的特点。
7、本发明不仅在于制备薄膜与纤维,也可以将改性的水性聚氨酯浆料用于织物、纸基等基材的涂层材料,并且具有优异的耐磨性能。
8、本发明利用其优良的自愈合以及形状记忆性能可以实现从二维膜材料到板材,管材等各种三维体材料的转化,整个操作过程绿色简单有效,不需要任何其他助剂,并且最终得到的体材料具有极好的力学性能。
附图说明
图1是本发明中所得的Tempo氧化纤维素-水性聚氨酯薄膜样品以及纤维样品的力学性能曲线。
图2是本发明中所得的Tempo氧化纤维素-水性聚氨酯板材样品的拉伸强度力学曲线。
图3是本发明中所得的Tempo氧化纤维素-水性聚氨酯板材样品以及管材样品的弯曲强度力学曲线。
具体实施方式
为了更清楚说明本发明内容,列举以下实施例,但本专利的范围并不局限于这些实施例。
实施例1
向反应釜内加入200份聚四氢呋喃醚二醇和100份异佛尔酮二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入24份二羟甲基丙酸,7份1,4丁二醇,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的丙酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水(35%固含量)1000r/min搅拌40min后得到水性聚氨酯乳液。再向另一反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液24份,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液。取Tempo氧化纤维素-水性聚氨酯乳液3份于100cm×100cm的聚四氟成膜板中室温干燥成膜,成膜厚度约为100μm。将脱模后的薄膜浸泡入浓度为0.1mol/L的CaCl2溶液中约5min,取出后进行定向牵伸约700%,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧薄膜。最后对薄膜进行力学性能的测试表征(测试前在RH=50%湿度下平衡24h)。
实施例2
向反应釜内加入200份聚四氢呋喃醚二醇和100份异佛尔酮二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入24份二羟甲基丙酸,7份1,4丁二醇,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的丙酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水(35%固含量)1000r/min搅拌40min后得到水性聚氨酯乳液。再向另一反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液24份,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液。取Tempo氧化纤维素-水性聚氨酯乳液3份于100cm×100cm的聚四氟成膜板中室温干燥成膜,成膜厚度约为100μm。将脱模后的薄膜浸泡入浓度为0.1mol/L的CuCl2溶液中约5min,取出后进行定向牵伸约700%,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧薄膜。最后对薄膜进行力学性能的测试表征(测试前在RH=50%湿度下平衡24h)。
实施例3
向反应釜内加入200份聚四氢呋喃醚二醇和100份异佛尔酮二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入24份二羟甲基丙酸,7份1,4丁二醇,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的丙酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水(35%固含量)1000r/min搅拌40min后得到水性聚氨酯乳液。再向另一反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液24份,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液。取Tempo氧化纤维素-水性聚氨酯乳液3份于100cm×100cm的聚四氟成膜板中室温干燥成膜,成膜厚度约为100μm。将脱模后的薄膜浸泡入浓度为0.1mol/L的ZnCl2溶液中约5min,取出后进行定向牵伸约700%,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧薄膜。最后对薄膜进行力学性能的测试表征(测试前在RH=50%湿度下平衡24h)。
实施例4
向反应釜内加入200份聚四氢呋喃醚二醇和100份异佛尔酮二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入24份二羟甲基丙酸,7份1,4丁二醇,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的丙酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水(35%固含量)1000r/min搅拌40min后得到水性聚氨酯乳液。再向另一反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液24份,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液。取Tempo氧化纤维素-水性聚氨酯乳液3份于100cm×100cm的聚四氟成膜板中室温干燥成膜,成膜厚度约为100μm。将脱模后的薄膜切成一定宽度(200μm±20μm)的长条状分别浸泡入浓度为0.1mol/L的CaCl2溶液中约5min,从各个离子液中取出若干根(2~8根)进行定向湿牵伸约700%同时进行加捻,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧纤维。最后对纤维进行力学及其他性能的测试表征(测试前在RH=50%湿度下平衡24h)。
实施例5
向反应釜内加入200份聚四氢呋喃醚二醇和100份异佛尔酮二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入24份二羟甲基丙酸,7份1,4丁二醇,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的丙酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水(35%固含量)1000r/min搅拌40min后得到水性聚氨酯乳液。再向另一反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液24份,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液。取Tempo氧化纤维素-水性聚氨酯乳液3份于100cm×100cm的聚四氟成膜板中室温干燥成膜,成膜厚度约为100μm。将脱模后的薄膜切成一定宽度(200μm±20μm)的长条状分别浸泡入浓度为0.1mol/L的CuCl2溶液中约5min,从各个离子液中取出若干根(2~8根)进行定向湿牵伸约700%同时进行加捻,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧纤维。最后对纤维进行力学及其他性能的测试表征(测试前在RH=50%湿度下平衡24h)。
实施例6
向反应釜内加入200份聚四氢呋喃醚二醇和100份异佛尔酮二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入24份二羟甲基丙酸,7份1,4丁二醇,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的丙酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水(35%固含量)1000r/min搅拌40min后得到水性聚氨酯乳液。再向另一反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液24份,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液。取Tempo氧化纤维素-水性聚氨酯乳液3份于100cm×100cm的聚四氟成膜板中室温干燥成膜,成膜厚度约为100μm。将脱模后的薄膜切成一定宽度(200μm±20μm)的长条状分别浸泡入浓度为0.1mol/L的ZnCl2溶液中约5min,从各个离子液中取出若干根(2~8根)进行定向湿牵伸约700%同时进行加捻,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧纤维。最后对纤维进行力学及其他性能的测试表征(测试前在RH=50%湿度下平衡24h)。
实施例7
向反应釜内加入200份聚四氢呋喃醚二醇和100份异佛尔酮二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入24份二羟甲基丙酸,7份1,4丁二醇,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的丙酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水(35%固含量)1000r/min搅拌40min后得到水性聚氨酯乳液。再向另一反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液18份,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液。取Tempo氧化纤维素-水性聚氨酯乳液1份于100cm×100cm的聚四氟成膜板中室温干燥成膜,成膜厚度约为50μm。取数张膜浸湿并牵伸层层叠加组装,干燥后得到Tempo氧化纤维素-水性聚氨酯板材;取数张膜浸湿并牵伸层层缠绕于聚四氟棒待干燥后脱模得到Tempo氧化纤维素-水性聚氨酯管材。
表1实施例所得高强度高韧性Tempo氧化纤维素-水性聚氨酯薄膜样品,纤维样品以及板材样品的性能测试结果
Claims (8)
1.一种超强超韧自愈合纤维素-聚氨酯杂化材料的制备方法,其特征在于:将水性聚氨酯乳液与Tempo氧化纤维素按照一定的比例进行物理共混,充分混合均匀铺于成膜板上进行成膜,然后将干燥后的薄膜浸泡于含有金属离子的溶液中一定时间,取出后将膜材沿平面方向进行湿牵伸,干燥后得到高强度高韧性的取向Tempo纤维素-水性聚氨酯膜;
水性聚氨酯乳液的制备:向反应釜内加入200份多元醇和100份二异氰酸酯65℃,400r/min搅拌1.5h,再升温到80℃继续搅拌2h,反应持续通氮气进行保护;再加入31份扩链剂,持续搅拌进行扩链反应3.5h,反应过程中加丙酮调节黏度,利用冷凝管对加入的酮进行回流利用;然后将反应温度缓慢降至45℃,加入25份三乙胺进行中和搅拌15min;最终在常温下加入660份蒸馏水1000r/min搅拌40min后得到水性聚氨酯乳液;
将脱模后的薄膜分别浸泡入浓度为0.01-2.00mol/L的Zn2+、Cu2+、Ca2+ 、Fe3+ 、Mg2+、Al3+单一金属或混合金属盐溶液中5min,取出后进行定向牵伸700%,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧薄膜。
2.如权利要求1所述的方法,其特征在于:Tempo氧化纤维素-水性聚氨酯乳液的制备:向反应釜内加入固含量为1.5%的Tempo氧化纤维素水凝胶100份,再加入200份的蒸馏水进行分散,室温下600r/min搅拌2h;再加入制备好的水性聚氨酯乳液24份,继续搅拌3h,后得到Tempo氧化纤维素-水性聚氨酯乳液;
Tempo氧化纤维素-水性聚氨酯乳液成膜:取Tempo氧化纤维素-水性聚氨酯乳液3份于100cm×100cm的聚四氟成膜板中室温干燥成膜。
3.如权利要求1所述的方法,其特征在于:所述二异氰酸酯包括异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯的至少一种。
4.如权利要求1所述的方法,其特征在于:所选多元醇为聚四氢呋喃醚二醇、聚碳酸酯二醇、聚丙二醇的至少一种。
5.如权利要求1所述的方法,其特征在于:所述扩链剂为二羟甲基丙酸、1,4丁二醇、丙三醇、乙二胺、三羟甲基丙烷的至少一种。
6.如权利要求1所述的方法,其特征在于:制备的改性水性聚氨酯乳液的固含量在25%-40%之间。
7.一种氧化纳米纤维素-水性聚氨酯乳液高强高韧纤维的制备方法,其特征在于:将权利要求1脱模后的薄膜切成一定宽度的长条状分别浸泡入浓度为0.01-2.00mol/L的Zn2+、Cu2+、Ca2+ 、Fe3+ 、Mg2+、Al3+单一金属或混合金属盐溶液中溶液中5min,从溶液中取出若干根进行定向湿牵伸100%-700%同时进行加捻,烘干得到高度取向的Tempo氧化纤维素-水性聚氨酯乳液高强高韧纤维。
8.一种超强超韧自愈合纤维素-聚氨酯乳液高强高韧板材、管材、棒材、球形、锥形的制备方法,其特征在于:将权利要求1成膜后的Tempo氧化纤维素-水性聚氨酯薄膜浸水后进行湿牵伸的同时进行层层叠加或将膜缠绕于模型圆柱、球、锥表面进行层层叠加。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111466799.XA CN114106392B (zh) | 2021-12-03 | 2021-12-03 | 一种超强超韧自愈合纤维素-聚氨酯杂化材料及制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111466799.XA CN114106392B (zh) | 2021-12-03 | 2021-12-03 | 一种超强超韧自愈合纤维素-聚氨酯杂化材料及制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114106392A CN114106392A (zh) | 2022-03-01 |
CN114106392B true CN114106392B (zh) | 2023-04-21 |
Family
ID=80366818
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111466799.XA Active CN114106392B (zh) | 2021-12-03 | 2021-12-03 | 一种超强超韧自愈合纤维素-聚氨酯杂化材料及制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114106392B (zh) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4426008A1 (de) * | 1994-07-22 | 1996-01-25 | Cassella Ag | Hydrophile, hochquellfähige Hydrogele |
CN108752913A (zh) * | 2018-05-30 | 2018-11-06 | 广东工业大学 | 一种离子型热塑性聚氨酯弹性体及其制备方法 |
CN110066381B (zh) * | 2019-04-28 | 2021-03-26 | 上海应用技术大学 | 含有da键和动态锌离子交联的自愈合聚氨酯的制备方法 |
CN110028686A (zh) * | 2019-04-29 | 2019-07-19 | 中国科学院长春应用化学研究所 | 一种纤维素纳米晶增强自修复水性聚氨酯材料及其制备方法 |
CN110592714B (zh) * | 2019-10-09 | 2022-06-03 | 福建工程学院 | 一种超强韧纳米组装纤维素长丝及其制备方法 |
CN114539573B (zh) * | 2020-05-29 | 2023-04-25 | 深圳硅基传感科技有限公司 | 具有三维网络结构的聚合物膜 |
CN112267167B (zh) * | 2020-10-14 | 2023-01-03 | 浙江理工大学 | 一种自愈性发光有机水凝胶纤维的制备方法 |
-
2021
- 2021-12-03 CN CN202111466799.XA patent/CN114106392B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN114106392A (zh) | 2022-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104628982B (zh) | 一种碱木质素基水性聚氨酯的制备方法 | |
CN101665675B (zh) | 一种水性聚氨酯粘合剂及超细纤维合成革的制备方法 | |
CN107057027B (zh) | 一种高固含量低粘度水性聚氨酯的制备方法 | |
JP5375255B2 (ja) | 蒸着用フィルムおよびガスバリアフィルム | |
CN107163217B (zh) | 一种纳米金刚石改性水性聚氨酯的制备方法 | |
CN107501500B (zh) | 聚酰胺-胺功能化石墨烯/超支化水性聚氨酯及其制备方法 | |
CN109456459B (zh) | 一种提高水性聚氨酯耐水或耐溶剂性的方法 | |
CN108264621B (zh) | 一种水性聚氨酯非均相扩链合成方法 | |
KR20190117532A (ko) | 시트상물 | |
CN102432798A (zh) | 一种环氧树脂改性阳离子水性聚氨酯乳液的制备方法 | |
CN110028686A (zh) | 一种纤维素纳米晶增强自修复水性聚氨酯材料及其制备方法 | |
CN105693981B (zh) | 桐油多元醇基可后交联阴离子聚氨酯及其制备方法 | |
CN110862509A (zh) | 一种水性无溶剂聚氨酯树脂及其制备方法 | |
CN108468226A (zh) | 一种复合改性水性聚氨酯合成革 | |
CN114106392B (zh) | 一种超强超韧自愈合纤维素-聚氨酯杂化材料及制备方法 | |
CN104341572A (zh) | 一种无溶剂的水性聚氨酯树脂的制备方法 | |
Wu et al. | Biodegradability of renewable waterborne polyurethane modified with vinyl-grafted gelatin by UV curing | |
CN109651582A (zh) | 水性聚氨酯油墨连接料及其制备方法 | |
CN113788929B (zh) | 一种自修复、可回收的生物基聚氨酯材料及其制备方法与应用 | |
CN112521581B (zh) | 一种合成革用水性聚氨酯面层树脂及其制备方法及应用 | |
CN114853971A (zh) | 一种可降解水性聚氨酯及其制备方法 | |
CN114045024B (zh) | 一种强韧耐磨磷酸钙寡聚物-水性聚氨酯材料及制备方法 | |
CN114806433B (zh) | 生物基pu刻字膜的制备方法及生物基pu刻字膜 | |
CN115594980B (zh) | 一种淀粉基可生物降解抗菌材料及其制备方法 | |
CN114411429B (zh) | 一种电子束固化防水透湿型水性聚氨酯织物涂层胶及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |